Coatings and Inks for Food Contact Material

Report 186

ISSN: 0889-3144

Coatings and Inks for Food Contact Materials

Martin J. Forrest

Volume 16, Number 6, 2005

Expert overviews covering the science and technology of rubber and plastics

RAPRA REVIEW REPORTS A Rapra Review Report comprises three sections, as follows: 1. A commissioned expert review, discussing a key topic of current interest, and referring to the References and Abstracts section. Reference numbers in brackets refer to item numbers from the References and Abstracts section. Where it has been necessary for completeness to cite sources outside the scope of the Rapra Abstracts database, these are listed at the end of the review, and cited in the text as a.1, a.2, etc. 2. A comprehensive References and Abstracts section, resulting from a search of the Rapra Polymer Library database. The format of the abstracts is outlined in the sample record below. 3. An index to the References and Abstracts section, derived from the indexing terms which are added to the abstracts records on the database to aid retrieval.

Source of original article Title

Item 1 Macromolecules

33, No.6, 21st March 2000, p.2171-83 EFFECT OF THERMAL HISTORY ON THE RHEOLOGICAL BEHAVIOR OF THERMOPLASTIC POLYURETHANES Pil Joong Yoon; Chang Dae Han Akron,University The effect of thermal history on the rheological behaviour of ester- and etherbased commercial thermoplastic PUs (Estane 5701, 5707 and 5714 from B.F.Goodrich) was investigated. It was found that the injection moulding temp. used for specimen preparation had a marked effect on the variations of dynamic storage and loss moduli of specimens with time observed during isothermal annealing. Analysis of FTIR spectra indicated that variations in hydrogen bonding with time during isothermal annealing very much resembled variations of dynamic storage modulus with time during isothermal annealing. Isochronal dynamic temp. sweep experiments indicated that the thermoplastic PUs exhibited a hysteresis effect in the heating and cooling processes. It was concluded that the microphase separation transition or order-disorder transition in thermoplastic PUs could not be determined from the isochronal dynamic temp. sweep experiment. The plots of log dynamic storage modulus versus log loss modulus varied with temp. over the entire range of temps. (110-190C) investigated. 57 refs. GOODRICH B.F.

Location

USA

Authors and affiliation

Abstract

Companies or organisations mentioned

Accession no.771897

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Previous Titles Still Available Volume 1

Report 35

Polymers in Household Electrical Goods, D.Alvey, Hotpoint Ltd.

Report 36

Developments in Additives to Meet Health and Environmental Concerns, M.J. Forrest, Rapra Technology Ltd.

Report 1

Conductive Polymers, W.J. Feast

Report 2

Medical, Surgical and Pharmaceutical Applications of Polymers, D.F. Williams

Report 3

Advanced Composites, D.K. Thomas, RAE, Farnborough.

Report 4

Liquid Crystal Polymers, M.K. Cox, ICI, Wilton.

Volume 4

Report 5

CAD/CAM in the Polymer Industry, N.W. Sandland and M.J. Sebborn, Cambridge Applied Technology.

Report 37

Polymers in Aerospace Applications, W.W. Wright, University of Surrey.

Report 8

Engineering Thermoplastics, I.T. Barrie, Consultant. Reinforced Reaction Injection Moulding, P.D. Armitage, P.D. Coates and A.F. Johnson

Report 38

Epoxy Resins, K.A. Hodd

Report 10

Report 39

Report 11

Communications Applications of Polymers, R. Spratling, British Telecom.

Polymers in Chemically Resistant Applications, D. Cattell, Cattell Consultancy Services.

Report 40

Internal Mixing of Rubber, J.C. Lupton

Report 12

Process Control in the Plastics Industry, R.F. Evans, Engelmann & Buckham Ancillaries.

Report 41

Failure of Plastics, S. Turner, Queen Mary College.

Report 42

Polycarbonates, R. Pakull, U. Grigo, D. Freitag, Bayer AG.

Report 43

Polymeric Materials from Renewable Resources, J.M. Methven, UMIST.

Volume 2 Report 13

Injection Moulding of Engineering Thermoplastics, A.F. Whelan, London School of Polymer Technology.

Report 44

Flammability and Flame Retardants in Plastics, J. Green, FMC Corp.

Report 14

Polymers and Their Uses in the Sports and Leisure Industries, A.L. Cox and R.P. Brown, Rapra Technology Ltd.

Report 45

Composites - Tooling and Component Processing, N.G. Brain, Tooltex.

Report 46

Report 15

Polyurethane, Materials, Processing and Applications, G. Woods, Consultant.

Quality Today in Polymer Processing, S.H. Coulson, J.A. Cousans, Exxon Chemical International Marketing.

Polyetheretherketone, D.J. Kemmish, ICI, Wilton.

Report 47

Report 16

Chemical Analysis of Polymers, G. Lawson, Leicester Polytechnic.

Report 17

Extrusion, G.M. Gale, Rapra Technology Ltd.

Report 48

Plastics in Building, C.M.A. Johansson

Report 18

Agricultural and Horticultural Applications of Polymers, J.C. Garnaud, International Committee for Plastics in Agriculture.

Volume 5

Report 19

Recycling and Disposal of Plastics Packaging, R.C. Fox, Plas/Tech Ltd.

Report 49

Blends and Alloys of Engineering Thermoplastics, H.T. van de Grampel, General Electric Plastics BV.

Report 20

Pultrusion, L. Hollaway, University of Surrey.

Report 50

Report 21

Materials Handling in the Polymer Industry, H. Hardy, Chronos Richardson Ltd.

Automotive Applications of Polymers II, A.N.A. Elliott, Consultant.

Report 51

Report 22

Electronics Applications of Polymers, M.T.Goosey, Plessey Research (Caswell) Ltd.

Biomedical Applications of Polymers, C.G. Gebelein, Youngstown State University / Florida Atlantic University.

Report 52

Report 23

Offshore Applications of Polymers, J.W.Brockbank, Avon Industrial Polymers Ltd.

Polymer Supported Chemical Reactions, P. Hodge, University of Manchester.

Report 53

Report 24

Recent Developments in Materials for Food Packaging, R.A. Roberts, Pira Packaging Division.

Weathering of Polymers, S.M. Halliwell, Building Research Establishment.

Report 54

Health and Safety in the Rubber Industry, A.R. Nutt, Arnold Nutt & Co. and J. Wade.

Report 55

Computer Modelling of Polymer Processing, E. Andreassen, Å. Larsen and E.L. Hinrichsen, Senter for Industriforskning, Norway.

Volume 3 Report 25

Foams and Blowing Agents, J.M. Methven, Cellcom Technology Associates.

Report 26

Polymers and Structural Composites in Civil Engineering, L. Hollaway, University of Surrey.

Report 56

Plastics in High Temperature Applications, J. Maxwell, Consultant.

Report 27

Injection Moulding of Rubber, M.A. Wheelans, Consultant.

Report 57

Joining of Plastics, K.W. Allen, City University.

Report 58

Physical Testing of Rubber, R.P. Brown, Rapra Technology Ltd.

Report 59

Polyimides - Materials, Processing and Applications, A.J. Kirby, Du Pont (U.K.) Ltd.

Report 60

Physical Testing of Thermoplastics, S.W. Hawley, Rapra Technology Ltd.

Report 28

Adhesives for Structural and Engineering Applications, C. O’Reilly, Loctite (Ireland) Ltd.

Report 29

Polymers in Marine Applications, C.F.Britton, Corrosion Monitoring Consultancy.

Report 30

Non-destructive Testing of Polymers, W.N. Reynolds, National NDT Centre, Harwell.

Report 31

Silicone Rubbers, B.R. Trego and H.W.Winnan, Dow Corning Ltd.

Volume 6

Report 32

Fluoroelastomers - Properties and Applications, D. Cook and M. Lynn, 3M United Kingdom Plc and 3M Belgium SA.

Report 61 Report 62

Coextrusion, D. Djordjevic, Klöckner ER-WE-PA GmbH.

Report 33

Polyamides, R.S. Williams and T. Daniels, T & N Technology Ltd. and BIP Chemicals Ltd.

Report 63

Conductive Polymers II, R.H. Friend, University of Cambridge, Cavendish Laboratory.

Report 34

Extrusion of Rubber, J.G.A. Lovegrove, Nova Petrochemicals Inc.

Report 64

Designing with Plastics, P.R. Lewis, The Open University.

Food Contact Polymeric Materials, J.A. Sidwell, Rapra Technology Ltd.

Report 65

Decorating and Coating of Plastics, P.J. Robinson, International Automotive Design.

Report 66

Reinforced Thermoplastics - Composition, Processing and Applications, P.G. Kelleher, New Jersey Polymer Extension Center at Stevens Institute of Technology.

Report 90

Rubber Mixing, P.R. Wood.

Report 91

Recent Developments in Epoxy Resins, I. Hamerton, University of Surrey.

Report 92

Continuous Vulcanisation of Elastomer Profiles, A. Hill, Meteor Gummiwerke.

Report 67

Plastics in Thermal and Acoustic Building Insulation, V.L. Kefford, MRM Engineering Consultancy.

Report 93

Report 68

Cure Assessment by Physical and Chemical Techniques, B.G. Willoughby, Rapra Technology Ltd.

Advances in Thermoforming, J.L. Throne, Sherwood Technologies Inc.

Report 94

Report 69

Toxicity of Plastics and Rubber in Fire, P.J. Fardell, Building Research Establishment, Fire Research Station.

Compressive Behaviour of Composites, C. Soutis, Imperial College of Science, Technology and Medicine.

Report 95

Report 70

Acrylonitrile-Butadiene-Styrene Polymers, M.E. Adams, D.J. Buckley, R.E. Colborn, W.P. England and D.N. Schissel, General Electric Corporate Research and Development Center.

Thermal Analysis of Polymers, M. P. Sepe, Dickten & Masch Manufacturing Co.

Report 96

Polymeric Seals and Sealing Technology, J.A. Hickman, St Clair (Polymers) Ltd.

Report 71

Rotational Moulding, R.J. Crawford, The Queen’s University of Belfast.

Report 72

Advances in Injection Moulding, C.A. Maier, Econology Ltd.

Volume 7

Volume 9 Report 97

Rubber Compounding Ingredients - Need, Theory and Innovation, Part II: Processing, Bonding, Fire Retardants, C. Hepburn, University of Ulster.

Report 98

Advances in Biodegradable Polymers, G.F. Moore & S.M. Saunders, Rapra Technology Ltd.

Report 99

Recycling of Rubber, H.J. Manuel and W. Dierkes, Vredestein Rubber Recycling B.V.

Report 100

Photoinitiated Polymerisation - Theory and Applications, J.P. Fouassier, Ecole Nationale Supérieure de Chimie, Mulhouse.

Report 73

Reactive Processing of Polymers, M.W.R. Brown, P.D. Coates and A.F. Johnson, IRC in Polymer Science and Technology, University of Bradford.

Report 74

Speciality Rubbers, J.A. Brydson.

Report 75

Plastics and the Environment, I. Boustead, Boustead Consulting Ltd.

Report 101

Report 76

Polymeric Precursors for Ceramic Materials, R.C.P. Cubbon.

Solvent-Free Adhesives, T.E. Rolando, H.B. Fuller Company.

Report 102

Report 77

Advances in Tyre Mechanics, R.A. Ridha, M. Theves, Goodyear Technical Center.

Plastics in Pressure Pipes, T. Stafford, Rapra Technology Ltd.

Report 103

Gas Assisted Moulding, T.C. Pearson, Gas Injection Ltd.

Report 78

PVC - Compounds, Processing and Applications, J.Leadbitter, J.A. Day, J.L. Ryan, Hydro Polymers Ltd.

Report 104

Plastics Profile Extrusion, R.J. Kent, Tangram Technology Ltd.

Report 79

Rubber Compounding Ingredients - Need, Theory and Innovation, Part I: Vulcanising Systems, Antidegradants and Particulate Fillers for General Purpose Rubbers, C. Hepburn, University of Ulster.

Report 105

Rubber Extrusion Theory and Development, B.G. Crowther.

Report 106

Properties and Applications of Elastomeric Polysulfides, T.C.P. Lee, Oxford Brookes University.

Report 80

Anti-Corrosion Polymers: PEEK, PEKK and Other Polyaryls, G. Pritchard, Kingston University.

Report 107

High Performance Polymer Fibres, P.R. Lewis, The Open University.

Report 81

Thermoplastic Elastomers - Properties and Applications, J.A. Brydson.

Report 108

Chemical Characterisation of Polyurethanes, M.J. Forrest, Rapra Technology Ltd.

Report 82

Advances in Blow Moulding Process Optimization, Andres Garcia-Rejon,Industrial Materials Institute, National Research Council Canada.

Report 83

Molecular Weight Characterisation of Synthetic Polymers, S.R. Holding and E. Meehan, Rapra Technology Ltd. and Polymer Laboratories Ltd.

Report 84

Rheology and its Role in Plastics Processing, P. Prentice, The Nottingham Trent University.

Volume 8

Volume 10 Report 109

Rubber Injection Moulding - A Practical Guide, J.A. Lindsay.

Report 110

Long-Term and Accelerated Ageing Tests on Rubbers, R.P. Brown, M.J. Forrest and G. Soulagnet, Rapra Technology Ltd.

Report 111

Polymer Product Failure, P.R. Lewis, The Open University.

Report 112

Report 85

Ring Opening Polymerisation, N. Spassky, Université Pierre et Marie Curie.

Polystyrene - Synthesis, Production and Applications, J.R. Wünsch, BASF AG.

Report 113

Report 86

High Performance Engineering Plastics, D.J. Kemmish, Victrex Ltd.

Rubber-Modified Thermoplastics, H. Keskkula, University of Texas at Austin.

Report 114

Report 87

Rubber to Metal Bonding, B.G. Crowther, Rapra Technology Ltd.

Developments in Polyacetylene - Nanopolyacetylene, V.M. Kobryanskii, Russian Academy of Sciences.

Report 115

Report 88

Plasticisers - Selection, Applications and Implications, A.S. Wilson.

Metallocene-Catalysed Polymerisation, W. Kaminsky, University of Hamburg.

Report 116

Report 89

Polymer Membranes - Materials, Structures and Separation Performance, T. deV. Naylor, The Smart Chemical Company.

Compounding in Co-rotating Twin-Screw Extruders, Y. Wang, Tunghai University.

Report 117

Rapid Prototyping, Tooling and Manufacturing, R.J.M. Hague and P.E. Reeves, Edward Mackenzie Consulting.

Report 118

Liquid Crystal Polymers - Synthesis, Properties and Applications, D. Coates, CRL Ltd.

Volume 13

Report 119

Rubbers in Contact with Food, M.J. Forrest and J.A. Sidwell, Rapra Technology Ltd.

Report 145

Multi-Material Injection Moulding, V. Goodship and J.C. Love, The University of Warwick.

Report 120

Electronics Applications of Polymers II, M.T. Goosey, Shipley Ronal.

Report 146

In-Mould Decoration of Plastics, J.C. Love and V. Goodship, The University of Warwick.

Report 147

Rubber Product Failure, Roger P. Brown.

Report 148

Plastics Waste – Feedstock Recycling, Chemical Recycling and Incineration, A. Tukker, TNO.

Volume 11 Report 121

Polyamides as Engineering Thermoplastic Materials, I.B. Page, BIP Ltd.

Report 149

Analysis of Plastics, Martin J. Forrest, Rapra Technology Ltd.

Report 122

Flexible Packaging - Adhesives, Coatings and Processes, T.E. Rolando, H.B. Fuller Company.

Report 150

Mould Sticking, Fouling and Cleaning, D.E. Packham, Materials Research Centre, University of Bath.

Report 123

Polymer Blends, L.A. Utracki, National Research Council Canada.

Report 151

Rigid Plastics Packaging - Materials, Processes and Applications, F. Hannay, Nampak Group Research & Development.

Report 124

Sorting of Waste Plastics for Recycling, R.D. Pascoe, University of Exeter.

Report 152

Report 125

Structural Studies of Polymers by Solution NMR, H.N. Cheng, Hercules Incorporated.

Natural and Wood Fibre Reinforcement in Polymers, A.K. Bledzki, V.E. Sperber and O. Faruk, University of Kassel.

Report 153

Polymers in Telecommunication Devices, G.H. Cross, University of Durham.

Report 154

Polymers in Building and Construction, S.M. Halliwell, BRE.

Report 126

Composites for Automotive Applications, C.D. Rudd, University of Nottingham.

Report 127

Polymers in Medical Applications, B.J. Lambert and F.-W. Tang, Guidant Corp., and W.J. Rogers, Consultant.

Report 155

Styrenic Copolymers, Andreas Chrisochoou and Daniel Dufour, Bayer AG.

Report 128

Solid State NMR of Polymers, P.A. Mirau, Lucent Technologies.

Report 156

Life Cycle Assessment and Environmental Impact of Polymeric Products, T.J. O’Neill, Polymeron Consultancy Network.

Report 129

Failure of Polymer Products Due to Photo-oxidation, D.C. Wright.

Report 130

Failure of Polymer Products Due to Chemical Attack, D.C. Wright.

Report 131 Report 132

Failure of Polymer Products Due to Thermo-oxidation, D.C. Wright. Stabilisers for Polyolefins, C. Kröhnke and F. Werner, Clariant Huningue SA.

Volume 12

Volume 14 Report 157

Developments in Colorants for Plastics, Ian N. Christensen.

Report 158

Geosynthetics, David I. Cook.

Report 159

Biopolymers, R.M. Johnson, L.Y. Mwaikambo and N. Tucker, Warwick Manufacturing Group.

Report 160

Emulsion Polymerisation and Applications of Latex, Christopher D. Anderson and Eric S. Daniels, Emulsion Polymers Institute.

Report 161

Emissions from Plastics, C. Henneuse-Boxus and T. Pacary, Certech.

Report 133

Advances in Automation for Plastics Injection Moulding, J. Mallon, Yushin Inc.

Report 162

Analysis of Thermoset Materials, Precursors and Products, Martin J. Forrest, Rapra Technology Ltd.

Report 134

Infrared and Raman Spectroscopy of Polymers, J.L. Koenig, Case Western Reserve University.

Report 163

Polymer/Layered Silicate Nanocomposites, Masami Okamoto, Toyota Technological Institute.

Report 135

Polymers in Sport and Leisure, R.P. Brown.

Report 164

Report 136

Radiation Curing, R.S. Davidson, DavRad Services.

Cure Monitoring for Composites and Adhesives, David R. Mulligan, NPL.

Report 165

Report 137

Silicone Elastomers, P. Jerschow, Wacker-Chemie GmbH.

Polymer Enhancement of Technical Textiles, Roy W. Buckley.

Report 138

Health and Safety in the Rubber Industry, N. Chaiear, Khon Kaen University.

Report 166

Developments in Thermoplastic Elastomers, K.E. Kear

Rubber Analysis - Polymers, Compounds and Products, M.J. Forrest, Rapra Technology Ltd.

Report 167

Report 139

Polyolefin Foams, N.J. Mills, Metallurgy and Materials, University of Birmingham.

Report 168

Report 140

Tyre Compounding for Improved Performance, M.S. Evans, Kumho European Technical Centre.

Plastic Flame Retardants: Technology and Current Developments, J. Innes and A. Innes, Flame Retardants Associates Inc.

Report 141

Particulate Fillers for Polymers, Professor R.N. Rothon, Rothon Consultants and Manchester Metropolitan University.

Report 142

Blowing Agents for Polyurethane Foams, S.N. Singh, Huntsman Polyurethanes.

Report 143

Adhesion and Bonding to Polyolefins, D.M. Brewis and I. Mathieson, Institute of Surface Science & Technology, Loughborough University.

Report 144

Rubber Curing Systems, R.N. Datta, Flexsys BV.

Volume 15 Report 169

Engineering and Structural Adhesives, David J. Dunn, FLD Enterprises Inc.

Report 170

Polymers in Agriculture and Horticulture, Roger P. Brown.

Report 171

PVC Compounds and Processing, Stuart Patrick.

Report 172

Troubleshooting Injection Moulding, Vanessa Goodship, Warwick Manufacturing Group.

Report 173

Regulation of Food Packaging in Europe and the USA, Derek J. Knight and Lesley A. Creighton, Safepharm Laboratories Ltd.

Report 174

Pharmaceutical Applications of Polymers for Drug Delivery, David Jones, Queen's University, Belfast.

Report 175

Tyre Recycling, Valerie L. Shulman, European Tyre Recycling Association (ETRA).

Report 176

Polymer Processing with Supercritical Fluids, V. Goodship and E.O. Ogur.

Report 177

Bonding Elastomers: A Review of Adhesives & Processes, G. Polaski, J. Means, B. Stull, P. Warren, K. Allen, D. Mowrey and B. Carney.

Report 178

Mixing of Vulcanisable Rubbers and Thermoplastic Elastomers, P.R. Wood.

Report 179

Polymers in Asphalt, H.L. Robinson, Tarmac Ltd, UK.

Report 180

Biocides in Plastics, D. Nichols, Thor Overseas Limited.

Volume 16 Report 181

New EU Regulation of Chemicals: REACH, D.J. Knight, SafePharm Laboratories Ltd.

Report 182

Food Contact Rubbers 2 - Products, Migration and Regulation, M.J. Forrest.

Report 183

Adhesion to Fluoropolymers, D.M. Brewis and R.H. Dahm, IPTME, Loughborough University.

Report 184

Fluoroplastics, J.G. Drobny.

Report 185

Epoxy Composites: Impact Resistance and Flame Retardancy, Debdatta Ratna.

Coatings and Inks for Food Contact Materials

Martin Forrest

ISBN: 978-1-84735-079-4

Coatings and Inks for Food Contact Materials

Contents 1.

Introduction ...............................................................................................................................................5

2.

Coating and Ink Products for Food Contact Materials ..............................................................................5 2.1

Polymers for Coatings and Inks ......................................................................................................5 2.1.1

Acrylic ................................................................................................................................6

2.1.2

Alkyd resins .......................................................................................................................6

2.1.3

Amino Resins (e.g., urea-formaldehyde resins) .................................................................7

2.1.4

Epoxy Resins ......................................................................................................................8

2.1.5

Cellulosics ..........................................................................................................................9

2.1.6

Polyesters – Saturated and Unsaturated ...........................................................................10

2.1.7

Polyurethanes ...................................................................................................................12

2.1.8

Rosin ................................................................................................................................13

2.1.9

Silicone Resins .................................................................................................................13

2.1.10 Vinyl Polymers .................................................................................................................14 2.1.11 Other Polymers (e.g., hydrocarbons) ...............................................................................15 2.2

2.3

3.

Constituents of Coatings ...............................................................................................................15 2.2.1

Crosslinking Agents ........................................................................................................15

2.2.2

Other Additives ................................................................................................................15

2.2.3

Solvents ............................................................................................................................15

Constituents of Inks ......................................................................................................................16 2.3.1

Solvents ............................................................................................................................16

2.3.2

Plasticisers ........................................................................................................................16

2.3.3

Driers ................................................................................................................................16

2.3.4

Photoinitiators ..................................................................................................................16

2.3.5

Colorants ..........................................................................................................................17

2.3.6

Other Additives ...............................................................................................................18

Coatings and Inks used in the Food Chain ..............................................................................................18 3.1

Food Packaging .............................................................................................................................18 3.1.1

Packaging Types ...............................................................................................................18

3.1.2

Coatings Used in Metal Packaging (Tables 5 to 9) ..........................................................19

3.1.3

Coatings and Adhesives for Flexible Packaging (Tables 10 and 11) ...............................22

3.1.4

Inks for Metal Packaging (Table 12) ................................................................................24

3.1.5

Inks for Paper and Board Packaging (Table 13) ..............................................................27

3.1.6

Inks for Flexible Packaging (Table 14) ............................................................................28

3.2

Harvesting and Processing of Food ..............................................................................................28

3.3

Storage and Transportation ...........................................................................................................30

3.4

Presentation, Dispensing and Cooking .........................................................................................30

1

Coatings and Inks for Food Contact Materials

4.

5.

6.

7.

2

Application Techniques for Inks .............................................................................................................31 4.1

Lithography ...................................................................................................................................31

4.2

Flexography ..................................................................................................................................31

4.3

Gravure .........................................................................................................................................32

4.4

Inkjet .............................................................................................................................................32

4.5

Influence of Substrate Type ...........................................................................................................32 4.5.1

Inks for Metal Packaging ................................................................................................32

4.5.2

Inks for Paper and Board .................................................................................................33

4.5.3

Inks for Flexible Plastic Packaging ..................................................................................34

4.5.4

Set Off ..............................................................................................................................34

Regulations Covering the Use of Inks and Coatings with Food .............................................................34 5.1

Regulation in the European Union ................................................................................................34

5.2

Council of Europe (CoE) Regulations ..........................................................................................35 5.2.1

Coatings ...........................................................................................................................35

5.2.2

Inks ...................................................................................................................................36

5.3

National Regulations within the EU .............................................................................................37

5.4

FDA Regulations ...........................................................................................................................38

5.5

Other Considerations for Industrial Use .......................................................................................38

Assessing the Safety of Inks and Coatings for Food Applications .........................................................40 6.1

Global Migration Tests ..................................................................................................................40

6.2

Specific Migration Tests ................................................................................................................41

6.3

Fingerprinting of Potential Migrants from Coatings and Inks ......................................................41

6.4

Determination of Specific Target Species in Coatings and Ink Products and in Food Simulants and Foods ............................................................................................................41 6.4.1

Monomers, Solvents and Low Molecular Weight Additives and Breakdown Products ...42

6.4.2

Oligomers .........................................................................................................................42

6.4.3

Plasticisers and Oil-type Additives ..................................................................................42

6.4.4

Polar Additives and Metal Containing Compounds .........................................................42

6.4.5

Cure System Species, Initiators, Catalysts and Their Reaction Products ........................42

6.4.6

Antidegradants, Stabilisers and Their Reaction Products ................................................43

6.5

Sensory Testing .............................................................................................................................43

6.6

Toxicological assessment of migrants ..........................................................................................43

Potential Migrants and Published Migration Data ..................................................................................44 7.1

Acrylates .......................................................................................................................................44

7.2

Amines ..........................................................................................................................................44

7.3

Aromatics from Unsaturated Polyesters .......................................................................................45

Coatings and Inks for Food Contact Materials

7.4

Aromatics from Photoinitiation Reactions and Photoinitiator additives ......................................45

7.5

BPA and BADGE and Derivatives ................................................................................................46

7.6

Epichlorohydrin ............................................................................................................................47

7.7

Bisphenol A ...................................................................................................................................47

7.8

Solvents .........................................................................................................................................47

7.9

Plasticisers ....................................................................................................................................47

7.10 Extractables from UV-Cured Coating for Cardboard ...................................................................47 7.11 Potential Migrants .........................................................................................................................48 8.

9.

Improving the Safety of Inks and Coatings for Food Use ......................................................................52 8.1

New Food Approved Pigments .....................................................................................................52

8.2

Water-Based Systems ....................................................................................................................52

8.3

UV/EB Curable Systems ..............................................................................................................53

8.4

New Initiators for UV Curable Inks ..............................................................................................53

Future Trends ..........................................................................................................................................53 9.1

Improvements in Recycling Systems ............................................................................................53

9.2

Biodegradability ............................................................................................................................53

9.3

Use of Coatings to Improve Barrier Properties of Food Packaging .............................................54

9.4

Antimicrobial Systems ..................................................................................................................54

9.5

Laser Marking to replace Conventional Inks ................................................................................54

9.6

Intelligent and Active Packaging ..................................................................................................54

9.7

Applications of Nanotechnology ..................................................................................................55

9.8

Developments in Analytical Techniques .......................................................................................55

10. Conclusion ...............................................................................................................................................55 Additional References .....................................................................................................................................56 Sources of Further Information and Advice ....................................................................................................57 Reference Books .....................................................................................................................................57 Reports ....................................................................................................................................................58 Professional, Research, Trade and Governmental Organisations ...........................................................58 Commercial Abstract Databases .............................................................................................................58 Acknowledgements .........................................................................................................................................59 Abbreviations ..................................................................................................................................................59 References from the Polymer Library Database .............................................................................................61 Subject Index ................................................................................................................................................109 Company Index .............................................................................................................................................125

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Coatings and Inks for Food Contact Materials

The views and opinions expressed by authors in Rapra Review Reports do not necessarily reflect those of Smithers Rapra Technology or the editor. The series is published on the basis that no responsibility or liability of any nature shall attach to Smithers Rapra Technology arising out of or in connection with any utilisation in any form of any material contained therein.

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Coatings and Inks for Food Contact Materials

1 Introduction For many years, Rapra Technology has carried out research projects for the UK Food Standards Agency (FSA). These have covered a wide range of polymer products (e.g., rubbers, silicone-based materials, ionexchange resins, laminate materials) and have provided the FSA with important information on the materials and manufacturing practices that are used in industry, as well as making an important contribution to the data, via extensive experiments, that is available with respect to the migratory behaviour of these products when they are in contact with food simulants and foodstuffs. This Review Report has, as its origin, an FSA project on Coatings and Inks that was carried out at Rapra from 2005 until 2007. The objective of this project was to assess the potential for the migration of substances from coatings and inks that were used in food packaging applications. As a significant amount of work had already been carried out on coatings that were in direct contact with food (e.g., can coatings), a boundary was set that only coatings and inks in nondirect food contact situations would be considered. As the scope of this review report is greater than the Rapra project (see below) and, due to the limitations of this particular format, it has only been possible to include some of the information that was acquired during the course of the FSA project. If the reader has a particular interest in coatings and inks used in these types of applications, they are therefore recommended to apply to the FSA for a full version of the final project report, which was published in March 2007. Coatings and inks for use with food have been a very topical subject over the last couple of years, mainly due to the culmination of the work that has been carried out by the Council of Europe (CoE). As a result of its efforts, we have seen the adoption of both a Resolution for Coatings, and a Resolution for Inks used on nonfood contact surfaces. The Inks Resolution has been controversial with industry bodies throughout Europe, who have claimed that its inventory list is incomplete and not representative of current industry practice (see Section 5.2). In addition to these regulatory developments, this is an active area for research, with a number of innovative and sophisticated products finding commercial applications, e.g., in active and intelligent packaging, and antimicrobials – see (Section 9). This report has attempted to cover all of the coatings and inks products used in food contact scenarios. Hence, direct and non-direct contact situations are included throughout the food chain, e.g., harvesting, processing, transportation, packaging and cooking. In

practice, this encompasses an extremely wide range of polymer systems and formulations, and an emphasis has been placed on coatings and inks used in food packaging, as this is usually regarded as representing the most important application category with respect to the potential for migration to occur. With respect to food packaging, all three of the major material classes are covered, i.e., metal, paper and board, and plastic. In addition to a thorough introduction of the polymers and additives that are used to produce coatings and inks, there are also chapters covering the regulation of these materials, the migration and analytical tests that are performed on them to assess their suitability for food contact applications, the migration data that have been published, and the areas in the field that are receiving the most attention for research and development. This report is one of a series of three. A report summarising the current situation of the use of rubber products for food contact applications was published in 2006 (84), and a report reviewing the use of siliconebased materials (including rubbers, resins and liquids) with food be published by Rapra shortly.

2 Coating and Ink Products for Food Contact Materials 2.1 Polymers for Coatings and Inks Coatings and inks are polymer-based products, with the polymer being the primary component in the former, and the binder for the pigment system in the latter. In both cases, the two main types of systems are: 1) Those where high molecular weight (mw) polymer is present from the outset – the solvation of the polymer by a solvent, or water, is critical in these cases. 2) Those where the polymer is formed in situ from the monomer(s), i.e., the curing types – a number of mechanisms can be responsible for the curing reaction. Some of the principal types of polymers that are used in coatings and inks products are discussed next. In addition, because there are occasions where conventional rubbers and thermoplastic polymers can be used as protective coatings (e.g., food storage), these are mentioned in Section 2.1.11.

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Coatings and Inks for Food Contact Materials

2.1.1 Acrylic Polyacrylate coatings and binders are based on acrylic or methacrylic esters. These polymers are created by addition type polymerisations of various combinations of monomers, including: Methyl esters of acrylic and methacrylic acids Ethyl and higher esters of acrylic and methacrylic acids Hydroxyethyl esters of acrylic and methacrylic acids Diol monoarylates or methacrylates, and Acid monomers (i.e., acrylic acid and methacrylic acid). Addition polymerisation is usually achieved by freeradical initiation (e.g., by photochemical processes), and other unsaturated monomers (e.g., styrenics) may sometimes be incorporated for process or product optimisation. In addition, acrylic polymers can be blended with acrylic monomers for viscosity control, which can remove the need for solvents, and polyfunctional acrylic monomers enable crosslinking polymerisation reactions to occur, i.e., curing reactions.

Other curing mechanisms exploit the polyfunctionality in hydroxyl groups that may be obtained by copolymerisation with hydroxyalkyl acrylates and methacrylates. Examples of cure via reaction of these side groups include: Etherification with melamine- or benzoguanamineformaldehyde resins polyacrylic−OH + HOCH2N< → polyacrylic–O–CH2N< + H2O Urethane formation with isocyanates polyacrylic−OH + O=C=N~ → polyacrylic−O−C(=O)−N~ Isocyanate-hydroxyl reactions are particularly active, allowing scope for ambient temperature cures, whilst etherification requires heat and forms the basis of stoving enamels. Hydroxyl groups are also effective for the ring-opening of epoxides, and therefore epoxy resins can be used for the cure of suitably functional acrylics. The activity of the (amine catalysed) ring opening by hydroxyl groups decreases in the series, ROH > ArOH > RCO2H, and therefore epoxy cures offer useful versatility and control for acrylics containing either hydroxyl or carboxylic acid groups.

Polyfunctional acrylic monomers can be obtained by reactions of acrylic acid with:

2.1.2 Alkyd resins Polyhydric alcohols Hydroxyl-terminated polyesters Bis(epoxides) such as bisphenol A diglycidyl ether (BADGE) (see epoxy resins) The reaction of acrylic acid with polyhydroxy alcohols is a prolific source of polyfunctional acrylic monomers. Examples of di-, tri- and tetra-functional products are: dipropylene glycol diacrylate (DPGDA) CH2=CHCO2(CHMeCH2O)2OCOCH=CH2 propoxylated glyceryl triacrylate (GPTA) (CH2=CHCO2CHMeCH2OCH2)2CHOCH2CHMeOCOCH=CH2 pentaerythritol tetra-acrylate (PETA) (CH2=CHCO2CH2)4C

6

Alkyd resins are polyesters derived from polyhydric alcohols and mixed acids including dibasic and monobasic types. The polyhydric alcohols include: glycerol (a commonly used compound), pentaerythritol, trimethyolpropane and sorbitol. The dibasic acids (or anhydrides) include phthalic (again commonly used), maleic, isophthalic, adipic and sebacic. The monobasic acids include fatty types with different levels of unsaturation for air-drying performance. These have their origins in natural oils, which themselves usually form the starting material for the production of alkyds. The first stage in production, at an elevated temperature (> 200 °C) is the hydrolysis or alcoholysis (with glycerol), and the second stage is the addition of the dibasic acid component with further heating up to 250 °C. The most commonly used types of oil include: a) tung b) linseed c) dehydrated castor

Coatings and Inks for Food Contact Materials

Table 1. Types of Alkyd Type

Oil content (%)

Phthalic anhydride (%)

Short oil resins

35-45

>35

Medium oil resins

46-55

30-35

Long oil resins

56-70

20-30

>71

<20

Very long oil resins

d) sunflower e) soya f) cottonseed g) olive h) coconut Fatty acids which may be incorporated directly include tall-oil fatty acids and C8 to C10 synthetic types. A wide range of different products are possible from these reactions. For convenience, alkyds are grouped into four different types, as shown in Table 1. The durability of the cured products decreases with increasing oil content, whereas the long and very long oil alkyds have better brushing properties. Very long oil alkyds form the basis of ink binders. Mineral spirit is commonly used as a solvent for such binder resins, although the presence of alcohols or glycol ethers can also lower viscosity.

2.1.3 Amino Resins (e.g., urea-formaldehyde resins) Amino resins are obtained from a complex sequence of reactions (e.g., addition, condensation and eliminations reactions) for example: H2NCONH2 + CH2O → H2NCONHCH2OH H2NCONHCH2OH + CH2O → HOCH2NHCONHCH2OH >NCONHCH2OH + H2NCONH~ → >NCONHCH2NHCONH~ + H2O ~NHCH2OH + HOCH2NH~ → ~NHCH2OCH2NH~ + H2O ~NHCH2OCH2NH~ → ~NHCH2NH~ + CH2O

A well established procedure reacts urea with a twofold molar excess of formaldehyde under alkaline conditions to yield an intermediate product mix of mono- di-, and tri-methyolureas, together with some residual urea and formaldehyde. The condensation takes place under acid catalysis, and may be achieved in two stages, the first to create a linear polymer, and the second to achieve a more complete condensation that creates a crosslinked network. Acid compounds such a phthalic anhydride are incorporated into the final curable formulation, the curing being achieved by heating. These, so-called ‘unmodified’ resins are used for ink binders but are generally regarded as unsuitable for coatings owing to their limited solubility in common solvents. The solubility limitations can be overcome by modification with alcohols where some of the methylol groups are alkylated, for example: >NHCH2OH + ROH → >NHCH2OR + H2O n-Butanol is commonly used for modification in this way, i.e., for ‘butylated urea-formaldehyde resins’. Another variation is the use of melamine (triamino1,3,5-triazine, C 3 H 6 N 6 ) instead of urea. The manufacturing sequence is essentially the same as for urea-formaldehyde resins, with addition under alkaline conditions and chain extension and crosslinking under acid conditions. The acid-catalysed etherification is also employed for modification, so that both methylated and butylated melamine-formaldehyde resins find commercial uses. As with the urea-formaldehyde resins, alkylation is used to enhance solubility in common solvents and the alkylated resins are preferred for coating formulations. Yet another variation is the use of a guanamine instead of melamine – a molecule where one amino group of the melamine is replaced by an alkyl aryl group. One such example is benzoguanamine (2,4-diamino-6-1,3,5triazine) (Figure 1).

7

Coatings and Inks for Food Contact Materials

Epoxies are cured by ring-opening of the oxirane group – either by reaction with active hydrogen compounds or by catalysed homopolymerisation. For coatings, these cures generally fall into two types: ambient temperature cures with polyfunctional amine or thiol co-agents or with polymerisation catalysts; and elevated temperature cures with polyfunctional hydroxyl co-agents (or a combination of epoxide and hydroxyl functionality, such as with anhydrides).

Figure 1 Structure of benzoguanamine

Benzoguanamine closely mirrors melamine in its addition and subsequent condensation reactions with formaldehyde. Benzoguanamine-formaldehyde resins and butylated benzoguanamine-formaldehyde are used in surface coatings. Any of these amino resins may be used alone, or in combination with other resins, such as epoxies or alkyds.

2.1.4 Epoxy Resins Epoxy curing reactions exploit the reactivity of the epoxide group. Epoxy resins contain at least two such groups per molecule: the BADGE provides the basis of many epoxy resins. BADGE and its homologues are obtained by the base catalysed reaction of epichlorohydrin with bisphenol A (BPA). BADGE (MW 340) is the lowest molecular weight bis-epoxide obtainable from this reaction, i.e., 2,2-bis[4-(glycidylo xy)phenyl]propane. The phenolic group is also capable of reacting with the epoxy groups present and so this is potentially a polymerising reaction, requiring a significant excess of epichlorohydrin to avoid high molecular weight products. These can be regarded as higher homologues of 2,2-bis[4-glyc idyloxy)phenyl]propane with the inclusion of the - O - C 6H 4- C M e 2- C 6H 4- O - C H 2- C H ( O H ) - C H 2repeat unit. Some polymerisation is helpful, as BADGE itself is a solid, having a melting point of 40-44 °C. The inclusion of a small amount of polymer allows for liquid (at ambient temperature) products.

8

The reactions with active hydrogen compounds are sequential in that the epoxide ring opening generates a hydroxyl group, which, in turn, may initiate further ring opening. This is illustrated in Figure 2, for the reaction of a primary amine with epoxy, where both N−H bonds may react with epoxy, as may the hydroxyl groups formed from each addition. The third reaction shown, i.e., that of the hydroxyl addition, is the form of the reaction where alcohols, or phenols, are used as co-agents. The use of polyfunctional co-agents (i.e., curing agents) is important for network development. Polyalkylene amines such as diethylenetriamine (DTA) and ethylene diamine (EDA), aromatic diamines such as 4,4′ iaminodiphenyl-methane (DDM) and aminoamides and their derivatives such as dicyandiamide [H2NC(=NCN)NH2, called ‘DICY’), provide low temperature curing and must usually be applied within a short time (e.g., within 1-2 days) of mixing. A slower reaction affords better control, and hydroxyl-functional curatives form the basis of stoving enamels. Polyfunctionality is obtained with phenol-formaldehyde (PF) resins, where the primary reactions are thought to be those of the phenolic (ArOH) or methylol (ArCH2OH) hydroxyls (depending on the PF resin type used), although other hydroxyl species (including the secondary alcohol formed by ring opening) will also be involved. Phenol formaldehyde resins offer some of the highest functionalities of epoxy curing agents, and careful selection of resin (PF and epoxy) grades is important if brittle products are to be avoided. In typical phenolicepoxy stoving enamels, a relatively long-chain bisepoxide molecule (e.g., higher homologue of BADGE) would be preferred. The condensation products of this with formaldehyde will contain both amino (>NH) and aminomethylol (>NHCH2OH) groups, depending on the extent of reaction. The inclusion of two, or more, different resins as co-agents in epoxy stoving formulations is not unusual. One benefit may lie in film forming

Coatings and Inks for Food Contact Materials

Figure 2 Examples of the reactions that are involved in the curing of epoxy resins

behaviour where the delay of skinning will enhance solvent evaporation to provide for better properties and improved surface gloss.

2.1.5 Cellulosics Cellulose is a naturally occurring high mw carbohydrate polymer of formula (C6H 10O 5) n. It is extensively hydrogen bonded and possesses remarkable strength/ weight characteristics. However, its extensive hydrogen bonding means that it cannot be melted, e.g., for melt processing, without thermal decomposition. Nor can it be dissolved in any solvent in its unmodified form. Given its availability, much effort has been devoted to the development of modified forms.

Nitrocellulose Nitrocellulose is a cellulose ester. It is a highly polar polymer which is easy to dissolve in polar solvents (esters, alcohols) and has good film-forming character on drying. Nitrocellulose (Figure 3) is obtained by steeping cellulose (e.g., cotton linters, paper pulp) in a mixture of concentrated nitric and sulfuric acids, at 20-40 °C. The composition of the acid mix determines the resultant mw. Compositions rich in sulfuric acid provide the lowest mw products, but grades for inks and lacquers (typical molecular weight of 50,000 or lower) are subject to mw reduction by heating with water under pressure at 130 –160 °C.

The hydroxyl functionality in cellulose allows for a number of modifications, notably esterification and etherification. Examples of products produced in this way include: • • • • •

cellulose acetate butyrate ethyl cellulose hydroxyethylcellulose methyl cellulose nitrocellulose

Figure 3 Nitrocellulose (cellulose nitrate) - typical repeat unit

9

Coatings and Inks for Food Contact Materials

The reactions of production are nitration (esterification) and hydrolysis (of formal −OCH2O−) groups, i.e.,: ~OH + HNO3 → ~ONO2 + H2O >CH−O−CH< + H2O → 2>CH−OH By reducing H-bonding associations, the esterification reduces crystallinity. Hydrolysis reduces the mw . Typical degrees of esterification for binder polymers are around two nitrate groups per glucose residue, with higher levels being reserved for propellants and explosives. Dried nitrocellulose has a glass transition temperature (Tg) of around 53 °C (depending on the degree of esterification) and therefore requires plasticisation for use in inks and lacquers. Plasticisers for nitrocellulose include the common types (e.g., phthalates, phosphates, etc.) together with natural products such as camphor and castor oil. Nitrocellulose is relatively water resistant although prone to oxidation. It is not readily amenable to crosslinking, and chemically active drying systems can only be created by blending with other resins. Alkyd, ketone, urea, maleate and acrylic resins are available for formulating with nitrocellulose binders.

Other Cellulose Esters Cellulose acetate is prepared by the acetylation of cellulose (e.g., by first steeping cellulose in acetic acid followed by treatment with acetic anhydride in the presence of sulfuric acid), a process which invariably esterifies all three hydroxyls per repeat unit. The product is cellulose triacetate. The acetate esters have better oxidation resistance than the nitrate esters, but cellulose triacetate is softer and more difficult to plasticise. Acetate levels can be reduced by partial hydrolysis, and the re-introduction of hydroxyl groups can benefit both strength and hardness. Cellulose acetates therefore represent a range of polymers with different degrees of esterification. They are used in films, fibres and lacquers. Lacquer grade polymers typically have around 2.32.4 acetate groups per glucose residue. The degree of substitution is also measured in terms of acetyl content (as a weight percentage) or as the equivalent yield of acetic acid. In the latter description, lacquer grades have 54-56% acetic acid yield (61-62.5% for the triacetate).

10

Further refinements in synthesis may be achieved by mixed esterification. Cellulose acetate butyrate (CAB) polymers generally offer better mechanical properties than the acetates, and better compatibility with other resins and organic solvents. They can be obtained esterified with a mixture of acetic and butyric anhydrides. Commercial grades for lacquers may have similar numbers of acetate butyrate groups with a very small level of hydroxyl groups (< 0.5) per glucose residue) introduced by a second stage hydrolysis.

Cellulose Ethers Cellulose ethers such as methyl or ethylcellulose are obtained by treating alkali cellulose with the appropriate alkyl chloride (e.g., ROH → RONa → ROMe). The first step is to treat cellulose with 50% aqueous sodium hydroxide at about 60 ºC to create the alkali cellulose. The subsequent treatment with the alkyl chloride is accomplished with heat under pressure, the reaction conditions controlling the degree of substitution. Only a small amount of substitution is needed to disrupt the cellulose structure and generate useful solubility. The solubility characteristics depend on the level of substitution: intermediate levels of substitution by methyl or ethyl groups (e.g., 1.3-2.4 groups per glucose residue) provide solubility in water, whereas higher levels give solubility in less polar solvents (even hydrocarbons at the highest levels of substitution). Commercial grades of methylcellulose have substitution in the 0.3-1.8 range and are generally exploited for their water solubility. However, higher substitution levels encountered in commercial grades of ethylcellulose where solubility in other solvents is exploited. Ethylcellulose at around 2.5 ethyl groups per glucose residue is compatible with a range of plasticisers and other resins. For any polymer, solubility depends on molecular weight and, for cellulose polymers, all these treatments are accompanied by a useful degree of molecular weight reduction (of the original cellulose). The treatment which usually delivers the highest levels of water solubility is hydroxyethylation.

2.1.6 Polyesters – Saturated and Unsaturated Polyesters for hard coatings are commonly based on aromatic diacids e.g., phthalic, isophthalic or terephthalic. MW control (for ease of flow, etc.)

Coatings and Inks for Food Contact Materials

can be achieved by reaction with diols in excess. Common examples include low mw glycols such as ethylene glycol, propylene glycol, diethylene glycol, and 1,4-butanediol. Additional monomers can also be incorporated to provide the functionality that is necessary for curing. What these are depends on the cure mechanism used. Water is a by-product of polyesterification and the extent of reaction is controlled by its removal. This can be hindered by high viscosity mixes, although modifications in reactor design can help. The chemistry of the reaction can also be altered to produce less water, or a different by-product. An example of the latter is the use of the methyl ester of the diacid, and the former by using the anhydride instead of the diacid. With phthalic anhydride, only one mole of water is produced for two moles of ester formed. For example: ~COOCO~ + ROH → ~COOR + HOCO~ ROH + HOCO~ → ROCO~ + H2O

Examples include glycerol and trimethylolpropane. This allows for crosslinking even with difunctional isocyanates. The hydroxyl/isocyanate reaction is sufficiently active to preclude storage-stable onecomponent mixes, although these are possible if a blocked isocyanate is used. A blocked isocyanate is a thermally-labile urethane, so that un-blocking is achieved by suitable heating. Phenol is a common blocking reagent, and it is released in the thermal unblocking, for example: RNCO + HOC6H5 → RNHCOOC6H5 → RNCO + HOC6H5 One mole of phenol is released for each equivalent of isocyanate. In effect, the alcohol on the polyester competes with the phenol for the available isocyanate, and the (monofunctional) phenol has the potential to interfere with network formation. However, in thin coatings at elevated temperature, the phenol can be lost by volatilisation: hence phenol blocking is usually reserved for stoving enamels.

Saturated Polyesters

Unsaturated Polyesters

Having a stoichiometric excess of alcohol in the original polyesterification results in a polyester with hydroxyl terminals. The cure of saturated polyesters utilises the reactivity of these end groups. The subsequent cure can be achieved by reactions such as:

Unsaturated polyesters have C=C bonds in the backbone, most commonly introduced via maleic anhydride or fumaric acid in the original polyesterification mix. A typical unsaturated polyester can be obtained by heating maleic and phthalic anhydrides with a stoichometric excess (e.g., 20%) of propylene glycol. The mixture is heated at 150-200 ºC for up to 16 hours whilst water is continually distilled off. A catalyst, e.g., p-toluene sulfonic acid, is sometimes used, and some xylene may be incorporated to assist removal of water by azeotropic distillation.

Etherification with melamine-formaldehyde, or benzoguanamine-formaldehyde resins: polyester−OH + HOCH2N< → polyester−O−CH2N< + H2O Urethane formation with isocyanates: polyester−OH + O=C=N~ → polyester−O−C(=O)−HN~ Melamine-formaldehyde, or benzoguanamineformaldehyde resins, are usually polyfunctional in methylol groups, and therefore crosslinking occurs even with difunctional polyesters. The thermal activation necessary for etherification allows for useful control of this cure which is commonly exploited in stoving enamels. Crosslinking can also be provided via polyfunctionality in the polyester, as is possible when a triol (or polyol), is incorporated into the original polyesterification mix.

The cure of an unsaturated polyester is by a free-radical polymerisation, and suitable mobility and reactivity is introduced into the resin by the incorporation of a co-monomer. Styrene is the common choice, although acrylates are also used, and the final stage of the resin formation is the incorporation of this monomer together with an inhibitor such as hydroquinone. The free radical cure of the resin is essentially a copolymerisation of the unsaturated polymer backbone with the unsaturated monomer. It is possible for oxygen to interfere with the reaction in the curing of thin films and steps to exclude it must be taken. Paraffin wax, which has relatively low solubility in the resin, and hence migrates to the surface, is usually used to create a physical barrier. Its addition, at around the 0.1% level, is accomplished using a small amount of solvent (e.g., toluene) as a carrier.

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Coatings and Inks for Food Contact Materials

Table 2. Breakdown Products of Diacyl Peroxides Breakdown Products

Peroxide

Hydrogen Abstraction

Radical Coupling

Benzene

Biphenyl 4,4-dichlorobiphenyl

Chlorobenzene

2,2 ́,4,4 ́-Tetrachlorobiphenyl

Dibenzoyl 4-Chlorodibenzoyl 2,4-Dichlorodibenzoyl m-dichlorobenzene

Initiator systems may also be added in solution, these solvents for blending are usually the only solvents used in unsaturated polyester coatings, in which the free monomer provides the major viscosity reduction for application. Unsaturated polyesters can be cured at room temperature by the use of either two-part initiation systems, or by photoinitiation. The two-part initiation can use either of two approaches to promote peroxide breakdown. One utilises drier chemistry to cause the catalytic breakdown of hydroperoxides. The catalyst used is a metal soap, typically of cobalt, but its action in this case is on intentionally added hydroperoxides, as distinct from the hydroperoxides, formed as a product of air oxidation, that are used in traditional drier chemistry. The hydroperoxides that are added include methyl ethyl ketone peroxide or cyclohexanone peroxide, their breakdown products include methyl ether ketone and cyclohexanone, respectively.

compounds. The chemistry can be illustrated with respect to hydroxyl addition. The initially-formed adduct itself contains active hydrogens, so that a sequential addition is possible: XNCO + HOR → XNHCOOR urethane formation XNCO + XNHCOOR → XNHCON(X)COOR allophanate formation This second addition binds two molecules of isocyanate per starting hydroxyl group, so that this sequence makes for a crosslinking reaction. The active hydrogen remains, and the sequence can continue. Hence, depending on the availability of isocyanate, the reaction with allophanate can be represented in a generic sense as an addition polymerisation of the form: nXNCO + XNHCOOR → XNHCO[N(X)CO]nOR

The other approach uses tertiary aromatic amines with acyl peroxides. This involves an electron-transfer process to promote diacyl peroxide breakdown, e.g., with N,N-dimethylaniline: ArCOOOCOAr + C6H5NMe2 → ArCOO− [C6H5NMe2]+ + ArCOO· but the generation of acyloxy radicals has the potential to produce unwelcome aromatics (e.g., benzene from dibenzoyl peroxide) which may preclude this approach from resins where food contact application is anticipated. For reference, the anticipated breakdown products of commercial diacyl peroxides are listed in Table 2 (195).

2.1.7 Polyurethanes Polyurethanes (PU) are formed as a result of addition reactions of isocyanates, usually with active hydrogen

12

Polyurethane curing chemistry is critically dependent on the nature of the co-reagents, their relative proportions, the presence and type of catalysts and the thermal history of the system. Both aliphatic and aromatic isocyanates may be employed- the former offering better resistance to solar radiation and the latter providing higher reactivities in cure. For the hydroxyl component of the cure, its activity with respect to isocyanate is governed by both polar and steric effects (219). Model compound studies show that the reactivity with isocyanate decreases as: CH3CH2OH > CH3OH > (CH3)2CHOH > (CH3)3OH ~ C6H5OH So, in hydroxyl-isocyanate cures, aliphatic hydroxyls provide the co-agents for cure, whilst aromatic (phenolic) hydroxyls provide potential blocking agents. In the latter case the isocyanate is introduced into the

Coatings and Inks for Food Contact Materials

cure formulation as is a phenol adduct (phenyl urethane). This adduct dissociates on heating: if the dissociation is in the presence of a more aliphatic hydroxyl then an aliphatic urethane will be formed: X−NHCOOPh → X−NCO + HOPh X−NCO + HOR → X−NHCOOR The aliphatic hydroxyl co-agents in polyurethane cures are usually low mw polymers. Examples include hydroxyl-terminated polyesters and polyethers and hydroxyl-containing acrylics. Even without catalysis, the hydroxyl-isocyanate reaction is sufficiently rapid to compromise storage stability prior to cure and polyurethanes are commonly two-pack systems. Catalysts include tertiary amines, metal soaps and organometallics. One pack formulations are possible by using blockedisocyanates (as described above), moisture-curing systems and those incorporating fully reacted, unreacted polyurethanes which cure by alternative chemistry (such as air-drying) or undergo physical drying by solvent evaporation. Moisture-curing polyurethanes are formulations containing a substantial excess of isocyanate in which the cure proceeds via an initial isocyanate hydrolysis: X−NCO + H2O → X−NH2 + CO2 This hydrolysis reaction generates active hydrogen, which undergoes sequential reactions (i.e., by urea and biuret formation) in the same manner as for the hydroxyl addition described earlier.

2.1.8 Rosin Rosin is a natural resin obtained from pine trees. It is a thermoplastic acidic product containing about 90% of so-called ‘resin acids’ – composed mainly of cyclic isoprenoid acids. The predominant resin acid is abietic acid which has an empirical formula of C20H30O2. Resins acids are unsaturated and therefore unstable with respect to oxidation. Stability can be improved by hydrogenation or by dehydrogenation (aromatisation) to yield so-called ‘modified rosins’. Rosins and modified rosins can be changed further by reactions such as salt formation (e.g., with sodium, potassium or calcium hydroxides) or esterification. Esterification with polyhydroxy alcohols, such as glycerol or pentaerythritol, provides a useful increase in mw.

Rosin esters, rosin salts, modified rosins and modified rosin esters, ranging in physical state from viscous liquids to hard friable solids, are used as binders in a variety of ink formulations. The method of incorporation into the ink depends on the rosin type, notably its acidity. For example, rosin resins may be incorporated as dispersions in linseed oil, as solutions in alcohol or hydrocarbons, or as solutions or dispersions in aqueous ammonia or other alkalies. Rosin resins are also components of coating formulations, for example or as modifiers for alkyds, or epoxies, or for cellulose nitrate lacquers.

2.1.9 Silicone Resins A silicone polymer has a backbone of alternating silicon and oxygen atoms, i.e., −RR′ Si−O−, where R and R′ may be alkyl, aryl, fluoroalkyl or hydrogen, but are more commonly methyl groups. Therefore, the most common repeating unit in a silicone polymer is dimethysiloxanel: −Me2Si−O−. Silicone resins are crosslinked products. In this case, the crosslinking mirrors other silicon systems (e.g., familiar RTV sealants and elastomers) with the curing process (silanol condensation, i.e., SiOH + HOSi → Si−O−Si) essentially being an extension of the reactions by which the original resin was prepared. Silicone resins are highly branched and are effectively crosslinking systems which are held at an intermediate state of conversion until the reaction can be completed as part of the final application, or fabrication stage. The polysiloxanes for resins are polyfunctional in silanol as a consequence of branch points obtained by the introduction of trifunctional, RSi(−O−)3, or tetrafunctional, Si(−O−)4, units into the siloxane backbone. In a typical process for silicone resin manufacture, the appropriate mix of chlorosilanes is dissolved in a solvent such as toluene or xylene and then stirred with water. At the end of the reaction, the organic layer is separated and washed free of the acid produced, and then partially distilled to enrich the solids’ content of the resulting solution. Whilst further heating or treatment with catalysts may be used to refine the mw distribution, the resin is often kept in this solution until the final cure is required, such as for coating or laminated products. All resin cures are carried out using heat and a suitable catalyst (metal soaps, organometallics, bases). Heat is essential for progressing a highly crosslinking cure,

13

Coatings and Inks for Food Contact Materials

where the onset of vitrification causes a transition from kinetic to diffusion control. On this basis the temperature of cure should be at least that of the highest temperature expected in service. Although somewhat softer (and less scratch resistant) than other thermosetting resins (epoxies, alkyds), silicone resins are valued for their heat resistance and water repellency. Heat is also capable of effecting silanol exchange reactions such that the molecular network is, to a degree, in a state of flux. Low molecular weight material can be created through these exchanges, and the principal migratory species in silicone resins are cyclic and linear oligomeric polysiloxanes. The versatility of silicone chemistry means that it is relatively easy to manufacture silicone resin products that are capable of curing at ambient or relatively low temperatures (e.g., 40 °C), after having been applied to the substrate in a solution form (e.g., in isopropanol) by methods such as dipping or spraying. Such resins are useful in a kitchen and general food preparation environment as they have very good dirt repellent properties and so aid the removal of food residues. To improve their heat resistance (e.g., up to 650 ºC) and chemical resistance, silicone resins are modified by the addition of, for example, epoxy groups. These polymers can be obtained as solutions (e.g., 75% w/w in solvents such as methoxypropylacetate) and the coatings resulting from such products, some of which have FDA approval, can be employed as heat resistant decorative coatings in the food industry. It is also possible to incorporate polytetrafluroethylene (PTFE) into such coatings to improve their non-stick performance. The identity and migration behaviour of species that originate from a variety of food-contact silicone products (rubbers, resins and fluids) are described in the final report of a recent FSA project on silicones managed by Rapra (a.1) In addition to being used as the primary binder material, low mw silicone polymers can be modified with organic groups, e.g., phenyl groups, polyether or polyester groups, and used as additives in UV curable coating formulations (e.g., polyester acrylates). Such additives have been shown to enhance the performance of the coatings in a number of ways, e.g., increased temperature stability, superior adhesion to substrates, increased stability towards hydrolysis and a reduction in surface tension (201).

14

2.1.10 Vinyl Polymers Examples of vinyl polymers that may be found as binders in inks and coatings, include polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH) and polyvinyl acetals. Much PVAc is obtained by emulsion polymerisation, a process which delivers the product in latex form. When dried it is brittle, but it is amenable to plasticisation and is soluble in a range of solvents. Although not amenable to subsequent cure, it has potential uses as a binder in aqueous and non-aqueous systems. It is also amenable to internal plasticisation by copolymerisation with a monomer such as 2-ethyhexyl acrylate. PVAc is the precursor to PVOH. The reaction is usually performed as an alcoholysis in methanol solution (often from a PVAc prepared in methanol solution) in the presence of sodium methoxide. The reaction can be represented schematically as: ROCOCH3 + MeOH → ROH + MeOCOCH3 The degree of substitution can be controlled by the reaction conditions with the most common commercial grades offering around 90% substitution. This level of substitution offers the highest solubility in water, as further hydrolysis increases inter-polymer H-bonding. Fully hydrolysed PVOH is only soluble in water upon heating. PVOH offers a particularly useful combination of properties: for example it offers good water solubility and a higher level of mechanical performance than normally associated with water-soluble polymers. PVOH is widely used as a binder in water-based inks and coatings. Polyvinyl acetals are obtained by condensation of the backbone hydroxyl groups with aldehydes. With formaldehyde, polyvinyl formal is obtained, and with butyraldehyde, polyvinyl butyral is obtained. A typical repeating unit in polyvinyl butyral has the form shown in Figure 4. The precursor to polyvinyl butyral is usually the fully hydrolysed PVOH. This is suspended in ethanol and heated in the presence of butyraldehyde and acid (e.g., H2SO4) catalyst, and the product polymer is then precipitated with water. Polyvinyl butyral contains residual hydroxyl groups, and the combination of functionality makes for useful solubility in a range of polar solvents from ketones and esters to glycol ethers

Coatings and Inks for Food Contact Materials

The basic ingredients of barrier or protective coatings can be broken down into four main classes: polymers, crosslinking agents, additives and solvents.

Figure 4

The types of polymers that are used to produce coatings have already been discussed in Section 2.1. The remaining constituents are covered next.

Structure of polyvinyl butyral

2.2.1 Crosslinking Agents and alcohols. To a degree, the properties can be tuned by control of the level of acetylation, but polyvinyl butyrals are generally soft, low melting point polymers.

2.1.11 Other Polymers (e.g., hydrocarbons) Where relatively thin films of rubber (e.g., ethylenepropylene-diene terpolymer) or thermoplastic polymer (e.g., polyolefin) are used to protect metal surfaces against corrosion (e.g., in storage tanks), they can also be regarded as coatings. In these cases, grades of rubber, or thermoplastics, that are approved for food contact use will be used and the type of polymer (and polymer compound) chosen will depend upon the nature of the food product (i.e., aqueous or fatty), and the physical properties (e.g., abrasion resistance) that the application requires. In addition to solid polymer products, latex type products are also used as coatings. These are often found on paper and board type packaging for the food industry. For example styrene-butadiene latexes are commonly used for these types of applications, as are terpolymers of acrylonitrile-butadiene-styrene (ABS), the latter offering greater strength and mottle resistance when compared to the former materials.

Crosslinking agents are additives, which act chemically on the polymer to effectively create a significant increase in the molecular weight, ultimately producing a complete three-dimensional network. This phenomenon can be regarded as drying via chemical reactions. The choice of crosslinking agent is specific to the polymer concerned and the relevant examples have been discussed with the individual polymer types in Section 2.1.

2.2.2 Other Additives Additives fall into several types, e.g., pigments, catalysts and various agents to assist flow, leveling or defoaming. Pigments include the same multitude of types that are discussed for inks in Section 2.3.5, and the catalysts for cure are discussed with the polymer types in Section 2.1. The various other additives include: i)

higher-boiling solvents (to those listed in Section 2.2.3) to promote levelling and film formation,

ii) surfactants to promote surface wetting, iii) silicates or metal chelates as thickening agents for viscosity control, and

2.2 Constituents of Coatings Coatings can be used for protection (e.g., to prevent the rusting of metal) or, in the case of packaging materials, for barrier or release performance. There are also cases where the coating has other functionality, e.g., for anti-mist performance. Coatings that are used in ‘release type’ applications may be silicone materials, or based on other polymers containing slip additives such as fatty amides. Protective or barrier coatings may be based on curing systems, or evaporating solutions of thermoplastic (i.e. noncrosslinking), or rubber-type, polymers.

iv) esters, soaps waxes or mineral or silicone oils for defoaming action.

2.2.3 Solvents Solvents are not always used. Where they are, they may fall into the following classes: •

Aliphatic hydrocarbons

•

Cycloaliphatic hydrocarbons

15

Coatings and Inks for Food Contact Materials

2.3.1 Solvents

•

Terpene hydrocarbons and terpenoids

•

Aromatic hydrocarbons

•

Chlorinated hydrocarbons

A list of solvents that are typically used in inks is given next:

•

Alcohols

•

Water

•

Ketones

•

Aliphatic hydrocarbons

•

Esters

•

Cycloaliphatic hydrocarbons

•

Ethers

•

Terpene hydrocarbons and terpenoids

•

Glycol ethers

•

Aromatic hydrocarbons

•

Alcohols

•

Ketones

•

Esters

•

Glycols

•

Vegetable oils

2.3 Constituents of Inks Printing inks can be solvent-borne or water borne: they can exploit reactive or non-reactive drying mechanisms. The principal ingredients are ‘vehicles’ and colorants. The vehicle is the liquid medium, which carries the colorant through the printing process to the substrate and provides stability and gloss to the printed product after drying. Vehicles include solvents, binder resins (i.e., polymers), and additives. Colorants include dyes and, more commonly, pigments. A range of polymer types, natural or synthetic, may be used as binder resins in inks. Natural resins include rosin types, whilst synthetic binder resins are commonly based on alkyd, amino or acrylic types. Again, the various polymers used are discussed in more detail in Section 2.1. The inks that are used in food applications usually have complex compositions. The following parameters have to be considered when formulating them: •

Type of substrate

•

Type of foodstuffs to be packed

•

Type of printing processes and printing equipment

2.3.2 Plasticisers Plasticisers are used in most systems which dry by solvent evaporation, such as gravure and flexography. Plasticisers must be compatible with the resin used, and be present at such a loading to provide flexibility and gloss to the product without impairing application. Nitrocellulose resins are commonly plasticised, and examples of the plasticisers that are used include: phthalates, adipates, phosphates and some vegetable oils.

2.3.3 Driers Driers are metal soaps which have been traditionally used to catalyse the air oxidation drying of vegetable oils as in alkyd cures. These are typically the naphthenate, octoate or linoleate salts of cobalt, lead and manganese, sometimes with calcium, zinc or barium salts for auxiliary action. The primary drier action is the catalysis of hydroperoxide breakdown, e.g.: ROOH + Co2+ → RO· + OH− + Co3+

•

Package-forming and filling processes

•

End user specifications

•

Compliance to health, safety and consumer protection regulations

•

Compliance with environmental policies for printing, manufacturing processes and end use.

2.3.4 Photoinitiators

Some of the more important constituents of these inks are described in the next sections.

Photoinitiation is the photoproduction of free radicals or ions capable of initiating a chain reaction such

16

ROOH + Co3+ → ROO· + H+ + Co2+ Secondary drier action is less clear, but may well involve the formation of ionic crosslinks with any acid groups present in the oil.

Coatings and Inks for Food Contact Materials

as polymerisation. A photoinitiator is therefore an ingredient which is capable of generating free radicals or ions (usually cations) on the absorption of light (usually UV light).

•

Photosensitisers Anthraquinones Benzophenones Camphorquinones

Cationic photoinitiators are effective for ring-opening polymerisations – as for example with epoxies. Commercial cationic photoinitiators are the socalled ‘onium’ salts, i.e., diaryliodonium, Ar2I+, and triarylsulfonium, Ar3S+. Common counter ions include: tetrafluoroborate, BF4− and hexafluorophosphate, PF6−.

Thioxanthones

2.3.5 Colorants Colorants fall into two main classes: dyes and pigments.

Cationic photoinitiators are a relatively new development. The more traditional free radical initiators are more widely used and generally enable faster curing. Free radical initiators are used with unsaturated monomers, most commonly acrylic. Photoinitiators for radical polymerisation fall into two types: molecules, which are capable of photodissociation and those, termed ‘photosensitisers’, which generate radicals by an intermolecular reaction. The mechanism of photodissociation can be illustrated with respect to the breakdown of benzoin ethers. Absorption of a UV photon generates an excited state, which can dissipate the excess energy by homolytic bond cleavage: Ph−C(=O*)−CH(OR)−Ph → Ph−C(=O)· + CH(OR)−Ph Carbonyl-containing species which have no easily available route to photodissociation can still function as photoinitiators by the process of photosensitisation. The mechanistic steps for photosensitisation are less well understood than the examples given previously, but are thought to require a co-agent for radical formation. In the case of benzophenone, a hydrogen abstraction reaction by the excited molecule can lead to radical formation: RH + *O=CPh2 → R· + C(OH)Ph2

Some examples of photoinitators are: •

Initiators by photodissociation Acylphosphine oxides and bis-acylphosphine oxides α-Alkyloxyacetophenones α-Aminoalkylphenones α-Hydroxyalkylphenones Benzoin ethers Benzyl ketals Halogenated acetophenones

Dyes are coloured substances used for coloration of substrates by processes such as physical adsorption, complex formation or, in some cases, covalent bond formation. Dyes are always soluble in their carriers, and cover a wider colour range than any other colorant class. However, as soluble species (i.e., they operate at the molecular dimension), they are transparent and lack the covering power of pigments. Dyes have speciality roles in printing. For example, they are used in inkjet printing, in ‘lakes’ for printing ink pigments and as toners to improve the colour rendering of pigments. Azo dyes form the largest and most versatile class of dyes. So-called ‘direct dyes’ (i.e., water-soluble dyes) which attach to substrates by hydrogen-bonding directly from solution are commonly used in inkjet dyes where the substrate is cellulose-based, e.g., paper. Common thermoplastic packaging films (e.g., polyolefins) do not provide a fast surface for these dyes. Pigments are coloured, colourless or fluorescent particulate solids – usually insoluble in, and unaffected by, the medium (‘vehicle’) in which they are dispersed. Transparent pigments are used for ‘process colours’ i.e., colours developed in combination (e.g., cyan + yellow → green). Pigments may be organic or inorganic. The most important class of organic pigments are the azo types. Others include metal complexes (e.g., copper phthalycyanine) and higher polycyclic compounds (e.g., anthroquinone, quinacridone, isoindolinone and perylene). As pigments are dispersed, and not dissolved, they impart stronger colours than dyes, giving better coverage. Hence, it is pigments rather than dyes that are most commonly encountered as colorants in inks. However, dyes can also be converted into a dispersed form by coating them on translucent particles (e.g., alumina). These are ‘lakes’ and this process extends the range of colours available as pigments.

17

Coatings and Inks for Food Contact Materials

Azo dyes and pigments Azo compounds form the most important class of dyes and pigments. They are obtained by ‘coupling’ reactions between diazonium salts and a range of species such as phenols, arylamines, arylsulfonate salts. This versatility enables a wide spectrum of colours to be manufactured. Members of the naphthalene series couple more readily than single ring compounds, and commercial azo dyes are often multi-ring molecules. An alternative route to azo compounds is by the oxidative coupling of hydrazones. By these two routes, a huge variety of azo compounds can be produced, including types with one (‘monoazo’), two (‘disazo’) three (‘trisazo’) or more (‘polyazo’) azo groups. For example, most of the orange and yellow pigments are disazo types based on substituted benzidines. When each of the coupling components are based on naphthyl or biphenyl derivatives, the resulting disazo, trisazo or polyazo molecules may contain six or more aromatic rings. These large molecules have reduced mobility within the matrix which, in turn, reduces their migration potential.

Phthalocyanines Metal free phthalocyanine [(C 6H 4C 2N) 4N 4], is a macrocyclic compound made up of four isoindoleclass units linked by four nitrogen atoms to form a conjugated chain. It is made by heating phthalonitrile (1,2-dicyanobenzene), [C6H4(CN)2], in the presence of bases at 180-200 ºC. Phthalocyanine pigments contain metals, such as copper, cobalt, nickel and iron, and provide a wide range of colours through functionalisation of the phthalocyanine ligand itself. Thus, whilst copper phthalocyanine is blue, chlorinated copper phthalocyanine and sulfonated copper phthaliocyanine provide two different shades of green. Copper phthalocyanine may be obtained by heating phthalonitrile and a copper salt in a suitable reaction medium, or by using a phthalic anhydride urea combination in place of phthalonitrile. Phthalocyanines are stable to atmospheric oxidation at temperatures up to 100 ºC, or higher, depending on the metal present, but phthalimide is a possible breakdown product if oxidation occurs.

setoff and sheet sticking), thickeners (e.g., cornstarch), anti-skinning agents (to prevent premature drying on rollers – could be an antioxidant). Monomers (e.g., acrylic) are additives in reactive systems.

3 Coatings and Inks used in the Food Chain The food chain is becoming increasingly complex, with an increasing choice for the consumer due to the proliferation of pre-prepared foods, rapid movement of packaged goods by road, and the increasing competitiveness of the global market. There is a net flow of materials along the food chain from the farmers and growers, through the manufacturers and processors, to the major supermarkets and food service outlets, e.g., caterers. This section highlights some distinct areas in the food production chain, and the types of coatings and inks that are used in those areas. Packaging has been given the most attention as it is the most important area due to a number of factors. It is the area in which the greatest number and range of coating and ink products are used in, and it also represents the highest potential for migration to occur as the contact times and areas (per unit of food) are the usually the greatest.

3.1 Food Packaging 3.1.1 Packaging Types It is convenient to divide the packaging that is used for food into three generic categories: a) Metals Coatings and inks can be used in the following sectors of metal packaging: • Beverage cans and ends • Food cans and ends • Caps and closures

2.3.6 Other Additives

• General line (standard, non-specific manufacturing line) used for dry food products

Other additives that are used in inks include: surfactants, antioxidants, defoamers, biocides, waxes (to prevent

• Aerosols and collapsible tubes used for food products

18

Coatings and Inks for Food Contact Materials

b) Flexibles (i.e., plastic) Coatings, adhesives, primers, varnishes and heat seals are used in multi-constructions of plastic films and foils c) Paper and Board Coatings, adhesives, primers, varnishes and heat seals are all used in this sector.

4) Tables 13

Inks for Paper and Board Packaging

5) Tables 14

Inks for Flexible Packaging

*Adhesive layers, such as the ‘tie layers’ in laminates, can be regarded as a coating and so this type of product has been included here. The information in these Tables is complemented by the discussion in Sections 3.1.2 to 3.1.7.

Some approximate data on the size of the market for these types of products is given in Tables 3 and 4. It is useful to try and illustrate the relative importance of the different polymer types used in the production of metal, flexible and paper and board packaging. This has been attempted in Tables 5 to 14 [a.2]. In these tables, the polymer types have been given a rating from 0 to 10. This denotes the relative importance of the polymers, with the least important being given a rating of 0 and the most important a rating of 10. These Tables can be broken down as follows: 1) Tables 5 to 9 Coatings used in Metal Packaging 2) Tables 10 and 11 Coatings and Adhesives* used in Flexible Packaging 3) Tables 12

Inks for Metal Packaging

Table 3. Current size of the UK and European Markets for Metal Packaging European Market (Billions of cans) 40 29

3.1.2 Coatings Used in Metal Packaging (Tables 5 to 9) Beverage Body and End Stock Externals (Coatings Used in Cconjunction With Inks) The UK market for alcoholic drinks is dominated by metal packaging whereas the soft drink market mainly uses polyethylene terephthalate (PET) bottles. Glass is only a small market for each (< 10 %). Body stock in the UK consists mainly of aluminium construction with a small proportion made from tinplate and this has an impact on the coatings and inks chosen. The preferred combination on aluminium can stock is polyester-based inks (see Table 12) with a water-based over varnish based on polyester or a polyester/acrylic technology. In Europe, countries with a strong steel industry tend to produce more beverage bodies from tinplate. The coating situation with tinplate is quite different to aluminium. Generally, a water-based, white basecoat, based on a polyester/acrylic combination, acts as an excellent base for inks requiring no over varnish. Known as ‘Novar’ inks in the trade they contain higher levels of lubricants to provide necessary slip and abrasion resistance through the filling lines and track work.

30

Table 5 shows the strong use of water dispersible polymers in varnishes and pigmented coatings, e.g., acrylic, polyester and epoxy.

5.5 7

Table 4. Current Size of the UK Non-metal Packaging Market Inks (Te)

Coatings/Sealants/ Varnishes (Te)

Adhesives (Te)

Flexible Packaging

7200

1500

5000

Paper/Board

2000

4000

4000

Food Labels

500

1000

1500

19

Coatings and Inks for Food Contact Materials

Table 5. Polymers Used in Metal Packaging - Beverage Bodies and Easy Open Ends Polymer Type

Relative Importance End Use (1-10)

Alkyds

0-1

Acrylics

Comments

None to very little

Polyesters preferred

7

Ends and bodies

Very common base resin for w/b coatings and varnishes

Polyesters

10

Ends and bodies

Higher quality base resin than acrylics for coatings/varnishes

Epoxies

9

Ends and bodies

Significant use as base resin for w/b externals of ends

Urethanes

1

None to very little

Food contact issue even for externals

Vinyl polymers

2

End stock

Chlorine containing vinyl resins being withdrawn

Phenolics

2

Ends and bodies

Crosslinking or colouring resin

Amino

4

Ends and bodies

Principal crosslinking resin for epoxy resin for clear/ coloured coatings

Acrylates

1

Base of bodies

Small interest for acrylate UV cured rim varnish

Cellulose

<1

None to very little

Maybe only as an additive

Hydrocarbon

0

Others

1

Maybe only as lubricant Lubricants

Small volumes of lubricants and additives are used including PE, PTFE, Carnauba wax and lanolin

w/b = water based

Can end stock is made of aluminium and the externals are primarily solvent-based epoxy amino technology. A very small percentage of ends will be decorated for promotional reasons. The vast majority of beverage ends use clear, gold or coloured external coatings. The coatings are applied using high speed coil application. The UK market primarily produces three piece welded food cans (80%) with approximately 20% produced using the drawn and wall ironed (DWI) process. A major proportion of three piece welded bodies are left uncoated on the exterior; no external decoration being needed as paper labels are used. However, the steel ends will always be coated with an epoxy-based material. Many of the easy open ends will be printed with opening instructions and others may be printed for promotional reasons. Water based epoxy wash coat dominates the external protection of DWI bodies; again no inks are used as paper labels are preferred. A small number of drawn steel ‘pie cans’ are produced in the UK which will receive an external combination of white basecoat, inks and varnishes.

20

More flexible coatings are used on both aluminium and steel draw redraw (DRD) cans to aid in the forming process. In addition, the Europeans still tend to decorate their cans with basecoats/inks and varnishes. In Europe the emphasis is more on quality and therefore direct printing of cans and ends is preferred rather than using paper labels. Table 6 shows the use of various other resins for these cans. The inks used on these products will follow the polymer combinations shown in Table 12. Generally, conventional inks are used on food cans and ends which are based on polyester technology. This market is quite diverse and there are many different types of caps and closures produced. The most prevalent type of closure is the steel vacuum closure which is used on glass jars for baby food, jams and pastes, etc. Various constructions are included such as Regular twist off (RTO) and Press Twist (PT) etc., on processed food glass jars. These external fittings use mainly use polyester or epoxy base coats in combination with inks and varnishes. Caps that are used on alcoholic glass bottles are of the aluminium Roll on Pilfer Proof (ROPP) construction. They require very flexible basecoats, inks and varnishes to withstand the extreme forming process. Typical choices will be based on polyester-polyurethane technology.

Coatings and Inks for Food Contact Materials

Table 6. Polymers used in Metal Packaging - External Food bodies and ends including welded three piece/Drawn/DRD and DWI cans and ends Polymer Type

Relative Importance End Use (1-10)

Comments

Alkyds

1

Very little

Being replaced by polyesters

Acrylics

2

Overprint varnishes

Provides good clear glossy finish

Polyesters

3

Ends

Growing use crosslinked with amino, phenolic and isocyanate

Epoxies

10

All sectors

Main base resin for ends(standard and EOE) and DWI washcoat

Urethanes

3

ROPP and other caps

Flexible and tough technology

Vinyl polymers

2

Diminishing use

Were used on DRD cans-replaced by polyesters and epoxies

Phenolics

6

All sectors

Important crosslinker for gold coatings

Amino

4

All sectors

Crosslinker for clear and white coatings/ varnishes

Acrylates

1

Three piece bodies

Basis for UV curable varnishes and also flow agents

Cellulose

<1

Small

Maybe as an additive

Hydrocarbon

<1

Small

Maybe as an additive

Cycloaliphatics

1

Three piece bodies

Base resin for cationic UV curable varnishes

PTFE/PE

<1

All sectors

Lubricants used to aid post forming

Carnauba

<1

All sectors

Lubricants used to aid post forming

Others :

EOE: Easy open end

Crown corks are still used on premium beer and beverage glass bottles and again use combinations of polyester basecoats, inks and varnishes based on polyester or epoxy ester technologies. Only a small proportion of general line cans produced in the UK are used for food products, with the vast proportion of general line cans being used for paints, wood varnishes and other non-food consumer products. The main food packaging use for general line cans is for decorated confectionary boxes, decorated boxes or cylinders for premium bottles of spirits, or for baby food powders. In the UK, in the last few years, there has been a considerable move away from thermally cured coatings and inks for these products to using both UV curable inks and varnishes. This is inspired by volatile organic compounds (VOC) regulations, quality and economics. The coloured basecoats, however, are normally solvent-based and produced from a range of resins, but mainly polyesters.

For the varnishes, UV technology is either free radical based (acrylate-based) or the higher performance cationic technology based on cycloaliphatic resins. The vast majority of aerosols produced in the UK are of welded tinplate construction. A small proportion of the total are produced using the Monobloc aluminium process. Both types of construction use direct print onto a base coated body which is subsequently varnished, with the mono bloc aluminium aerosols mainly using conventional solvent borne basecoats, and conventional inks and varnishes based on flexible polyester technology. The main three piece tinplate producers are now moving to UV curable inks and varnishes. Again, solvent basepolyester or epoxy resins are used for the basecoats. Aluminium collapsible tubes are included in this table, although as none are manufactured in the UK, the

21

Coatings and Inks for Food Contact Materials

Table 7. Polymers Used in Metal Packaging - Caps Closures to Include Vacuum Closures/RTO/ ROPP/PT/Crowns etc. Polymer Type

Relative Importance (1-10)

Vacuum Closures (incl: RTO/ PT/Lug type/)

Roll on Pilfer Proof

Crown Corks

Comments

Alkyds

1

Yes

Yes

Combined with vinyl to give good flexibility-being replaced by better polyester technology

Acrylics

1

Yes

Yes

Far greater use in Europe

Polyesters

10

Yes

Yes

Main resin type preferred for flexibility and good heat resistance and colour retention

Yes

Base of traditional epoxy ester technology being replaced by polyester base limited flexibility

Yes

Ideal for the more extreme draw of ROPP but used for all

Yes

Epoxies

4

Yes

Urethanes

6

Yes

Vinyl polymers

2

Yes

Yes

Combined with alkyd technology, but now being replaced

Phenolics

2

Yes

Yes

Crosslinker for gold epoxy -based clear externals

Amino

6

Yes

Crosslinker for polyester technology

Acrylates

1

Cellulose

0

Hydrocarbon

0

Yes

Yes

Yes

Possible

Base for UV technology with limited draw. Proven for RTO products

Base for cationic varnishes

Others: Cycloaliphatic

1

Yes

No

Possible

PTFE/PE

<1

Yes

Yes

Yes

relatively small number used for pharmaceuticals and food pastes are imported mainly from Europe. This type of packaging has been mainly replaced by rigid plastic polyethylene (PE) tubes.

Lubricants, used in small quantities

a) General purpose b) Medium performance c) High performance Examples of each of these three are described in the next sections:

3.1.3 Coatings and Adhesives for Flexible Packaging (Tables 10 and 11) The types of flexible packaging in the market can be broken down as follows (a.3):

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General Purpose This type of packaging is typically used for products such as snacks and crisps. In addition to the metalised inner

Coatings and Inks for Food Contact Materials

Table 8. Polymers used in Metal Packaging - General Line (Including, Packaging for Dry Foods, e.g. Baby Food, Coffee and Confectionery) Relative Importance (1-10)

End Use

Comments

Alkyds

1

Size coat

Sizeless systems now preferred

Acrylics

5

Base for white coatings and varnishes

Good heat resistance and appearance

Polyesters

10

Base for white coatings and varnishes

Excellent combination of properties and crosslinked with amino or urethanes

Epoxies

2

Traditional base for epoxy ester varnishes

Epoxy esters prone to yellowing

Urethanes

4

Superior technology

Combination with polyester

Vinyl polymers

1

Historical base for size/white and varnish

Vinylalkyds being replaced by polyesters or acrylics

Phenolics

1

Used as crosslinker in clear golds

Combination with epoxy

Amino

4

Clear transparent or white basecoat

Combination with polyester

Acrylates

5

Basis for UV free radical varnishes

UV technology replacing thermal technology in UK

Cellulose

0

Hydrocarbon

0

Basis for cationic UV varnishes

More flexible cationic technology is more versatile than free radical. Replacement of conventional set to continue

Polymer Type

Others:

Cycloaliphatic

4

plastic layer (~18 μm thick) and outer plastic layer (again ~18 μm thick), there will be a 2 μm adhesive layer and a 5 μm print layer. The presence of the metallised layer provides a degree of oxygen, moisture and light barrier.

Medium Performance This type of flexible packaging is typically used for products such as bacon, cheese and boil in the bag foods. It often has an outer layer of Nylon (~20 μm thick), a 4 μm print layer, a 2-3 μm adhesive layer and then a 30 μm polyethylene layer. In common with the general purpose packaging, it has some barrier properties to oxygen, is puncture resistant, thermoformable and can withstand up to 100 °C for 60 minutes.

High Performance These are typically referred to as ‘retort packs’ and they have the most complicated construction, which imparts a total barrier, puncture resistance, high heat resistance

(e.g., 130 °C for 30 minutes), some thermoforming capability and chemical resistance to the product inside. A typical six layer construction would be: Polyester outer

18 mm

Print layer

5 mm

Adhesive layer

3-4 mm

Aluminium foil

20 mm

Adhesive layer

4-5 mm

Cast polypropylene (PP)

30 mm

The information in Table 10 takes into account the great potential for food manufacturers to import reels of the relatively light weight laminated constructions from mainland Europe. In this market there is a 45/50/5 split in the use of solvent-free/solvent-based and water-based adhesive technologies. It is expected with VOC emission regulations becoming more stringent the solvent-free option will grow. For the vast majority of final uses, polyurethane technology is the resin of choice for both solvent-based and

23

Coatings and Inks for Food Contact Materials

Table 9. Polymers Used in Metal Packaging - Collapsible Tubes, Three Piece Steel and Aluminium Monobloc Aerosols Polymer Type

Relative Importance (1-10)

Collapsible Tubes

Three Piece Aerosols

Monobloc Aerosols

Comments

Alkyds

<1

Yes

Acrylics

4

Yes

Yes

Lower cost option to polyesters

Polyesters

10

Yes

Yes

Dominates the external size/ white and clear basecoats and overprint varnishes

Epoxies

3

Yes

yes

Used more on three piece aerosols than monoblocs

Urethanes

6

Yes

Yes

Isocyanate capped PU used extensively with polyesters

Vinyl polymers

0-1

Possible

Phenolics

2

Yes

Crosslinker/tinter for epoxybased gold coatings

Amino

5

Yes

Clear crosslinker alternative to polyurethane

Acrylates

1

Yes

Base for UV curable varnishes

Cellulose

0

Hydrocarbon

0

Yes

Yes

Mainly replaced by polyesters

Could be still used on cones and domes

Others: Cycloaliphatic

2

PTFE/PE

<1

Carnauba

<1

Yes

Possible

Base for the more flexible and better adhering UV technology for varnishes

Yes

Yes

yes

Small volume used as internal lubricants

Yes

Yes

yes

Small volume used as internal lubricants

solvent-free adhesives. The polyurethane backbone may use polyester or polyether chemistry depending on the quality needed. Water-based adhesives tend to use a combination of dispersible acrylic and epoxy technology crosslinked with amine resins. The multi-layer construction of flexible packaging always means that there are combinations of adhesives and coatings with printing inks. Table 14 covers printing ink polymers and additives. This area is complex, which makes analysis difficult and it is a lot smaller in volume terms compared to coatings. Table 11 shows that there is a vast split in types of resin technology used, with some of the

24

significant resins which tend to dominate this sector e.g., polyamides and natural rubbers in cold seals, being highlighted. Ethylene vinyl acetate products are used in heat sealable lids.

3.1.4 Inks for Metal Packaging (Table 12) The bulk of metal decorating inks are applied using lithography and rely on ‘paste type inks’. There are four main sectors covered by Table 12: beverage, food cans and ends, caps and closures, and general line and aerosols. A brief discussion of each of these is presented next.

Coatings and Inks for Food Contact Materials

Table 10. Polymers Used in Flexible Packaging - Adhesives Used for Laminating Plastic Films/Foil/ Paper and Metallised Polymer Type

Relative Importance (1-10)

SolventBased

Alkyds

0

Acrylics

2

Polyesters

7

Yes

Epoxies

2

Yes

Urethanes

10

Vinyl polymers

0

Phenolics

0

Amino

0

Acrylates

1

Cellulose

0

Hydrocarbon

0

SolventFree

WaterBased

UV or EB Comments Cure

Acrylic functionality aids water dispersability

Yes

Yes

Used as backbone for high performance adhesives or curatives

Yes

Yes

Yes

Used in conjunction with amine curatives

Yes

Polyether or polyester urethane technology is the most widely used adhesive technology in the UK and Europe

Yes

Could be background resin for UV or EB technology

Others : Amine

2

Yes

Yes

Used in conjunction with an epoxy

Polyether/ polyol

6

Yes

Yes

Yes

Can either be used as part of the PE/PU backbone in the adhesive part or as a curative in its own right with an isocyanate capped PU

Silane/silanol

4

Yes

Yes

Yes

Used as an adhesion promoter in the curative

Amide

1

Yes

Yes

Yes

Beverage Cans The marketing of all aluminium and tinplate beverage cans relies heavily on a high quality image on the exterior of the thin walled cans. This is the biggest sector for metal decoration and the application is carried out at high speed, ‘in the round.’ Many combinations of basecoats, inks and over print varnishes are used to provide the right image for a particular product.

Yes

Erucamide or oleamide-based lubricants used to adjust bond strengths

The ink technology that is used is based on polyester resins cured with amino crosslinkers. Pigmentation can represent 30% of the formulations, small amounts of diluents (e.g., tridecanol) are used to improve the flow, and lubricants based on PTFE are frequently used to provide the slip to enable post-necking operations to be achieved. For all the other metal decorating sectors, sheets are printed flat and then post formed.

25

Coatings and Inks for Food Contact Materials

Table 11. Polymers Used in Flexible Packaging - Primers/Heat Seals and Varnishes Relative Importance (1-10)

End Use

Comments

Alkyds

2

Varnishes

In conjunction with amino resins for heat resistance

Acrylics

5

Lidding heat seals

Can be applied as waterbased in conjunction with vinyls e.g., yoghurt pots

Polyesters

3

Heat seals

Good performance

Epoxies

2

Sterilisable trays/coloured cartons

Can be used with phenolics and thermoplastic dispersion e.g., PP base for coloured coatings for drawable trays

Urethanes

4

Varnishes

High chemical and heat resistance

Vinyl polymers

6

Lidding heat seals or barrier cartons

Traditional polymer base for heat sealspolyvinylidere chloride major barrier coating

Phenolics

2

Sterilisable trays

Crosslinker for epoxy based coatings and/ or heat seals

Amino

2

Varnishes

Used in conjunction with alkyd and polyester resins

Acrylates

2

Varnishes

Low heat resistance

Cellulose

3

Varnishes

Nitro cellulose, low cost and low temperature drying

Hydrocarbon

0

Polymer Type

Others: Polyamide

5

Cold seals

Release additive

Ethylene vinyl acetate

5

Heat seals/lidding

Water-based EVA replacing high VOC solvent based systems

Maleinised PP

3

Sterilisable trays

Used as thermoplastic dispersion with thermoset epoxy phenolic

Polyethylene -imine

1

Primer for extrusion lamination

Improves adhesion for direct extrusion lamination

Natural rubber

5

Cold seals

Provides cohesive strength

Stearates/soaps

1

Anti-mist Coatings

Absorbs water and allows clear view of products packed

EVA: Ethylene vinyl acetate

Food Cans and Ends Few tinplate food cans are decorated in the UK. Some ends are decorated prior to forming. The few can components that are printed tend to use conventional polyester inks without crosslinkers. In Europe, the emphasis is more on quality and here many cans and ends are printed. It is also the case that the smaller portions packed in drawn cans are distortion

26

printed to provide an accurate and high quality brand image after post-forming.

Caps and Closures The caps and closure markets rely on a printed image on these components to provide differentiation for products packed in glass bottles or jars. Conventional inks are used although there is a growing interest in the use of flexible UV curable technology.

Coatings and Inks for Food Contact Materials

Table 12. Polymers Used in Inks for Metal Packaging Polymer Type

Relative Importance (1-10)

Rosin esters

0

Hydrocarbon Resins

0-1

End Use

Comments

Diluent

Only as a minor diluent, e.g., tridecanol or 260-290 °C hydrocarbon distillate

Phenolics

0

Cellulose resins

0

Acrylic

0

Vinyl resins

0

Polyamide

0

Polyurethane

0

Amino

2

Beverage externals

Used to crosslink polyesters

Alkyds

3

All metal packaging sectors

Conventional ink systems not requiring crosslinking

Ketone resins

0

Polyester

10

1. Beverage external decoration 2. General line/aerosols

1. Crosslinked with amino 2. Used for polyester acrylate in UV

Epoxy

4

All metal packaging sectors

Used for epoxy acrylate in UV.

UV/EB curable polymers

7

All metal packaging sectors

Free radical UV technology based on mainly epoxy acrylate with some polyester acrylate

PV

0

Silicone/silicate

0

PTFE

1

Lubricant

Provides necessary slip to the surfaces

Titanates/chelates/ maleic resins

0

General Line and Aerosols For these sectors there has been a recent move away from conventional ink technology, relying on thermal drying of alkyd technology, to UV curable technology. UV curable inks are now applied to base coated tinplate which is subsequently formed into welded aerosols, milk cans, confectionery tins, and other components. UV curing technology for flat sheet metal decorating (FSMD) inks use a combination of polyester and epoxy acrylate technologies photo crosslinked using free radical initiators. Cationic UV technology for inks is not used because of the difficulties in achieving a correct ink-water balance.

3.1.5 Inks for Paper and Board Packaging (Table 13) As with FSMD, UV technology is being used in 80% of the cases for paper and board secondary food packaging. This technology is generally based on free radical curing resins e.g., polyester or epoxy acrylates. UV curable varnishes are widely used on food cartons and labels. The conventional inks used in this sector are based on alkyd technology modified with hydrocarbon resins with minor modifications made with lubricants based on PTFE and polyethylene waxes.

27

Coatings and Inks for Food Contact Materials

Table 13. Polymers Used in Inks for Paper and Board Polymer Type

Relative Importance (1-10)

End Use

Comments

Diluent

Only as a minor diluent in conventional inks

Conventional inks

20% of the food paper/board market

Rosin esters

0

Hydrocarbon resins

1

Phenolics

0

Cellulose resins

0

Acrylic

0

Vinyl resins

0

Polyamide

0

Polyurethane

0

Amino

0

Alkyds

4

Ketone resins

0

Polyester

5

Resin used in conjunction with acrylate for UV

Epoxy

5

Resin used in conjunction with acrylate for UV

UV/EB curable polymers

10

Mainly UV 80% of market Some EB at Tetrapack Combination of polyester and epoxy acrylates

PVB

0

Silicone/silicate

0

PTFE/PE Titanates/chelates maleic resins

0-1

Lubricant

0

3.1.6 Inks for Flexible Packaging (Table 14) The fastest growing packaging market today uses high quality images produced by reverse printing the exterior clear plastic film layers of flexible packaging constructions. Inks are normally applied using flexographic or gravure high speed printers. The most widely used resins for these inks are based on a combination of nitrocellulose and polyurethane resins dissolved in fast (i.e., volatile) solvents such as ethyl acetate or isopropyl alcohol. In the UK and Europe, the industry prefers to use low viscosity solvent-based inks, while in the USA water-based acrylic technology is preferred from an environmental and solvent emissions point of view. Nitrocellulose resins are used to provide excellent dispersion of the pigments in inks. Thermoplastic polyurethanes and other resins are used to plasticise and improve the adhesion characteristics of the formulated inks.

28

Other resins such as polyamides and polyvinyl butyrals (PVB) have limitations. Polyamides, although providing superior gloss and adhesion properties, are not as effective in heat sealing conditions and suffer from bad odour. PVB are generally used by confectioners as they have low odour characteristics, but only offer below average print flow and heat seal characteristics. The use of nitrocellulose resins is a safety concern and ink suppliers are trying to replace these by introducing new film forming technology based on high mw polyurethane resins. This approach is seen to be the future as it offers lower migratory technology.

3.2 Harvesting and Processing of Food The process of harvesting food can bring it into contact with coating products. Some examples are:

Coatings and Inks for Food Contact Materials

Fruit and Vegetables Picking and transportation to the processing plant. Meat

Slaughtering and preparation ahead of processing.

Fish

Netting and processing on board. Exposure to painted/ varnished surfaces.

Cereals

Poultry

Coatings on harvesting equipment, milling and storage in bags. Slaughtering, cleaning and preparation for packaging or selling.

Foods are also processed in a wide variety of ways, e.g., sterilisation, drying, chemical preservation, curing and fermenting. Although stainless steel is often the material of choice for the majority of the food contact surfaces in food processing halls, it is possible for food products to, potentially, encounter other coatings, for example: i)

Special acrylic-based coatings on the walls

ii) Polyester or epoxy-based powder coating products on metal substrates iii) Cold cure, two pack epoxy or polyurethane coatings on the floors iv) PTFE coated standard conveyor systems

Table 14. Polymers Used in Inks for Flexible Plastic Packaging Polymer Type

Relative Importance (1-10)

End Use

Comments

Rosin esters

0-2

Hydrocarbon resins

0

Minor use

Phenolics

0

Not of interest due to formaldehyde concern

Cellulose resins

10

Nitro cellulose is used in almost all inks applied via the flexography and gravure processes

Acrylic

2

Vinyl resins

6

Move to withdraw chlorine containing polymers

Polyamide

6

Odour issue from amine and solvents possible

Polyurethane

10

High performance ink media reducing the NC content

Amino

0

Alkyds

0

Ketone resins

1

Polyester

0

Epoxy

Minor use in gravure

Water-based only

Mainly coatings

Mainly in USA

Mainly two pack odour issue

To modify NC

0-1

Used in small quantities as an adhesion promoter

UV/EB curable polymers

2

Acrylated PU can be used for UV curable systems

PVB

5

Silicone/silicate Titanates/chelates/ maleic resins

Preferred base resin system for confectionary/cold seal

0-1 5

Not suitable for heat sealable end uses Waxes

Adhesion promoters

Essential additives for inks

NC: Nitrocellulose

29

Coatings and Inks for Food Contact Materials

Table 15. Places in the Food Chain Where Contamination Has Taken Place Place of Contamination

Percentage (%)*

Unknown

27.4

Known (listed below)

72.6

Catering

2.3

Food processing plant

5.4

Kitchen in private homes

6.9

Farm

15.7

Restaurants

38.8

Other

30.9

*Sample size: 7,115 **Including hotels, cafes, public houses and bars, and schools

In addition to these, silicone-based coatings have an important role to play, as their versatility means that materials can be manufactured (i.e., epoxy-silanes, silanes, siloxanes, silicones) that can be used to produce hygienic coatings on a variety of substrates such as walls, general surfaces and pipe work. Use of low temperature, UV curing technology can also mean that such coatings can be used on heat sensitive substrates, such as thermoplastics. (a.4). The performance of these, and other coatings, can be enhanced if quaternary ammonium end groups are present on low mw silicone-based additives, as these confer antimicrobial properties. This type of development in coating technology is important as improvements to hygiene in food processing plants has become an important topic in recent years (203). Data published in 2002 by the FAO/WHO Collaborating Centre for Research and Training in Food Hygiene and Zoonoses (a.5) illustrated the most important places where the food involved in outbreaks became contaminated. This information is summarised below in Table 15. Other data in the report includes an assessment of 18,351 foodborne disease outbreaks, of which a contributing factor could be found for 13,310, and 14% of these were thought to relate to improper hygienic conditions that allow contamination during processing. Contaminated surfaces will have contributed to this category.

to protect more reactive/interactive substrates (e.g., steel and aluminium). For example, the types of speciality coatings that can be used in this type of application include epoxy-phenolic with a glass flake additive, and sprayable elastomeric polysulfide systems. In addition, elastomeric polysulfide sealants, epoxy polyamide holding primers and epoxy grouts can also be used. These types of coatings and coating related products can also be used in other areas of the food and beverage industries. When food products, such as potable water have to be stored in open topped containers (e.g., in small reservoirs, storage tanks and silos) it is necessary to have an appropriate membrane over the top in order to keep harmful and contaminating agencies out. It is possible to produce such membranes using two–component epoxypolysulphide liquid coating systems that have Water Regulations Advisory Scheme (WRAS) approval for potable water (a.6). These coatings can also be used on a fabric carrier in order to produce a bund type liner. Food sacks or empty cans are transported on pallets which may be painted or varnished. This gives rise to the possibility that the empty cans could be contaminated by traces of the odourous components used in these coatings. The switch to pallets made from thermoplastic materials eliminates this possibility. Liquids such as milk are often transported in stainless steel tankers and so no contact with any coatings occurs. However, beer and lager are transported in coated aluminium casks, with this coating usually being spray applied and epoxy/phenolic based. Within the home, the use of refrigerators to store food is the norm, and there can be problems due to the build up of cold tolerant bacteria such as Listeria spp or Salmonella spp. It is now possible to treat the surface of a refrigerator with a coating containing a silver glass ceramic antimicrobial additive that has been shown in tests to significantly reduce the build up of Listeria (155).

3.4 Presentation, Dispensing and Cooking Packaged products may be exposed to shelving that is polyester or epoxy coated. However, this can be more of an issue with fresh and chilled foods where there is less of a barrier between the food and these coatings.

3.3 Storage and Transportation Where food needs to be stored in bulk containers, these can be stainless steel, but it is also possible to use coatings

30

As with the food processing halls and transportation, the coatings that are used are of the chemical and heat resistant variety to enable fast and efficient cleaning.

Coatings and Inks for Food Contact Materials

Drinks sold in cans are inherently protected from external contamination by the packaging. However, the possibility of contamination of can exteriors from the cleaning chemicals used to clean the surfaces of the vending machine needs to be considered and guarded against.

The over-print varnish (usually un-pigmented) may be of the same form as the ink, if the application area requires the definition achieved by lithography or may be of the lithographic type (see next) if the application is by a simple roller.

The use of silicone-based resins to impart non-stick surfaces to cooking equipment such as baking trays, cake tins and loaf tins, and frying pans is increasing, with this technology often replacing PTFE based coatings. These products are being marketed for both use in the domestic environment as well as commercial kitchens. These types of products were included in the recent FSA project undertaken by Rapra (a.1)

The use of low volatility solvents inhibits drying and so a post-printing heating step is often used. When used with heat-resistant substrates, this heat step can also be used to ensure that the ink is fully cured. On more heat-sensitive surfaces, e.g., paper, absorption of the solvent plays a part in the drying process. In the case of UV-curing inks, more than one irradiation step may be used in the printing stage – for example, immediately after the application of a colour where there is risk of smudging when the next colour is applied.

4. Application Techniques for Inks

UV-curing ink formulations for lithography may utilise only low levels of acrylic monomers and rely on multifunctional acrylic polymers to provide the necessary consistency and cure activity.

4.1 Lithography Lithography is one of the oldest printing techniques. It utilises a flat plate or smooth roller which is treated to accept ink in a selective way. The surface most commonly used is metal, mainly aluminium, although it is possible to use other materials such as ceramics. The surface is treated to provide different degrees of hydrophilicity/hydrophobicity to define the required image. In one form of the process, the plate is then treated with an aqueous solution prior to inking with a solvent-based formulation. In another form, the non-image areas are treated with a silicone-based product before inking (this is referred to as ‘waterless lithography’). When the ink is transferred to the substrate for printing via a roller (or train of rollers), the process is called ‘offset lithography’. Conventional lithography has sequential treatments of aqueous and different coloured ink solutions (and possibly a varnish to complete), and successful ink formulations must be resistant to emulsification (which would result in ink bleed to the non-image areas). Lithographic inks are usually of higher viscosity than for other processes and quite commonly are in a paste form. Traditional paste inks are oil-based and use oxidative curing. Shear plays a part in the ink-transfer process and the solvents in litho inks must be less volatile than in other inks to avoid drying on the rollers. Typical solvents in oil-based litho inks are petroleum distillates in the boiling range 260-320 ºC or, more recently, long-chain esters derived from vegetable oils, by processes such as alcoholysis, for example.: glyceryl oleate + methanol → glycerol + methyl oleate

Lithography offers some of the finest definitions seen in printed packaging and is associated with some of the highest quality products.

4.2 Flexography Flexography is a relief printing process. A mirrored master of the required image is created in relief on a flexible polymeric printing plate. Flexography uses liquid inks - which can be solvent-based, water-based or UV-curing formulations. It is also capable of operation on a range of substrates, including rough ones such as corrugated cardboard. The type of solvent that is chosen for the ink must be compatible with the polymer used in the printing plate. For this reason, aggressive aromatic solvents are not usually acceptable, and commonly used ink formulations usually employ alcohol or ester solvents to ensure that a wide range of resins types can be used for the process. In addition, the high solvent levels in liquid inks means that their volatilisation makes a significant contribution to the drying process and ensures that there is less reliance on other drying mechanisms. This in turn means that it is possible to use a wide range of polymer binders in the flexographic inks themselves. Traditionally, flexographic printing plates were made from vulcanised rubber. The relief is created by vulcanising the rubber, under pressure, against a

31

Coatings and Inks for Food Contact Materials

suitably profiled tooling such as an etched metal mould (e.g., photoengraved magnesium). Solvent resistance is a particular issue with natural rubber, the non-polar synthetic rubbers, and silicone rubber. It is not possible to use inks based on aromatic hydrocarbons with these materials. Specialty rubbers (e.g., PU, acrylics, fluoroelastomers, and fluorosilicones) offer differing levels of solvent resistance, and liquid moulding/curing technologies (PU and silicone rubbers) provide the scope for moulding against softer tooling (e.g., photo-polymerised plastic). Newly available photopolymers now enable the direct manufacture of resilient flexographic plates without having to use moulding processes, and have given improvements in definition, for better half-tone reproduction, and so on. Innovations in the materials and technology of plate production are helping to overcome the traditional quality issues associated with compression of the relief at the point of printing, referred to as ‘ink squash’. Flexography is emerging as the dominant process for printing on flexible packaging, and is gaining increasing importance on boxes and cartons. Flexible packaging substrates (i.e., plastic films) are more complex than other substrates in that they are often multilayer to provide an appropriate balance of strength, clarity, permeability and materials’ usage. Printing on flexible film is a high speed process which requires sophisticated mechanisms for tension control. These capabilities, coupled with increasing sophisticated performance requirements mean that lamination and printing are often in-line operations. Lamination after printing, so that the printed surface is sandwiched between two layers, provides so-called ‘reverse printing’ and dispenses with the need for an overprint varnish.

4.3 Gravure Gravure is a relief printing process where the image areas are recessed on the printing plate, in contrast to flexography, where the image area stands proud. The plate is made from metal, usually made by chemicallyetching copper plated steel. The etched-copper surface is then chromium plated for improved hardness and service life. Gravure provides for high definition printing and requires low viscosity inks for penetration of the smallest recesses in the plate. The use of low molecular weight, i.e., volatile, solvents allows for rapid

32

drying by evaporation, and gravure can achieve very fast printing speeds. However, the high cost of plate manufacture means that gravure is usually restricted to long print runs. Ink formulations for gravure are selected on the basis of their flow characteristics and the substrate for printing, ensuring that no compatibility issues arise with respect to the printing plate material.

4.4 Inkjet The mechanics of inkjet printing (nozzle size, etc.) require low viscosity formulations which are mostly dye rather than pigment based. Where pigments are used, they must be exceptionally well dispersed (i.e., particle sizes of 0.5 μm or less). In order to maintain suitably low viscosities without problematic evaporation losses (blocking nozzles, etc.), waterbased inks are generally preferred. Inkjet printing is applicable to a wide range of substrates, and is widely used for printing ‘sell by’/’best before’ dates and bar codes.

4.5 Influence of Substrate Type 4.5.1 Inks for Metal Packaging Metals do not provide an absorbent surface and hence the only drying mechanisms are by the evaporation of solvent, and curing. Crosslinking technology figures in most inks and coatings for metal substrates. The bulk of metal decorating inks are applied using lithography and rely on paste type inks. For beverage containers, made of aluminium, much ink technology is based on polyester resins, cured with amino resins, with a water-based overprint varnish, based on polyester or polyester/acrylic technology. On mainland Europe, the strong steel industry leads to a higher proportion of beverage containers from tinplate. Inks and coatings for tinplate differ from those for aluminium not the least because of a need to provide higher lubricity and abrasion resistance for the harder metal. Lubricants based on PTFE may be used in inks for either tinplate, or aluminium, where useful slip properties are required. Lubricity is important for coated aluminium containers if a shaping operation (e.g., for roll-on screw tops or Monobloc aerosols – see next) is applied after decoration.

Coatings and Inks for Food Contact Materials

For food cans, tinplate predominates mostly using threepiece welded construction. A large proportion of threepiece welded bodies are left uncoated on the exterior as paper labels are used for decoration. A small number of drawn steel ‘pie cans’ are produced in the UK, which will receive an external combination of white basecoat, inks and varnishes. Direct metal decoration is also more common for food cans from mainland Europe. Conventional inks based on polyester technology are generally used. Metal caps and closures are encountered on jars and bottles and may be steel or aluminium, with aluminium universal in the ROPP screw top. The latter require very flexible basecoats to withstand the extreme forming process. Similar flexibility is required for the decoration of aluminium aerosol containers which are used for cream in the UK and other foodstuffs (e.g., ketchup) elsewhere. Aluminium aerosols are commonly made by the Monobloc route where a single aluminium slug is drawn to provide the (one-piece) base and sides of the aerosol can which is usually decorated before shaping the top (‘necking’) and profiling for the valve seat. For printing of Monobloc beverage cans, the aluminium profile is supported on a mandrel, and automated failsafe procedures are put in place to prevent the accidental contamination of the inside of the can which would occur if an empty mandrel was presented to the lithographic plate (i.e., to transfer print to the inside of the next can which arrives on the mandrel). Such accidental transfer is called ‘set off’, and additional mechanisms for this are discussed later in this section. Within the UK, a large number of aerosols (e.g., for cream) are still produced by three piece welded construction with tinplate. As with other tinplate decoration, conventional solvent-based polyesters are widely used in the inks and coatings. For caps and closures, conventional inks are used although there is a growing interest in the use of UV curable technology. The same trend applies in general line and aerosol printing where thermal drying based on alkyd technology is being replaced by UV curable technology. UV technology for FSMD inks use a combination of polyester and epoxy-acrylate technologies photocrosslinked using free radical initiators. Cationic UV technology for inks is not used because of retardation of cure due to pigment interactions.

UV curable inks are now applied to base coated tinplate, which is subsequently formed into welded aerosols, milk cans, confectionery tins, and other components. Also used for food are the so-called ‘general line cans’. These are steel cans of various shapes and sizes used for a variety of products, more typically in non-food (e.g., for paint), but these types of cans are used for the bulk packaging of foodstuffs, or where additional presentation is required. Examples include: decorated confectionary or biscuit boxes, decorated boxes or cylinders for premium bottles of spirits and baby food powders. For these products, there has been a considerable move away from thermally cured coatings to using UV inks and varnishes, mainly due to VOC (volatile organic hydrocarbon) regulations and economics. The coloured basecoats, however, are solvent based and produced from a range of resins but mainly polyesters. Polymer binders for inks that are used on metal substrates are summarised in Table 12.

4.5.2 Inks for Paper and Board Drying by absorption (i.e., penetration of the substrate) can play a part in the drying processes that occur when inks are used on paper and board. This allows for the use of more mobile (i.e., less viscous) ink formulations than with metal substrates. This can compensate somewhat for the limited scope for heat-activated curing, although many papers and boards have coated surfaces, which necessarily allow for rapid uptake. Set off may be an issue unless a speedy chemical cure can be incorporated. As with flat sheet metal decorating, UV curing is used in the majority of the cases for food packaging involving paper and board. UV technology is generally based on free radical curing resins, e.g., polyester or epoxy acrylates. UV curable varnishes are also widely used on food cartons and labels. Conventional inks are based on alkyd technology modified with hydrocarbon resins. Minor modifications are made with lubricants based on PTFE and polyethylene waxes. Polymer binders for inks used with paper and board products are summarised in Table 13.

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Coatings and Inks for Food Contact Materials

4.5.3 Inks for Flexible Plastic Packaging The substrates for plastic packaging include various laminated films, whether all-polymer, or laminates which also include foil, paper or metalised layers. Thermal or adhesive lamination may be used. PU is often the resin of choice for both solvent-based and solvent-free adhesives. The PU backbone may use polyester or polyether chemistry depending on the quality needed. Water-based adhesives tend to use a combination of dispersible acrylic and epoxy technology crosslinked with amine resins. This fast growing packaging market creates for high quality images by ‘reverse printing’ the exterior clear plastic film layers of flexible packaging constructions. Inks are normally applied using flexographic or gravure high speed printers. The most widely used resins for these inks are based on a combination of nitro-cellulose and PU resins dissolved in fast-drying solvents such as ethyl acetate or isopropanol. Nitrocellulose resins are used to provide excellent dispersion of the pigments in inks. Thermoplastics PU and other resins are used to plasticise and improve the adhesion characteristics of the formulated inks. Some limited usage applies to other resins such as polyamides and polyvinyl butyrals (PVB). Polyamides, although providing superior gloss and adhesion properties, are not as effective in heat sealing conditions and suffer through bad odour. PVB are generally used by confectioners as they have low odour characteristics but only offer below average print flow and heat seal characteristics. The use of nitrocellulose resins is a safety concern and ink suppliers are trying to replace these by introducing new film forming technology based on high molecular weight PU resins. This approach is seen to be promising for the future as it offers lower migratory technology. Polymer binders that are used for inks in flexible plastic packaging applications are summarised in Table 14.

4.5.4 Set Off The term ‘set off’ applies to the unintentional transfer of inks and coatings substances from the decorated outer surface of packaging to the inner, food contact surface. The accidental printing of an empty mandrel is one such mechanism of set off. Other mechanisms include the transfer of material when printed sheets are stacked, or

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are tightly rolled or, in the case of printed paper or board, possible diffusion through the substrate. Although of greater barrier performance than paper or board, plastic films may not be completely impermeable. Transfer in stacked or rolled sheet is more likely with poorly adhering decoration or if the cure is incomplete. Such deficiencies point to batch or process problems which can impact on all the material processed at the time. On this basis, such set off is unlikely to be missed by QC checks and procedures. The quick and effective detection of set off is usually a stringent requirement of the manufacturers’ customers. A non-destructive test method has been developed by the workers at the Central Services Laboratory, DEFRA, to measure the invisible set off of inks and lacquer on the food contact surface of food packaging (143).

5 Regulations Covering the Use of Inks and Coatings with Food There are a number of regulatory documents that can be used to demonstrate the safety of coatings and inks intended for food use. A recent review of the regulations for food packaging that exist in both the Europe and the USA has been published by Rapra (179). In addition, a recent overview of the legislation and testing of food contact materials, as it applies to additives, was given by Sidwell at the 2006 Addcon Conference in Cologne (39). Each of the principal regulatory documents that are relevant to coatings and inks are briefly described in the relevant sections next.

5.1 Regulation in the European Union There are no specific harmonised regulations in the EU that cover the use of either coatings or inks with food. However, the Framework Regulation 1935/2004 applies to all materials intended for food contact and so it must be complied with by all manufacturers of printing inks and coatings. This document states that food contact materials and articles: a) Shall be manufactured in compliance with good manufacturing practice b) Shall not transfer their constituents to foodstuffs in quantities which could endanger human health, and

Coatings and Inks for Food Contact Materials

c) Shall not bring about an unacceptable change in the composition of the foodstuff or a deterioration in its organoleptic characteristics. In an annex to the regulation, printing inks are listed among the substances that may be covered by specific measures, although at the time of writing these measures will be far in the future as it is thought that no work on printing inks is in progress in the EU. In addition to the Framework Regulation, manufacturers must also comply with specific substance documents such as: i)

BADGE/BFDGE/NOGE Regulation 1895/2005/ EC*

ii) Vinyl Chloride Monomer Directive 78/142/EEC *where: BFDGE = bis(hydroxyphenyl)methane bis(2,3-epoxypropyl)ethers NOGE = novolal glycidyl ethers Regulation 1895/2005/EC, covering food contact materials, articles, surface coatings and adhesives, took into account new toxicological data and placed restrictions on the use of these epoxy derivatives. For example, the use of BFDGE and NOGE were prohibited as from 1st January 2005 and 1st March 2003, respectively, with the exception of heavy duty coatings in tanks having a capacity greater than 10,000 litres. For BADGE, and its hydrolysis products, a migration limit of 9 mg/kg of food was set, and for BADGE chlorohydrins the limit is 1 mg/kg of food. This legislation is of historical interest with the EU as it was the first to set out any rules that are specific to food contact coatings. One EU document that does refer specifically to coatings and inks is the Regenerated Cellulose Film Directive – Directive 93/10/EEC (as amended by Directives 93/111/EEC and 2004/14/EC). The positive list in this regulation does not include dyes, pigments and adhesives, and substances used for these purposes are not allowed to migrate into food in detectable amounts. If a plastic coating is to be applied to the film, only substances in the lists of authorised substances in the Plastics Directive 2002/72/EC (as amended) can be used and the whole film has to comply with the overall and specific migration limits laid down in this Directive. There is in existence a draft version of a ‘Superregulation’ for plastics which includes products

that are comprised of multi-material layers on the condition that the food contact surface is a plastic. The definition of these products is such that the print and the print substances could be regarded as a layer. This document also specifies that printing ink, when used to manufacture articles for food contact, should be included in the determination of overall migration. It is also worth mentioning in this section, the Synoptic Documents that are issued by the EU. These summarise the status of the substances listed and give the current evaluations by the Scientific Committee for Food (SCF). The Synoptic Document that is of relevance here is entitled ‘Draft of provisional list of monomers and additives used in the manufacture of plastics and coatings intended to come into contact with foodstuffs’. Although it has been in existence for a number of years, this working document is a provisional and incomplete list of all the monomers and additives that are used for food contact plastics and coatings (excluding silicones) within the member states of the EU. It is a working document and is not legally binding, and updated lists are issued as different substances are evaluated by the SCF. These substances are submitted by industry, often through trade organisations, and are then examined by the SCF from a toxicological viewpoint and classified into one of ten lists – numbered 0 to 9. There is also a List W (Waiting List) for substances that are not yet included in the positive lists of the member states. Although these substances appear in the Synoptic Document they cannot be included in the EU list as they lack the data required by the SCF.

5.2 Council of Europe (CoE) Regulations 5.2.1 Coatings There is a CoE Resolution on coatings intended to come into contact with foodstuffs – Resolution ResAP (2004). This document covers the following types of food contact coating: a) Coatings for metal packaging b) Flexible packaging coatings c) Heavy duty coatings A ‘coating’ being defined by the Resolution as ‘the finished material prepared mainly from organic materials applied to form a layer/film on a substrate in such a way as to create a protective layer and/or impart technical performance’.

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Coatings and Inks for Food Contact Materials

In addition to the Framework document, this Resolution has two Technical documents associated with it: 1. Technical document No.1. Contains an inventory of substances to be used in the manufacture of coatings intended to come into contact with foodstuffs. This list has been compiled with the help of The European Council of Paint, Printing Inks and Artist’s Colours Industry (CEPE). 2. Technical document No. 2. This document contains the scientific background for the elaboration of the Resolution The Inventory is divided into two categories, monomers and additives, all of which have some national member state or FDA authorisation. Both of these sub-lists are divided into those which are already fully evaluated and included in SCF/ European Food Safety Asscoiation (EFSA) lists, and those that have not yet been fully evaluated by SCF/EFSA (called the Temporary Appendix). The Temporary Appendices to the monomer and additive lists are time limited with a deadline for evaluation of five years from the date that the Resolution is adopted. Although this Resolution, in common with other CoE Resolutions, has no legal status, it is regarded as being useful in demonstrating compliance until such time as the EU has fully incorporated surface coatings into its legislative framework. In addition to being manufactured according to ‘good manufacturing practice’ (GMP) using the monomers and additives listed in the Inventory, the Resolution states that the Resolution on polymerisation aids – AP (92)2 should also be adhered to. The Resolution also stipulates an overall migration limit of 10 mg/dm2, or 60 mg/kg of food for certain specified situations, as measured by EU methods (see Section 6.1). The Resolution also states that coatings should not transfer migrating components, not listed in Technical document No. 1, which have a molecular weight of less than 1000 daltons in quantities which could endanger human health. If such migrants are detected, they should be subjected to appropriate risk assessment taking into account dietary exposure as well as toxicological and structure-activity considerations (see Section 6.6). For those coatings that are based on silicone type polymers, there is a specific CoE Resolution, APRes (2004). Both silicone rubbers and silicone resins are covered by this Resolution. Blends of silicone rubber with organic polymers (EPDM rubber) are also covered by the Resolution provided that the silicone monomer units are the predominant species by weight. There is an overall migration limit of 10 mg/dm2 of the surface

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area of the product or material, or 60 mg/kg of food. There are restrictions on the types of monomer that can be used to produce the silicone polymers and there is an inventory list : ‘Technical document No.1 – List of substances used in the manufacture of silicone used for food contact applications. Where rubber type protective coatings are used, there is no specific EU legislation, but there is a CoE Resolution, APRes (2004). The Resolution contains an inventory of additives (Technical document No. 1) and a small section on breakdown products – nitrosamines and amines. In addition, there are four other technical documents, covering such things as good manufacturing practice, and test conditions and methods. The Resolution also places rubber products into one of three categories according to their application and the migration that may occur. Migration testing is required for only the first two of these, where an overall migration limit of 60 mg/kg food applies.

5.2.2 Inks The CoE has recently issued a Resolution on ‘Packaging inks applied to the non-food contact surface of materials and articles intended to come into contact with foodstuffs’ – Resolution AP(2005)2. As the title suggests, inks that come into direct contact with food are not covered by this Resolution. Also excluded are inks used on the outside of glass bottles and metal cans (as the substrate material is regarded as being a comprehensive barrier). Its main purpose is to regulate the inks used on the outside of plastic, and paper and board type food packaging. One of the problems that were encountered in the drafting of the resolution was the understandable reluctance of industry to release detailed information on the formulation of ink products. The Resolution states that the ink supplier is responsible for the composition of the ink. There are three technical documents that accompany the Resolution: 1) Technical document No. 1: Contains an inventory of substances being used in the industry, an exclusion list, and specific migration limits where possible. 2) Technical document No. 2: This is a GMP Guide, in two parts. The first part addresses inks and has been drawn up by CEPE, the second, which addresses the plastic and paper and board substrates has been prepared by the European Forum of Flexible Packaging Industry and the International Confederation of Paper and Board Converters (CITPA).

Coatings and Inks for Food Contact Materials

3) Technical document No. 3: This document provides guidance on the conditions that should be used for the testing of packaging inks applied to the non-food contact surface of food packaging.

ii) The printed or overprint varnished layer of finished printed materials or articles should not come into direct contact with food.

These industry concerns have led to groups such, as the British Coatings Federation (BCF) in the UK, to compile their own, alternative Inventory lists. A draft version of the BCF list (as it stood in June 2006) is included as an Appendix in the final report for the FSA Coatings and Inks project (a.8). There are also other industry driven documents such as the EuPIA Guideline, Declaration of Conformity and Good Manufacturing Practice. These documents, which are available from the EuPIA web site (www.eupia.org) were issued to states within Europe during 2005 and 2006. There is also a EuPIA funded investigation into ink additives that have not been evaluated and listed, and a commitment to reduce the migration limit of ‘no concern’ for these non-evaluated substances to 50 ppb by 2010, with a further reduction to 10 ppb by 2015, which will bring inks in line with other food contact materials (a.7).

iii) There should be no or only negligible visible setoff or migration from the printed or varnished nonfood contact layer to the food contact surface.

5.3 National Regulations within the EU

The main CoE Ink Resolution requirements can be summarised as follows: i) The packaging inks should be manufactured and applied on the support in accordance with the guidelines for good manufacturing practice and with the recommendations of the converters as set out in Technical Document No. 2

iv) The overall migration and specific migration level (SML) for the substances in the inventory lists apply. v) Migrated printing inks shall not be detectable at the lowest concentration at which a substance can be measured with statistical certainty by a validated method of analysis, i.e., a detection limit of 10 ppb or below. This Resolution has attracted some controversy, with industry groups in the EU (e.g., The European Printing Ink Association (EuPIA) – a sector of CEPE) saying that there will be problems with its implementation, and in some cases that it is unworkable in its present form. (a.7). There are a number of reasons cited for this, for example: a) The Inventory is incomplete, with only representative examples of generic groups present, and many key raw materials are missing altogether, e.g., there are no adhesion promoters (used with flexible packaging inks on polyolefin films), no phenolic resins (used in most sheetfed offset litho inks), and no photoinitiators (used in UV-cured inks). b) The majority of the substances have not been evaluated and so migration studies have to be carried out using a demanding and, in some cases unfeasible, 10 ppb detection limit. The end result could be that some inks become unavailable.

The regulations that exist within certain states in the EU can be used to demonstrate compliance with the Framework Regulation. For coatings, the most comprehensive of these is the Dutch Verpakkingen-en Gebruiksartikelenbesluit (Hoofdstuk X). This contains a positive list of permitted starting substances and is widely used within the EU. In those cases where thermoplastic polymers are used as the coating (e.g., on a metal substrate), the plastic food contact materials and articles Directive 2002/72/EC can often be used to demonstrate food safety. However, food use coatings are far more likely to be of the thermosetting type (see Section 2.1), which are more complex and not fully covered by 2002/72/EC. In these cases, reference to the CoE Resolution on Surface Coatings (see Section 5.2), or the published opinions of the Scientific Committee on Food/European Food Safety Authority (SCF/EFSA) can be used to demonstrate compliance. In Germany, Recommendation XV of the BfR regulations covers silicone rubbers and silicone resins – both of which can be used as coatings. The relevant sections stipulate acceptable starting materials and additives that may be used in processing and manufacture – both types and maximum levels. There are overall limits for volatile organic material as well as total extractable material, and specific limits for certain starting substances, e.g., residual peroxides in the case of silicone rubbers. In the case of rubber coatings, there are a number of national regulations that can apply. The most prominent of these include (32):

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Coatings and Inks for Food Contact Materials

a) French requirements - Arrete of November 9th 1994, Journal Official de la Republique Francaise, 1994. b) D u t c h r e g u l a t i o n s - Ve r p a k k i n g e n e n gebruiksartikelenbesluit (Chapter III). These are similar to the CoE Rubber Resolution. c) Italian requirements - Supplemento ordinario alla Gazetta Ufficiale della Repubblica Italiana, 1973. d) United Kingdom requirements - Statutory Instrument 1987 No 1523 Materials and Articles in Contact with Foodstuffs. The French and Italian regulations cited previously are the general food contact documents and so other coatings materials, in addition to rubber, are also covered by them. Food contact materials in Belgium are regulated under the Royal Arrete of May 1992 on Materials Intended for Contact with Foodstuffs. A total of seven EU Member States (Belgium, France, Germany, Italy, the Netherlands, Spain the UK,) have some form of National positive list of permissible substances for use in manufacturing food contact materials in addition to the EU Directives. A listing of national food packaging legislation is available from the European Commission and additional information is available in book written by Ashby, Cooper, Harvey and Tice (212). With respect to inks, there a very few National regulations within Europe. An exception is Chapter XXXVI of the German Recommendation BfR, which has a general statement on colorants and optical brighteners in the food contact material. This states that they should not migrate into foodstuff and that no testing is required for packages intended for dry, non-fatty food.

5.4 FDA Regulations The food regulations for polymer and resinous coatings are given in the FDA Code of Federal Regulations (CFR) 21.These documents, which are used globally for the formulation of a large number of coating products, list authorised starting substances and lay down test conditions and migration limits. Coatings for specific substrates can be found in the following sections of CFR 21:

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Metal substrates and repeated use

175.300

Polyolefin films

175.320

Paper coatings

176.170

The current regulations in the US for both coatings and adhesives have been reviewed by Baughan (196). At the same PLACE conference, Lin and co-workers (197) presented a paper describing developments and improvements that had been made to the migration tests that are necessary to establish if electron beam (EB) and UV cured coatings and adhesives complied with the FDA regulations. The contribution of relatively new analytical techniques, such as liquid chromatography (LC) mass spectrometry (MS)/MS, to this type of work is featured. Inks are very rarely used in direct contact with food because there are virtually no ink formulations that comply with the FDA. For example, there a very few carbon black pigments which are acceptable to the FDA and, to achieve coloured inks, only food colorants are permissible. This latter requirement severely limits the methods that can be used for the application of the ink. In addition, manufacturers of food contact inks have to ensure that no carry over was possible from equipment that had been used in the manufacture of non-contact products (e.g., for external decoration on cans and metal tins etc), which are not required to be FDA compliant.

5.5 Other Considerations for Industrial Use In addition to the Regulations described in Sections 5.1 to 5.4, there are other reference documents that industrialists need to be aware of: a) REACH EU Regulation This Regulation covers the Registration, Evaluation and Authorisation of Chemicals (REACH) of chemicals and might have an impact on the substances used in coatings and inks in the future. The cost of compliance may mean that some small volume chemicals disappear from the market place, although implementation may take over 10 years for some substances. Importantly, as polymers are exempt from the Regulation those used in the manufacture of coatings and inks will not need to be registered. b) CEPE Exclusion list for Printing Inks In addition to its GMP guides, CEPE has published an exclusion list for printing inks. The substances on this list are present in the Dangerous Substances Directive (67/548/EEC), and pigments colorants based on antimony, arsenic, cadmium, chromium

Coatings and Inks for Food Contact Materials

(VI), lead, mercury and selenium. Some solvents are also on the list, as are cyclohexane, and some stilbenes, butylphenols and benzophenones compounds. This CEPE list is not identical to the CoE exclusion list. c) British Coating Federation Documents The BCF has issued a guide to printing inks for food wrappers and packagings. At the time of writing it is also working on an inventory designed to be an alternative to that contained within the CoE Resolution on Inks – Technical document No. 1 (Section 5.2). The reason that the BCF believes that an alternative list is necessary, is that whereas the CoE Inventory list mainly originated from national legislation their list relates to those substances currently used in Industry. To help understand the regulatory status of the BCF listed substances, the two lists have been compared in the final report of the Rapra FSA project (A03055) (a.8) and those substances not in the COE Inventory list have been highlighted. This exercise showed that a relatively large number of substances in the BCF list are not included in the CoE list. d) Good Manufacturing Practice The coatings and ink industries have their GMP guidelines to ensure that their products are manufactured to the highest standards. e) CEPE Code of Practice for Coated Articles where the food contact layer is a coating This extensive and wide ranging, industry driven, code of practice will be taken by the Commission as a base for a specific regulation on coatings. Work on this document is on-going at the time of writing - Draft 10 was published on 30th June 2006. This code and its guidelines, which has similarities to the Plastics Super Regulation and the 4th amendment to the Plastics Directive 2002/72/EC (see Section 5.1), and which describes how compliance with the Framework Regulation 1935/2004/EC can be demonstrated for direct food contact coatings, are voluntary in nature and individual companies may decide to apply them either fully or partly, according to their own judgement. A list of the companies supporting the code can be obtained from CEPE. The Code of Practice applies to the food contact surfaces of the following: i)

Coated light metal packaging up to a volume of 10 litres.

ii) Coated metal pails and drums with volumes ranging from 10 to 250 litres. iii) Coated articles with volumes 250 to 10,000 litres. iv) Heavy duty coated articles having a volume >10,000 litres. v) Coated flexible aluminium packaging. Sectors which will be incorporated at a later date when more details are available are: i)

Printing inks in direct food contact.

ii) Coated primarily used to seal food packaging. iii) Gaskets for metal closures. iv) Coated flexible plastic packaging. v) Coatings and inks for paper and board. The Code of Practice does not apply to: i)

Repeated use, non-stick coatings, which remain regulated by the specific chapters of BfR, VGB, and FDA applicable to them.

ii) Extrusion coated materials or articles where the extrusion coating being a plastic, should comply with the provisions of Directive 2002/72/EC, as amended. iii) Laminated packaging articles or components where the food contact layer, being a plastic, should comply with the provisions of 2002/72/EC, as amended. iv) Printing inks and coatings applied to the nonfood contact surface of food packaging materials and articles intended to come into contact with foodstuffs. v) Coatings on paper and board which remain regulated by specific chapters of BfR, VGB and FDA applicable to them. vi) Coatings on regenerated cellulose which are covered under Commission Directive 93/10/EEC and its amendments. vii) Can end sealants based upon rubbers and elastomers which remain covered by rules applicable under national legislation. viii) Tin coatings, wax coatings and adhesives

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Coatings and Inks for Food Contact Materials

6 Assessing the Safety of Inks and Coatings for Food Applications As this review illustrates, many different types of polymers and types of polymer product (e.g., thermoplastic, thermoset and rubber) can potentially be used for coatings in food applications (see Sections 2.1.1 to 2.1.11).This in turn means that a large number of different regulations and requirements may have to be addressed, in order to decide upon the correct conditions (e.g., choice of simulant, test samples, times and temperatures) under which to carry out food migration testing. This point is illustrated by the summary of regulations which is provided in Section 5. For direct food contact coatings, the CEPE Code of Practice (see Section 5.5) provides a great deal of useful information on how compliance with the Framework Regulation 1935/2004/EC can be demonstrated. An overall migration limit of 60 mg/kg is provided, and SML for particular substances are provided in the Annexes. In addition, guidance on the food simulants for the migration testing is provided, as are guidelines on assessing exposure to migrating substances and basic rules for demonstrating compliance with the overall migration limit (OML) and the SML. Inks for food use, on the other hand, do not present such a complicated problem as they represent a specific product category in themselves, are mainly used on the non-food contact service of food packaging, and the binders in them do not span such a wide range of polymers types and chemistries. There is an on-going effort to ensure that migration data is as accurate as possible. For example, the EU recently funded a research project (EU AIR 94-1025) to facilitate the introduction of migration control into GMP and into enforcement policies and a part of this project involved the re-evaluation of the analytical approaches to extract and identify potential migrants from food contact materials. The results of this part of the project are published in the journal, Packaging Technology and Science (191) and the journal Food Additives and Contaminants (206) There is also a continuing need to detect migrating substances at lower levels. For example, toxicologists have suggested that species which are ingested in amounts exceeding 1.5 mg/day should be identified and toxicologically evaluated. Identification and quantification of species at such a low level will cause problems and these are discussed in a paper by Grob (208). The conclusion reached is that it will be difficult

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to achieve, the comprehensive analysis of coating migrants down to concentrations that are presently regarded as safe with the analytical instrumentation currently available.

6.1 Global Migration Tests This is the usually the simplest test to perform and it is used to determine if the product is suitable for a particular food use application by passing the global migration limit that is stipulated by all of the various regulations covered in Section 5. The methodology of the test varies depending on the regulation that is being addressed, as does the way of expressing the data and the limits that have to be met. Specific details can be obtained from the various pieces of legislation. For example, in the EU, the global migration tests that apply to coatings and inks, and other food contact materials, are described in the following documents: i)

Council Directive 82/711/EEC of 18th October 1982, as amended by Commission Directive 93/8/ EEC of 15th March 1993

ii) Commission Directive 97/48/EC of 29th July 1997 iii) Council Directive 85/572/EEC of 19th December 1985 The food simulants that are specified in these Directives are: a) Aqueous foods - Distilled water b) Acidic foods – 3% acetic acid c) Alcoholic food – 10% ethanol d) Fatty food – olive oil Migration testing using these simulants should be performed under the worst foreseeable contact times and temperatures that can be envisaged for the application. For example, long-term storage at room temperature is represented by testing for ten days at 40 °C. The 82/711/EEC document provides a correlation table for migration test conditions. The analytical methods for testing overall, and specific migration, have been standardised at the European level by CEN (the European standardisation body).

Coatings and Inks for Food Contact Materials

6.2 Specific Migration Tests These tests are used to target specific chemical compounds for which there is a toxicological concern and a SML, i.e., listed substances. In common with the global migration test, the tests specified (target species and test conditions) vary from regulation to regulation, but some species appear regularly due to the degree of concern associated with them. There are a number of cases where there are specific analytical test methods documented, particularly in cases where there are resolutions or regulations on a particular migrant. For example: i)

Free vinyl chloride monomer – Analytical methods described in Commission Directives 80/766/EEC and 81/432/EEC

ii) Determination of 4-methyl-1-pentene in food simulants – CEN/TS 13130-25:2005 (a.9) iii) Determination of bisphenol A in food simulants – CEN/TS 13130-13:2005 (a.10) iv) Determination of 1-octene and tetrahydrofuran in food simulants – CEN/TS 13130-26:2005 (a.11) The test methods that should be used for specific migrants from coatings that can be regarded as plastics are described in EN 13130-1 (a.12) There are also cases where a particular species has attracted a lot of analytical attention in recent years. A good example of this is BADGE from can coatings and a number of approaches for its determination have been documented (200).

6.3 Fingerprinting of Potential Migrants from Coatings and Inks It is often useful to produce a qualitative or semiquantitative fingerprint of the low molecular weight species in coatings and ink products that have the potential to migrate into food. Gas chromatographymass spectroscopy (GC-MS) is often used for this due to its high resolution and the identification power of the mass spectrometer. In order for the data to be representative, it is important that the coating and ink product is in the form in which it is used in the final end use product. As both of these materials usually have to undergo a curing or drying stage, this should be carried out prior to any analysis step, or samples taken from the final product in situ. The latter option can present a

problem with inks when only small amounts of material are used, for example., in printing. The considerations detailed previously will mean that the samples are in the solid phase, and so the headspace GC-MS techniques are the most applicable, with the dynamic version having the advantage over the static in that it requires less sample. The solvent extraction GC-MS technique may be applicable where larger areas of coating and print are available for analysis. This method has the disadvantage, however, of the initial solvent front obscuring early eluting (i.e., low molecular weight) species. The relatively recent commercialisation of two dimensional GC-MS instruments has provided the analyst with greater resolving power, coupled with improved detection limits and enhanced deconvolution software (142). As in-house, coatings and inks specific databases are developed for LC-MS, the inclusion of this technique into the fingerprinting process will complement GC-MS data by contributing information on thermally labile, relatively large (e.g., oligomers), and highly polar (e.g., organic salts) potential migrants. Albert and co-workers (197) have reviewed, and compared, the use of modern liquid chromatography methods, such as LC-MS and LC-MS/MS, with the GC-MS technique for the analysis of potential migrants from FDA compliant, EB and UV curable food packaging coatings and adhesives. In addition to comparing the analytical capability of these systems, the effect that various processing variables (e.g., curing voltage and dosage) had on the extractable data were also evaluated.

6.4 Determination of Specific Target Species in Coatings and Ink Products and in Food Simulants and Foods The use of specified tests to determine species that have SML has been covered in Section 6.2. There are reasons why further analytical testing is often required, for example to ensure that a coating or ink has been formulated using only additives and ingredients that are present in a particular positive list, or to quantify a potential migrant for which there is as yet no specific migration test or SML. A review of the analytical methods that can be used to identify and quantify a range of species that can be found in food contact materials has been written by Veraart and Coulier (29). For convenience, species have been placed into functional categories next and the analytical techniques used to detect and quantify them explained.

41

Coatings and Inks for Food Contact Materials

6.4.1 Monomers, Solvents and Low Molecular Weight Additives and Breakdown Products Monomers are either gaseous or relatively volatile liquids and so GC and GC-MS based techniques are usually used to determine them in both the final coating and ink product and the food simulant/food product. To simplify the analysis, a static headspace, or dynamic headspace, sampler is often used to isolate the analyte from the sample matrix (a.13), an extraction procedure often presenting problems due to the masking effect of the solvent. There are important examples, however, where analysis, sometimes following chemical derivatisation work is used. This approach was used by Paz-Abuin and co-workers (210) to carry out specific migration work on two epoxy resin coatings for use with drinking water. The amine curing agents were determined by high performance liquid chromatography (HPLC) with pre-column derivatisation, whereas the epoxy resin monomer was quantified using HPLC without any derivatisation. A reverse phase HPLC system with fluorescence detection was used in both cases. In addition to antidegradants and curatives (which are mentioned next), other additives (e.g., pigments) can also produce breakdown products which are regarded as harmful. For example, Michler’s ketone, can be a degradation product of certain violet dyes used in printing. This compound is regarded as a potential carcinogen and so methods to assess its migratory behaviour into food simulants have been developed (a.14) The use of GC-MS to determine the levels of photoinitiators and acrylic esters which have the potential to migrate from inks into food simulants has been described by Papilloud and Baudraz (207). The study covered the migratory behaviour of nine different acrylate monomers and six different photoinitiators in a range of aqueous and fatty food simulants.

6.4.3 Plasticisers and Oil-type Additives These additives are essentially high boiling point liquids and so the most appropriate technique to use is LC-MS. A range of synthetic plasticisers such as phthalates, adipates, mellitates and sebacates can be detected using the atmospheric pressure chemical ionisation mode. If data on non-polar hydrocarbon oils is required, then an atmospheric pressure photoionisation head (which can detect non-polar species is required) or, if the oil has a sufficiently high aromatic character, in-line UV or fluorescence detectors can be used.

6.4.4 Polar Additives and Metal Containing Compounds For additives that are highly polar (salts or ionic compounds), for example, antistats, thickening agents and surfactants, there are two analytical techniques which can be of use to the analyst: an LC-MS fitted with an electrospray head, and anion and cation ionchromatography. Both of these have the potential drawback that they are much easier to use on aqueous samples, rather than fatty ones- an intermediate extraction step often being required in the latter case. In certain cases, compounds which have a metal component (e.g., platinum catalysts used in certain silicone products) are present in the coating or ink product. In order to determine these types of migrants at a low (i.e., ppm) level, techniques such as atomic absorption spectrophotometry and Integrated coupled plasma have to be used. One complicating factor which needs to be borne in mind with this type of analysis is that a value for the target metal will be obtained irrespective of which compound/additive it is in; interferences can therefore occur and knowledge of the product’s composition and/or the service history of the sample are important.

6.4.5 Cure System Species, Initiators, Catalysts and Their Reaction Products 6.4.2 Oligomers Prior to the commercialisation of LC-MS instruments, supercritical fluid chromatography was widely used for the analysis of oligomers. As the molecular weight range of LC-MS instruments can be extended up to 4000 daltons this capability makes them ideal for the detection and quantification of oligomers. For example, it has been shown that silicone oligomers can be detected by LC-MS in food simulants (108), and (a.1).

42

These species are usually low, or relatively low molecular weight organic compounds of intermediate polarity and as such as ideally suited for determination by GC-MS. Problems can occur if the species are very thermally labile and/or reactive, and in these cases (as in the cases of metal salts – see previously) LC-MS is the preferred technique. It is also easier to use LC-MS with a number of the approved food simulants as they can be injected directly into the instrument, being compatible with the mobile phase.

Coatings and Inks for Food Contact Materials

6.4.6 Antidegradants, Stabilisers and Their Reaction Products This class of additives is generally less thermally labile and reactive than the preceding one and so GC-based methods can be used for a number of them. Where high processing temperatures dictate the use of relatively high molecular weight, oligomeric type stabilisers, LC-MS methods have to be used.

6.5 Sensory Testing This category covers subjective testing by a panel of trained human assessors to identify taints and odours in food packaging. The number of assessors in the panel is determined by the sensitivity that is required for the test, i.e., the statistical reliability. Although the test is subjective, experience has shown that a well trained panel will produce consistent results. The transfer of a taint is more important from a legal point of view, whereas an odour has more importance from a marketing point of view. For the evaluation of the odour of printed paper, board, plastic or any other material, test pieces are stored in jars for a certain time. The odour present in the jar air is then assessed by the panellists and the intensity rated on a scale such as 0 (no odour) to 4 (strong odour). To evaluate taint, test pieces are stored with a test food (e.g., chocolate) in a jar and then the taint of the food is assessed and rated by the experts. There are a number of ways of performing this operation. For example, in a ‘triangle test’, one portion of food has been stored with the material to be tested, the other two are reference samples, and the assessors have to select the odd one out. In a ‘multi-comparison test’, the assessors are given a reference food sample that is regarded as having a value of 0 and then they score the intensity of the taint of an analysis sample using a scale usually of 0 (no taint – i.e., same as reference) to 4 (strong taint). There are no specific international standards for assessing odour and taint as a result of inks and coatings, but there is a general ISO standard, ISO 13302:2003 (a.15) that addresses the modification of the flavour of foodstuffs due to packaging materials. There is also a specific standard for paper and board, EN 1230-1 (a.16) and two draft standards on sensory analysis in general, ISO 4120:2004 (a.17) and ISO 5492:2005 (a.18). Because carrying out sensory testing for odour by a human panel is time consuming, and of increasing

importance in a number of other manufacturing sectors (e.g., automotive), a great deal of effort has been expended in the search for a device that can act an effective and reliable ‘electronic nose’. It now seems that such an instrument, which is based on a chemical sensor array, will soon be acceptable for routine analysis within the food and packaging industry. An investigation by van Deventer (a.19) on volatile chemicals from inks on plastic films showed that the quartz sensors of an electronic nose system were able to discriminate between packages with different levels of retained solvents, and Frank and co-workers (a.20) demonstrated that an instrument containing eight sensors and eight microbalances gave a good correlation with human assessment panels concerning retained solvents in printed wrapping foils.

6.6 Toxicological assessment of migrants Defining the starting substances for coatings and inks can depend upon which part of the industry a person comes from – the ingredients industry or coatings manufacturing. The list that results (monomers, additives, polymerisation aids, resins, oligomers, additives) is therefore very extensive. This large list, coupled with the complex chemistry associated with the manufacture of the starting substances and the chemical reactions that take place to produce the finished products, leads to a very complex mixture of substances having the potential to migrate into food simulants and food. A CoE working group has shown that it is impossible to evaluate all of these substances from the toxicological point of view according to EU guidelines. One way of dealing with this problem for substances that are not listed (i.e., their toxicity is not known), is to use a ‘tiered’ approach, which takes into account dietary exposure as well as toxicological and structure-activity considerations, the aim being to reduce the number of toxicological evaluations that are required. For example: 1) Tier One Substances which migrate into food or food simulant at less than 10 ppb should not be evaluated. 2) Tier Two Many substances used in coatings can be reduced to smaller units (e.g., the oligomers and polymers to the

43

Coatings and Inks for Food Contact Materials

monomers). As this smaller unit represents the ‘worse case scenario’ in terms of toxicity it is toxicologically assessed and the result applied to the oligomers and so on.

commercial products (which may be mixtures), and high MS acquisition rates, or the use of two dimensional (i.e., GCxGC) instruments may be necessary to resolve the individual components (see Section 6.4).

In accordance with EU guidelines of toxicity testing, the following applies: i)

>10 ppb up to < 50 ppb Three mutagenic tests

ii) >50 ppb up to < 5ppm

Three mutagenic tests, 90 days feeding study

iii) >5 ppm

Three mutagenic tests, 90 days feeding study, 2 years feeding study

3) Tier 3 The decision to use Tier 2 is based on state of the art knowledge and/or QSAR. If any scientific knowledge and/or QSAR show that toxicity of a monomer is not equal or less than the toxicity of the oligomer/polymer, an evaluation of the oligomer/polymer has to take place using the same toxicity guidelines as given for Tier 2. Note: QSAR = Quantitative Structure-Activity Relationship. A mathematical model that relates a quantitative measure of chemical structure (e.g., a physicochemical property) to a property or to a biological effect (e.g., a toxicological endpoint). QSAR are being used more extensively to save time, money and in the interests of animal welfare.

7 Potential Migrants and Published Migration Data 7.1 Acrylates The lower acrylates are known irritants, and ethyl acrylate is regarded by the IARC as a Group 2B carcinogen. However, there are many acrylate monomers used in ink and coating formulations and these lower acrylates may be far from representative. Of higher molecular weight, and commonly used in UV-curing inks are the acrylate esters of polyhydric alcohols. These types of acrylates have been detected and quantified by GC-MS (207). Reference materials having molecular weights up to 470 were determined with a detection limit of 20 ng. The quantification of these monomers in food migration samples can prove difficult owing to the complexity of

44

7.2 Amines The aromatic amines can be of particular concern as some of these compounds are classed as carcinogens. Although the most potent carcinogens are found amongst two-ring aromatics (benzidine, naphthylamine), even single ring compounds such as ortho-toluidine or ortho-anisidine (2-methoxyaniline) are found on the IARC listings. Both of these single ring aromatics have been detected in aqueous extracts of printed multi-layer plastics, and ortho-anisidine has also been detected in olive oil extracts (a.21). The same studies also found 2,4-dimethylaniline in both aqueous and olive oil extracts. For all three amines, detection in olive oil was by headspace GC-MS (detection limit 20 μg/kg) and, in water, solid-phase extraction was used followed by GC-MS (detection limit 0.1 μg/kg). A significant amount of research work has been carried out on the amines which are the precursors and hydrolysis products of the isocyanates in PU, notably the three aromatic amines, the 2,4- and 2,6- isomers of toluene diamine (2,4- and 2,6-diaminotoluene), and 4,4´-methylenebis(aniline). Potential sources are the PU used in coatings and ink binders, or in the laminating adhesives used for multilayer packaging. All three amines were detected in aqueous extracts of laminated films using derivatisation followed by GC-MS (a.22). Solid-phase derivatisation with trifluoracetic anhydride (RNH2 → RNHCOCF3) was used, and the respective detection limits were in the range 0.1-0.4 μg/l. Derivatisation is necessary with these types of compound to avoid peak tailing in GC analysis. Other reagents which can be used for this purpose include hexafluorobutyric anhydride, as in the OSHA 1910 method for airborne species, with GC electron capture detection for the subsequent analysis step. Derivatisation can also be performed to enhance sensitivity to UV detection, and this forms the basis for the global analysis of primary aromatic amine by diazotisation and coupling with(1-naphthyl)ethylenediamine dihydrochloride (a.23) (a.24). This method has a detection limit of 8 μg/kg (total aromatic amine quantified with respect to aniline), and provides a valuable screening technique. A recently reported technique which provides good sensitivity without derivatisation uses electrospray

Coatings and Inks for Food Contact Materials

ionisation with tandem mass spectrometry (a.25) The technique is rapid as there is no chromatography step and the reported detection limits were 2-3 ng/ml in aqueous ethanol extracts.

styrene continued to evolve as a result of on-going depolymerisation. The levels determined (at 200 ºC) included: up to 37 mg/kg of ethylbenzene, up to 180 mg/ kg of benzaldehyde and up to 1330 mg/kg of styrene.

One aromatic amine which does not arise specifically from colorants or PU is 4,4´-bis(dimethylamino) benzophenone [(Me2NC6H4)2C=O, Michler’s ketone]. Michler’s ketone is a photoinitiator for UV-curable inks. Although its potential carcinogenicity excludes its direct use in food contact materials, Michler’s ketone is a well-established initiator, and concerns have been raised over its introduction into food packaging via recycled fibres (a.14).

The dynamic headspace GC, or GC-MS, method is unsuitable for the determination of these aromatics in foodstuffs, or aqueous simulants, because of the interference of water. Gramshaw and Vandenberg extended their studies into foodstuffs using a workup procedure which included azeotropic distillation and pentane extraction to find up to 188 μg/dm2 styrene in pork cooked in contact with an unsaturated polyester for 1.5 hours at 175 ºC.

7.3 Aromatics from Unsaturated Polyesters

7.4 Aromatics from Photoinitiation Reactions and Photoinitiator additives

Amongst the species considered here are: acetophenone, benzaldehyde, benzene, ethylbenzene and styrene. Benzene and ethylbenzene are classified by IARC as Group 1 and Group 2A carcinogens, respectively. Benzaldehyde is harmful by ingestion and has a potential to cause allergic reactions. Benzene can be found in unsaturated polyester resins due to it being a relatively minor component of the styrene feedstock. Styrene being the most commonly used reactive diluent for these types of resins. Dynamic headspace GC with flame ionisation or MS detection has been used for the determination of low molecular weight aromatics in cured unsaturated polyesters (214). At 200 ºC, volatilisation of ethylbenzene and benzaldehyde was complete after 1 hour, whilst

Amongst the species considered here are: benzene, benzophenone, and the thio- or iodoaromatics from cationic photoinitiation, in addition to the photoinitiators themselves. Benzene is a carcinogen and a potential by-product of cationic photoinitiator action. Benzene has been detected in packaging and foodstuffs (a.26) and studies have been carried out to determine benzene and other aromatics in headspace volatiles and toluene extracts of UV cured inks (a.27). No benzene was detected, although a number of other aromatics compounds were detected, as shown below in Table 16. With regard to the three compounds that have been detected at the highest levels, diphenyl disulfide (also

Table 16. Aromatic Compounds Detected from UV Cured Ink By-product

Level mg/m2

Diphenyl sulfide

8.0

Standard (Uvacure 1592)

Benzene

-

Nd

Iodonium standard

Toluene

-

Nd

IGM440

Iodotoluene

-

DNQ

Meerkat

Biphenyl

4.2

Isopropylthioxanthone

15.7

Polecat

Biphenyl

-

Bobcat

Isopropylthioxanthone

9.1 (ITX)

Sample Triarylsulfonium

Comments

DNQ

Nd = Not detected by the method DNQ = Detected but not quantified

45

Coatings and Inks for Food Contact Materials

called phenyl sulfide) is a severe irritant to the respiratory and digestive tract, and biphenyl is an irritant to both of these, but there is little information to hand on the acute or chronic toxicity of isopropylthioxanthone (ITX). Work that was reported on ITX as a result of it being detected in infant formula (see below) concluded that the existing in vivo genotoxicity studies do not indicate a genotoxic potential for ITX. The other initiator that was involved in this incident, 2 ethylhexyl-4-dimethylaminobenzoate (EHDAB), is not regarded a genotoxic or a teratogen.

milk-and soya-based products the level of ITX ranged from 54 to 219 ug/l, and the level of EHDAB from 27 to 134 ug/l. Investigations at the time are believed to have revealed that the initiators found their way into the food products as a result of being transferred to the food contact site of the packaging by the phenomenon known as off-set (see Section 4.5). Details of EFSA’s opinions on ITX and EHDAB can be found on their web site (www.efsa.europa.eu).

The extraction medium is important for aromatic compounds of this type. For UV-cured epoxy films initiated with a mixed triarylsulfonium phosphate (Cyracure UVI-6990), much higher levels of extractables were observed with 50% ethanol rather than 10% ethanol or water: up to 272 ppb diphenyl sulfide was taken up in 50% ethanol (213). HPLC with UV detection was used for these extract analyses. A method for the detection by GC of the photoinitiator residues in aqueous media has also been developed (207). In this case, solid-phase extraction (on C18-modified siloxanes) was used, followed by methanol desorption for the work up of the extracts.

7.5 BPA and BADGE and Derivatives

Benzophenone is a photosensitiser, which may cause digestive tract irritation. GC-MS has been used to test for migration of this compound from cartonboard packaging (193). In this study, 143 out of 350 samples of printed cardboard used with foodstuffs surveyed contained detectable benzophenone. In food, the highest level (7.3 mg/kg) was found for a high fat chocolate product packaged in direct contact, with 24% of the food samples surveyed having levels between 0.5 and 5.0 mg/kg. In those cases where there was no direct contact with the food, a six-fold reduction in the amount of benzophenone present was found. Recently there have been reports of the photoinitiators, ITX and EHDAB, being found in products that are packed in printed cartons, such as milk and fruit juices. A notification from the Italian authorities under Article 50 of the Regulation (EC) No 178/2002 on the Rapid Alert System for Food and Feed showed the occurrence of ITX in liquid milk for babies at a level of 250 ug/l. As part of the investigation that ensued, the presence of EHDAB, often used as a synergist with ITX, was also revealed in food samples. Following a request from the Commission, a survey of ITX and EHDAB in a wide range of carton packed drinks, varying from water and fruit juices to flavoured milk, was carried out by industry. In this study, the full results of which are reported in The EFSA Journal (a.28) ITX was found to vary from 120 to 305 ug/l in milk products intended to be consumed by babies and very young children. No data on EHDAB was reported for these samples. In

46

BPA and, to a lesser extent, BADGE are of concern for endocrine disruption, and much effort has been devoted to the investigation of the possible migration of these from cured epoxies. BADGE is an important epoxy monomer and BPA is its immediate precursor. Whilst the focus of this work has been on direct food-contact coatings (i.e., can coatings), epoxies have widespread application in packaging as adhesives, coatings and binder resins for inks. Of course, the expectation is that direct food contact provides the worst-case scenario, where μg/kg levels of BPA and mg/kg levels of BADGE have been detected in certain foodstuffs (a.29) (a.30) and (211). Studies on the resin itself showed that BADGE migration levels decreased with increasing time of cure (217), whilst a further heating step reversed the trend (209). The influence in thermal history seen here reflects the transition from kinetic to diffusion control in the progress of cure (218) and (215), and impact of state of cure on migration behaviour (a.31). Recently efforts have been made to improve analytical capability with respect to BADGE derivatives and related compounds. The former include low molecular weight BADGE oligomers, and the latter includes BFDGE. HPLC coupled with UV, fluorescence and electrospray ionisation MS have all been used for the detection of BADGE oligomers of up to 1000 daltons (173). The technique was applied to can coatings where a cumulative total of up 0.7 μg/dm2 of coating was determined for BADGE-related species below 1000 daltons by acetonitrile extraction. HPLC coupled with fluorescence detection has been used for the simultaneous determination of BADGE and BFDGE by two separate research groups (a.32) (a.33). A limit of detection in various food simulants approaching ppb (μg/l) levels was claimed.

Coatings and Inks for Food Contact Materials

Excluding the oligomers from this analysis allows GCMS to be used, and Czech researchers have recently reported the determination of BPA, BADGE, BPF, BFDGE by this technique (a.34) The limits of detection in acetonitrile or food-stimulant extracts of coatings were below 1 μg/dm2 for all four analytes. BPF and BFDGE were virtually undetectable in the coatings studied.

7.6 Epichlorohydrin Epichlorohydrin (1-chloro-2,3-epoxypropane), is a carcinogen and a precursor to epoxy resin monomers. A method for the detection of epichlorohydrin in epoxy coatings by n-pentane extraction and analysis by GC with flame ionisation detection or selective-ion mass spectroscopy has been developed (a.35) The respective limits of detection were 0.05 μg/ml for the former, and 0.02 μg/ml for the latter. However, no epichlorohydrin was detected. The analysis of foodstuffs for epichlorohydrin has figured in one study where headspace GC-MS with selective ion detection was used to give a sensitivity of 0.02 mg/kg (a.36) No epichlorohydrin was detected in this survey.

7.7 Bisphenol A Although there is conflicting evidence regarding the safety of BPA, it has been targeted by organisations such as Friends of the Earth (FoE) and placed within a group of chemicals that are regarded as known, or suspected endocrine disruptors, and/or are bioaccumulative. FoE have been successful in persuading a number of major retailers (e.g., Marks and Spencer, Boots and B&Q) to sign a pledge committing them to identify products that contain such chemicals and phase them out by 2008 (a.37). To help the retailers, FoE provided official lists, such as those issued by the Swedish, Danish and Dutch governments, and the companies used these to help themselves draw up a list of 15-20 priority substances. For example, one of the substances on the list were epoxy resin lacquers, containing BPA, which were used on the food contact side of the metal lids on food jars. These were phased out during 2004 and replaced by a non-epoxy resin lacquer (194).

7.8 Solvents Where solvents are used, they are required for application purposes, and efficient drying would be

expected to drive much of the solvent from the product. Nevertheless, migration of solvent residues from printing inks can be a possible source of off-flavour in food (a.38) Given the wide volatility range of solvents exploited in the control of film formation, it might be expected that some of the higher boiling solvents (e.g., glycol ethers) might remain in the dried film product. Residual alkylbenzenes (C10-C13 chain length) have been found to migrate into hamburger rolls and into a Tenax food simulant (a.39) Printed hamburger collars had alkylbenzene contents in the range 70-500 mg/kg, and migration from the collar resulted in levels of 2 mg/kg in the hamburger rolls.

7.9 Plasticisers Work by the Norwegian Food Safety Authority showed that a plasticiser used in ink formulations, n-ethylo/p-toluene-sulfonamide (N-ETSA), migrated into packaged cheese at a level of 13 mg/kg. Although there is no specific migration limit for N-ETSA in particular, European legislation prescribes a limit of 0.1 mg/kg for sulfonamides having a similar chemical structure. The level found by the Norwegians is obviously significantly higher than this, but these types of problems can be avoided by the use of polymeric type plasticisers/flexibilisers that have a greatly reduced potential to migrate. This targeted piece of research is complemented by a surveillance exercise of food packaging materials undertaken by the same authority. When a printed laminate was tested, N-ETSA was found to have migrated into the water and oil olive simulants. Other plasticiser and ink related species were also detected and quantified (59).

7.10 Extractables from UV-Cured Coating for Cardboard Gaube and Ohlemacher (216) have reported on the parameters that affect the extractables of cationic UVcured coatings that are applied to cardboard. Specific migration and extraction experiments were carried out to determine the affect of changing parameters such as pre-treatment of the cardboard, and the formulation of the coating, on the concentration of the cationic photoinitiator (Bis[4-(diphenylsulfonio)-phenyl]sulfidebis-hexafluorophosphate) and the epoxy monomer (3,4-epoxycyclohexylmethyl-3´,4´-epoxycyclohexane carboxylate).

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Coatings and Inks for Food Contact Materials

7.11 Potential Migrants A recent research project looking at the potential migrants present in coatings and inks used on the nonfood contact side of food packaging was carried out at Rapra Technology (a.8). This project was sponsored by

the UK FSA and, as a part of the final report, important species that had the potential to migrate were tabulated. This information is reproduced in Table 17. A subjective importance rating based on toxicity, potential abundance, mobility and molecular weight is provided in Table 17.

Table 17. Possible Impurities and Breakdown Products Identified by the FSA Coatings and Inks Project Listed in this Table are species not included in either the CoE or BCF Inventory lists. The entries here are based on the chemistry discussed in the final FSA report (copy available from the FSA – see Section 10), and reference should be made to the appropriate section of this report for due context. This compilation is intended to illustrate some of the possibilities and is not intended to be exhaustive. A subjective importance rating based on toxicity, potential abundance, mobility, and molecular weight are also provided. (1 = High, 2 = Medium, 3 = Low) Relative importance

CAS No

Substance

ADI/TDI or SML etc.

Source

79-06-1

Acrylamide

Not established Possible carcinogen

Precursor to polyacrylamide (water-soluble binder)

1

95-23-8

5-Aminobenzimidazolone, (5-amino-1,3-dihydro-2Hbenziimidazol-2-one)

Aromatic amine SML = Not detectable

Precursor/breakdown product of PY 194

1

873-74-5

4-Aminobenzonitrile

Aromatic amine SML = Not detectable

Possible breakdown product of PY 181

1

62-53-3

Aniline

Aromatic amine SML = Not detectable

Precursor/breakdown product of PR 2, PY 1 & PY 12

1

1

71-43-2

Benzene

Carcinogen

Possible breakdown product of sulfonium photoinitiator. Possible impurity in unsaturated polyester binders

25834-80-4

2,4-Bis(p-aminobenzyl)aniline

Aromatic amine SML = Not detectable

Possible precursor/ breakdown product of PU binders

1

−

Bis(thiophenyl)benzene

Lack of information

Possible breakdown product of sulfonium photoinitiator

1

6358-64-1

4-Chloro-2,5dimethylaniline

Aromatic amine SML = Not detectable

Precursor/breakdown product of PY 83

1

101-77-9

4,4′-Diaminodiphenylmethane, (4,4 methylenedianiline)

Aromatic amine SML = Not detectable

Possible precursor/breakdown product of PU binders. Possible curing agent in epoxy binders

1

91-04-1

3,3′-Dichlorobenzidine

Aromatic amine SML = Not detectable

Precursor to PY 12, 13, 14, 17, 55 & 83

1

119-90-4

3,3′-Dimethoxybenzidine, (o-dianisidine)

Aromatic amine SML = Not detectable

Precursor to PO 16

1

95-68-1

2,4-Dimethylaniline, (2,4-xylidine)

Aromatic amine SML = Not detectable

Precursor/breakdown product of PY 13

1

48

Coatings and Inks for Food Contact Materials

Table 17. Continued Relative importance

CAS No

Substance

ADI/TDI or SML etc.

Source

94-70-2

2-Ethoxyaniline, o-phenetidine

Aromatic amine SML = Not detectable

Precursor/breakdown product of PR 170

1

90-94-0

2-Methoxyaniline, o-anisidine

Aromatic amine SML = Not detectable

Precursor/breakdown product of PY 17

1

95-53-4

2-Methylaniline (o-toluidine)

Aromatic amine SML = Not detectable

Precursor/breakdown product of PR 12, PY 14

1

106-49-0

4-Methylaniline (p-toluidine)

Aromatic amine SML = Not detectable

Precursor/breakdown product of PY 55

1

99-08-1

m-nitrotoluene (3-nitrotoluene)

Possibly some genotoxicity

Possible breakdown product of PY 1, PR 3 & PR 12

1

95-80-7

2,4-toluenediamine, (2,4 diaminotoluene)

Aromatic amine SML = Not detectable

Possible precursor/breakdown product of PU binders

1

823-40-5

2,6-toluenediamine, (2,6 diaminotoluene)

Aromatic amine SML = Not detectable

Possible precursor/breakdown product of PU binders

1

2835-68-9

p-Aminobenzamide

SML = 0.05 mg/kg (only to be used in PET)

Precursor/breakdown product of PY 181

2

100-66-3

Anisole (methoxybenzene); (methyl phenyl ether)

Lack of information

Possible breakdown product of PY 194

2

55-21-0

Benzamide

Not in 2002/72/EC

Possible breakdown product of PR 170

2

92-52-4

Biphenyl

Fungicide used with oranges

Possible breakdown product of sulfonium photoinitiator

2

2409-55-4

2-Tert-butyl-4-methylphenol

Relatively common breakdown product

Possible breakdown product of BHT (antioxidant)

2

2460-77-7

2,5-Di-tert-butyl-1,4benzoquinone

Lack of information

Possible breakdown product of BHT

2

1620-98-0

3,5-Di-tert-butyl-4hydroxybenzaldehyde

Lack of information

Possible breakdown product of BHT

2

106-46-7

p-Dichlorobenzene, (1,4-dichlorobenzene)

SML = 12 mg/kg (2002/72/EC)

Possible breakdown product of PR 2

2

−

2,4-Diethyl-9H-thioxanthen9-ol

Lack of information

Possible breakdown product of DETX

2

91-01-0

Diphenyl-2-methanol (benzhydrol)

Limited information found

Possible breakdown product of benzophenone

2

139-66-2

Diphenyl sulfide (phenyl sulfide)

Lack of information

Possible breakdown product of sulphonium photoinitiator

2

4088-22-6

Distearylmethylamine

Lack of information

Possible breakdown product of dimethyldioctadecylammonium chloride

2

100-41-4

Ethylbenzene

Common impurity in styrenics

Possible impurity in unsaturated polyester binders

2

−

4,4′-Ethylenebis(2,6-di-tertbutylphenol)

Lack of information

Possible breakdown product of BHT

2

−

4-Hydroxymethylphenyl-4′methyldiphenyl sulfide

Lack of information

Possible breakdown product of 4-benzoyl-4′methyldiphenyl sulfide

2

49

Coatings and Inks for Food Contact Materials

Table 17. Continued Relative importance

CAS No

Substance

ADI/TDI or SML etc.

Source

92-70-6

β-Hydroxynaphthoic acid, (3-Hydroxy-2-naphthoic acid), (2-Hydroxy-3naphthoic acid)

Lack of information

Precursor/breakdown product of PR 48:2

2

−

p-Iodoisobutylbenzene

Lack of information

Possible breakdown product of diaryliodinium photoinitiator

2

624-31-7

p-Iodotoluene

Lack of information

Possible breakdown product of diaryliodinium photoinitiator

2

538-93-2

Isobutylbenzene (2-methyl-1-phenylpropane)

Lack of information

Possible breakdown product of diaryliodinium photoinitiator

2

2855-13-2

Isophorondiamine (5-amino-1,3,3-trimethylcyclohexane-methylamine)

Lack of information

Possible precursor/breakdown product of PU binders

2

−

2-Isopropyl-9H-thioxanthen- Probably considered in 9-ol EFSA review of ITX

Possible breakdown product of ITX

2

Hexamethylenediamine

SML = 2.4 mg/kg

Possible precursor/breakdown product of PU binders

2

SCF list 8

Possible modifier in alkyd binders

2

Lack of information

Possible breakdown product of PO 64

2

Lack of information

Possible precursor/ breakdown product of PU binders

2

Lack of information

Precursor/breakdown product of PR 3

2

Possible precursor to polyester binder. Precursor/ breakdown product of neopentyl glycol plasticisers

2

124-09-4 26266-77-3

(1,6-hexanediamine) Hydroabietyl alcohol 5-Methylbenzimidazolone

−

1761-71-3

135-19-3

126-30-7

(5-methyl-1,3-dihydro-2Hbenziimidazol-2-one) 4,4′-Methylenebis(cyclohexylamine) β-Naphthol (2-hydroxynaphthalene) Neopentyl glycol

SML = 0.05 mg/kg in (2,2-dimethyl-1,3-propanediol) 2002/72/EC

104-40-5

4-Nonylphenol

TDI (NP) = 0.005 mg/kg body weight/day

Precursor to ethoxylated nonylphenol surfactants

2

11066-49-2

Isononylphenol

TDI (NP) = 0.005 mg/kg body weight/day

Precursor to ethoxylated nonylphenol surfactants

2

140-66-9

4-(tert-octyl)phenol, [4-(1,1,3,3-tetramethylbutyl)phenol]

Lack of information

Precursor to ethoxylated octylphenol surfactants

2

85-41-6

Phthalimide

Lack of information

Precursor/breakdown product of PB 15 and 15:1-15:6

2

638-65-3

Stearonitrile

Lack of information

Possible breakdown product of stearic acid amide

2

50

Coatings and Inks for Food Contact Materials

Table 17. Continued CAS No

Substance

ADI/TDI or SML etc.

Source

−

3,3′,5,5′-tetrabis(tert-butyl)4,4′-stilbenequinone

Lack of information

Possible breakdown product of BHT

108-88-3

Toluene

124-04-9

Adipic acid

Some toxicity

Listed in 2002/72/EC. No SML

Possible breakdown product of diaryliodinium photoinitiator. Possible impurity in unsaturated polyester binders

Relative importance 2

2

Possible precursor to alkyd binders

3

Breakdown product of DMPA initiator. Possible impurity in unsaturated polyester binders

3

3

100-52-7

Benzaldehyde

Listed in 2002/72/EC. Warning given re: possible tainting of food

91-76-9

Benzoguanamine (2,4-Diamino-6-phenyl1,3,5-triazine)

QMA = 5 mg/6 dm2

Possible precursor to amino binders

74-87-3

Chloromethane, (methyl chloride)

bp – 24 °C

Possible breakdown product of cationic surfactants

461-58-5

Cyanoguanidine (dicyanodiamide)

Listed in 2002/72/EC. No SML

Possible curing agent in epoxy binders

3

−

N,N-Dimethylcocoalkylamine

Not listed in 2002/72/EC but probably of low toxicity

Possible breakdown product of (cocoalkyl)trimethylammonium chloride

3

−

Di-n-octyltin mono(2ethylhexyl mercaptoacetate monochloride)

Possible breakdown product Controlled by SML(T) of of di-n-octyltin bis(20.006 mg/kg expressed as tin ethylhexyl mercaptoacetate in 2005/79/EC (in PVC)

3

693-23-2

Dodecandioic acid, (1,10decanedicarboxylic acid)

In 2002/72/EC No SML

104-76-7

2-Ethyl-1-hexanol, (isooctyl Low toxicity alcohol)

110-17-8

Fumaric acid

97-65-4

Possible precursor to polyester binder

3

Precursor to 2-ethylhexyl phthalate plasticisers

3

Listed in 2002/72/EC. No SML

Possible precursor to alkyd binders

3

Itaconic acid (methylenesuccinic acid)

Listed in 2002/72/EC. No SML

Possible impurity in watersoluble binders

3

108-78-1

Melamine

SML = 30 mg/kg in 2002/72/EC

Possible precursor to amino binders

3

−

Mono-n-octyltin bis(2ethylhexyl mercaptoacetate) monochloride

Possible breakdown product Controlled by SML(T) of of mono-n-octyltin tris(20.006 mg/kg expressed as tin ethylhexyl mercaptoacetate) in 2005/79/EC (in PVC)

3

−

Mono-n-octyltin mono(2ethylhexyl mercaptoacetate) dichloride

Possible breakdown product Controlled by SML(T) of of mono-n-octyltin tris(20.006 mg/kg expressed as tin ethylhexyl mercaptoacetate) in 2005/79/EC (in PVC)

3

−

Oxides of nitrogen

Nitrous oxide is used as a propellant gas with food products

3

Possible breakdown product of nitrocellulose binders

51

Coatings and Inks for Food Contact Materials

Table 17. Continued Relative importance

CAS No

Substance

ADI/TDI or SML etc.

Source

111-20-6

Sebacic acid

Listed in 2002/72/EC. No SML

Possible precursor to alkyd binders

3

50-70-4

Sorbitol

Listed in 2002/72/EC. No SML

Possible precursor to alkyd resins

3

77-99-6

Trimethylolpropane

SML = 6mg/kg in 2002/72/ EC

Possible precursor to alkyd resins

3

ADI: TDI: DETX: BHT: NP: QMA: bp: SML (T): DMPA: PVC:

Acceptable daily intake Tolerable daily intake 2,4-diethylthioxanthane Butylated hydroxyl toluene Nonyl Phenol Maximum permitted quantity of substance in the finished product Boiling point Total of substances/moieties listed 2,2 Dimethoxy-2-phenylacetophenane Polyvinylchloride

In many coatings and inks products, the drying (curing) mechanisms rely on reactive systems and the reaction products are included in Table 17. Some substances such as styrene, BADGE and the photoinitiator ITX have already been the subjects of migration studies (see Section 7.4). Other important by-products of initiator action include benzaldehyde, benzene, biphenyl and diphenyl sulfide. Aromatic amines are used in the manufacture of azo dyes and pigments, and amines are also potential breakdown products from the hydrolysis of amides, unreacted isocyanates or the action of heat on cationic surfactants, all used with inks and coatings. Commission Directive 2002/72/EC details that materials and articles manufactured by using aromatic isocyanates or colorants prepared by diazo-coupling, shall not release primary aromatic amines (expressed as aniline) in a detectable quantity - detection limit = 0.02 mg/kg of food or food simulant, analytical tolerance included. In the list of possible important impurities and breakdown products in Table 17, fifteen non-permitted aromatic amines are detailed. A further important precursor/pigment breakdown product that is included is the potentially genotoxic substance nitrotoluene. Many starting substances currently used in food use coatings and inks are not listed in Inventory lists (e.g.,

52

such as the Council of Europe’s – see Section 5.2) and have not yet been evaluated by the European Food Safety Authority (EFSA).

8 Improving the Safety of Inks and Coatings for Food Use 8.1 New Food Approved Pigments Work is on-going to widen the range of pigments that can be used for food contact applications, and a steady stream of new products from the manufacturers is being brought onto the market. In addition to providing alternatives to pigments that do not have food approval, other improvements cited are the ability to used in higher loadings and the wider range of manufacturing processes and conditions for which the pigments are compatible (89), (119) and (132)

8.2 Water-Based Systems The exposure of humans to phthalate ester compounds has been a concern now for many years, with the first major press release by MAFF warning of the potential

Coatings and Inks for Food Contact Materials

for migration from packaging materials, particularly cling film, coming in the middle of the 1980s. The most widely used phthalate, di-ethylhexyl phthalate has been linked in animal studies to damage to the kidneys and liver, and has been labelled as a probable human carcinogen (199) and (204). Phthalate plasticisers are still used in some coating and ink formulations and this has assisted the development of a new generation of water-based coatings, which are free of phthalates (80). In addition, these coatings, which can be used for a wide range of applications, have the additional benefit of being free from VOC, which assists manufacturers in their endeavours to meet environmental emission targets for these types of compounds. However, there is now a further move, to newer technology using UV/EB curing systems (see Section 8.3).

of substances used in UV/EB curable coatings, ink and adhesive materials (46).

8.4 New Initiators for UV Curable Inks As mentioned previously, UV curable inks are gaining in popularity over conventional solvent and water based inks. Although this technology offers a number of benefits, it is appreciated that one area where there is scope for more work is in the development of a greater range of initiators that do not produce breakdown and reaction products that can cause taint and odour problems in food contact applications (115).

8.3 UV/EB Curable Systems

9 Future Trends

For a number of years now there has been a move away from water-and solvent-based coating and ink systems and towards the use of formulations that can be cured by utilising either the energy produced by an UV source or an EB. In addition to offering advantages in ease of handling, superior flow characteristics and low odour, the technology results in a lower level of potential migrants in the final product – an obvious benefit for food contact applications (202) (205). However, although offering some common benefits, the two technologies are quite different and the EB curing mechanism is regarded as having a number of advantages over the ultraviolet light curing mechanism for food packaging applications (174) (172). Examples of these advantages include: a higher degree of reaction (giving a lower level of extractables), a higher processing speed, and that fact that no initiator breakdown products are generated.

In addition to the constant improvements in the safety of coatings and inks, which are described in Section 8, there are also a number of technological improvements surrounding the coatings and inks industry that are worth mentioning. Some principal examples of these, together with the citation of some relevant recently published literature, are covered next.

Despite the advantages that these techniques offer, there are still some manufacturing problems that are encountered. For example, a problem that can be experienced when off set printers use UV ink technology is poor adhesion to the substrate (either plastic or metal), due to either poor wetting or film shrinkage, or a combination of the two. This is being addressed by applying modifications to the technology (e.g., the development of new resins), and by raising the surface energy of certain substrates (e.g., polyolefins) by using in-line techniques such as Corona discharge treatments (110). To facilitate the expansion and acceptance of UV/EB technology for food contact products, the RadTech Food Packaging Alliance has been formed and it has sponsored the production of migration data on a number

9.1 Improvements in Recycling Systems Although the use of multi-layer, laminate products for the packaging of food can cause problems when it comes to recycling them at the end of their life (see Section 9.2), systems are being developed that can cope with packaging that has a coating or is multi-layered. An example of this is a plant that can recycle polyethylene terephthalate (PET) beer bottles to generate a food grade resin that can be re-used in drinks bottles (150).

9.2 Biodegradability Biodegradability and compostibility are becoming increasing attractive attributes for all food contact products, as the need to reduce the amount of waste that is placed into conventional landfill sites. This is a particularly advantageous property for products that are made up of a number of different polymer based components, which makes recycling an unattractive option due to separation problems. An example of the new, multi-component biodegradable products that are coming onto the market is lunch

53

Coatings and Inks for Food Contact Materials

box sheet, where the film, adhesive and ink are all biodegradable. This enables the complete product to be placed into a composter for disposal (124).

9.3 Use of Coatings to Improve Barrier Properties of Food Packaging Coatings can be used to improve the barrier properties of food packaging films, and hence increase the shelf life of food and beverages. In addition to decreasing the amount of permeation that takes place, these coatings can also have secondary benefits when used in laminating products, such as improving the interlayer adhesion (44).

able to withstand both high temperature processing and acidic environments and, being a hydrophobic protein, has ‘Generally recognised as safe’ status in the USA for use in cheese products (198). In addition to Nisin, chitosan (a polysaccharide and deacetylated form of chitin) also shows promise as a natural antimicrobial for use in paper binders (192). Gergely has recently reviewed the regulatory situation in the EU with respect to additives in food contact materials that exhibit antimicrobial activity (154).

9.5 Laser Marking to replace Conventional Inks

Nanotechnology is being incorporated into a wide range of manufacturing sectors, and one application of it in food packaging is to improve the barrier properties of films. This can be achieved by the use of thin polymer films that contain nanoclay particles (136).

Continual improvements in laser technology have resulted in a system for plastics that offers indelibility coupled with high speed (58). Given that a laser pigment for this type system has received FDA approval, this type of technology could begin to mount a credible challenge to conventional inks in the future.

Grande has recently discussed the latest developments in barrier technologies, including coatings, with respect to polyethylene terephthalate polyester bottles (73).

9.6 Intelligent and Active Packaging

9.4 Antimicrobial Systems Interest in the use of antimicrobial products for the food industry is growing. Their has been a lot of activity in the development of antimicrobial additives for food contact rubbers and, in order to create a antimicrobial coating for rubbers, silver nanoparticles have been deposited onto the surface of food contact silicone rubbers (32). These types of products are also being developed for the coatings and inks industries. A particular example is a white pigmented powder coating type paint for the food processing industry that has antimicrobial functionality due to the presence of silver ions (131). The use of a silver glass ceramic antimicrobial additive for the inner surfaces of refrigerators has already been mentioned in Section 3.3. In the food packaging area, antimicrobial technologies (e.g., in the form of an internal coating) have the potential to extend the shelf life of perishable products. In the case of the food processing industry, paints are being developed that contain anti-microbial additives such as silver glass and silver zeolite (131). The anti-microbial properties of paper and board type food packaging materials can be improved by the use of polymer binder solutions that have been treated with Nisin, a bacteriocin produced by Lactococcus lactis. This natural anti-microbial agent has the benefits of being

54

A definition of intelligent packaging is the kind of packaging that uses devices within the pack or as part of the package itself to sense and register certain changes in the pack and its contents. Areas of intelligent packaging that are attracting an increasing amount of attention are the development of time-temperature indicators and, for foods that have been packaged under inert environments, oxygen sensors. In the case of oxygen sensors, it is important that they are non-evasive and an example of the type of product which is of relevance in this report is the use of an oxygen sensor that can be printed as an ink onto packaging (177). Active packaging is the term used to describe packaging products that are not simply passive protectors of the food within them, but interact with the product to maintain its integrity and increase its shelf life. Examples of active packing include (190): a) The scavenging of ethylene to slow the ripening of fruits and vegetables b) The scavenging of oxygen to prevent things such as the development of odours, changes in colour, and mould growth. c) Use of gases such as carbon dioxide or sulfur dioxide to prevent microbiological growth.

Coatings and Inks for Food Contact Materials

9.7 Applications of Nanotechnology The use of nanotechnology to improve the barrier properties of food packaging has been mentioned in Section 9.3. Another area where nanotechnology shows considerable promise is where nanoparticles in inks can be used to improve the capability of radio frequency identification technology. In addition to conventional bar code type information, this would also enable addition information such as the state of the food in the packaging to be accessed. Another area that is under development and evaluation is the use of nanoparticles as pigments in inks. The use of nanotechnology to produce intelligent packaging is also being investigated by a team at Strathclyde University (158). It was the increasing use, and potential use in the future, of nanotechnology in food packaging applications that led the FSA to fund a project to assess the impact that this technology could have on the safety of food contact materials. Information on this project, which started in 2005, can be found on the FSA’s web site (see Sources of Information.

9.8 Developments in Analytical Techniques Analytical chemistry plays a vital role in the assessment of food safety of all food contact materials and is invaluable in the determination of the specific migration behaviour of selected, targeted species. For many years, HPLC was, in practice, the only available technique for the determination of thermally labile and/or relatively high molecular weight migrant species. However, in the past five years or so LC-MS instruments have proliferated to the extent that they have now replaced HPLC in the majority of laboratories. These instruments are a much better complement for GC-MS, than HPLC, and enable the analyst for the first time to routinely generate data on a full range of compounds (i.e., thermally labile, stable and polar substances, such as salts) up to 1000 daltons, which is the established upper limit for chemical absorption in the gastrointestinal tract. LC-MS enables more accurate conformity checks to be performed on coatings and inks formulations, as well as adding to the understanding of the migration behaviour of their low molecular weight constituents and reaction and breakdown products. Development work also continues to provide analytical instrumentation which offers commercially accessible improvements in important parameters such as molecular weight range, detection limits, software assisted peak deconvolution, analysis speed, accuracy of library

searching and species selectivity. The introduction of mid-priced multi-hyphenated techniques such as GCxGC-time-of flight MS and LC-MSxMS are examples of this. In addition to contributing to conformity work, and the analysis of food simulants, these instruments with their greater resolving power and selectivity are also improving routine, direct analysis of food products, where the potentially large range of low molecular weight species can cause interference problems.

10 Conclusion This review has provided the reader with an overview of the types of coatings and inks that are used for food contact materials, an introduction to the technology that is associated with their manufacture and an overview of the legislation that is associated with these types of products. It has also provided a summary of the migration data that is available and a description of the advances that are being taken by industry to improve the safety and functionality of these types of products. Food contact legislation for coatings and inks within the EU has been a very active area recently, with both a CoE resolution on coatings, and one for inks for non-direct food use, having been adopted within the last couple of years. The latter document has proved to be controversial, with industry groups such as the BCF and EuPIA being far from happy with it, and providing their own inventory list and guideline documents in response. For the analysis of coatings and inks, the commercial proliferation of LC-MS instruments, with their enhanced capability compared to the much older HPLC technique, and complimentary status to GC-MS, will be of great benefit to analysts who are carrying out tasks ranging from reverse engineering and failure diagnosis to migration studies. This technique will enable all of this work to be carried out with greater ease and effectiveness, and may assist in the work required to generate EU regulations for both coatings and inks. The product groups within the inks and coatings sector are experiencing a number of important developments. Some of these address environmental concerns, such as the move from solvent-based systems to water-based products, and the increased use of biodegradable materials, whereas others, such as the use of nano-materials, the use of antimicrobial agents, and those to produce active/ intelligent packaging, are designed to create products that provide the customer and the retailer with products having greater degrees of safety and quality.

55

Coatings and Inks for Food Contact Materials

Coatings and inks for food contact materials will continue to be a very active and dynamic area of the polymer industry for the foreseeable future.

Subject to Limitation - Part 13: Determination of 2,2-Bis(4-Hydroxyphenyl)Propane (Bisphenol A) in Food Simulants, 2005. a.11.

CEN/TS 13130-26, Materials and Articles in Contact with Foodstuffs - Plastics Substances Subject to Limitation - Part 26: Determination of 1-Octene and Tetrahydrofuran in Food Simulants, 2005.

a.12

EN 13130-11, 2004, Materials and Articles in Contact with Foodstuffs – Plastics Substances Subject to Limitation - Part 1: Guide to Test Methods for Specific Migration, 2004.

a.13

S.M. Jickells, C. Crews, L. Castle and J. Gilbert, Food Additives and Contaminants, 1990, 7, 2, 197.

a.14

J. Salafranca and R. Franz, Deutsche Lebensmittel Rundschau, 2000, 96, 10, 355.

a.15

ISO 13302, Sensory Analysis - Methods for Assessing Modifications to the Flavour of Foodstuffs Due to Packaging, 2003.

a.16

EN 1230-1, Paper and Board Intended for Contact With Foodstuffs - Sensory Analysis - Part 1: Odour, 2001.

a.17

ISO 4120, Sensory Analysis - Methodology - Triangular Test, 2004.

a.18

ISO 5492, Sensory Analysis – Vocabulary, 2005.

a.19

D. van Deventer and P. Mallikarjunan, Innovative Food Science Emerging Technology, 2002, 3, 1, 93.

a.20

M. Frank, U. Ulmer, J. Ruiz, P Visani and U Weimar, Analytica Chimica Acta, 2001, 431, 1, 11.

a.21

C. Brede, I. Skjevrak and P. Fjeldal, Colour Substances in Food Packaging Materials, SNT Arbeidsrapport, Oslo, Norway, 2003.

a.22

C. Brede, I. Skjevrak and H. Herikstad, Journal of Chromatography A, 2003, 983, 1-2, 35.

a.23

L. Castle in Proceedings of the PIRA conference, Plastics and Polymers in Contact with Foodstuffs, Coventry, UK, 2003.

a.24

K. Bouma and E. Wijma, Migration of Primary Aromatic Amines from Multilayer Films for Food Packaging, The Netherlands Inspectorate for Health Protection and Veterinary Public Health, Report No. ND1FC004/01, 2002.

Additional References a.1

M.J Forrest et al, Food Standards Agency Project A03046 – Chemical migration from silicones used in connection with food contact materials and articles, Food Standards Agency, London, UK, 2003-2005.

a.2

R. Good, Contribution to Food Standards Agency Project A03046 – Chemical migration from silicones used in connection with food contact materials and articles, Food Standards Agency, London, UK, 2003-2005.

a.3

a.4 a.5

a.6 a.7

a.8

a.9

a.10

56

R. Good, Presentation on Speciality Coatings and Varnishes for Metal & Flexible Packaging, Food Packaging Interactions, Campden and Chorleywood Food Research Association, Chipping Campden, UK, 2005. K. Johns in Proceedings of Silicone in Coatings IV, Guildford, UK, 2002, Paper No.13. WHO Surveillance Programme for Control of Foodborne Infections and Intoxications in Europe, 7th Report 1993-1998, EDS., C. Tirado and K. Schmidt, FAO/WHO Collaborating Centre for Research and Training in Food Hygiene and Zoonoses, Berlin, Germany, 2000. Trade Literature, Stirling Lloyd Polychem Ltd, Knutsford, UK, 2002. C. Whitehead in Proceedings of European Food Packaging Regulations: Support from your Printing and Coating Suppliers, EuPIA seminar, Solihull, UK, 2006. M.J. Forrest et al, Food Standards Agency Project A03055 – An Assessment of the Potential of Migration of Substances from Inks and their Associated Coatings, Food Standards Agency, London, UK, 2005-2007. CEN/TS 13130-25, Materials and Articles in Contact with Foodstuffs - Plastics Substances Subject to Limitation - Part 25: Determination of 4-Methyl-1-Pentene in Food Simulants, 2005. CEN/TS 13130-13, Materials and Articles in Contact with Foodstuffs - Plastics Substances

Coatings and Inks for Food Contact Materials

a.25

N. Palibroda, J. Brandsh, O. Piringer and R. Brandsh, Journal of Mass Spectrometry, Letters, 2004, 39, 12, 1484.

Sources of Further Information and Advice

a.26

MAFF, Survey of Benzene in Food Contact Plastics, Food Surveillance Information Sheet, No 35, September, MAFF, London, UK, 1994.

a.27

S.L. Herlihy, B. Rowatt and R.S. Davidson, RadTech Europe Papers of the Month – August 2004, RadTech Europe, The Hague, Netherlands, 2004.

There are a number of routes that a researcher can take to obtain further information. It is not possible within this format to provide a comprehensive list, but this section provides a summary of the key areas where knowledge can be found, with a number of examples included in each category.

a.28

The EFSA Journal, 2005, 293, 1.

a.29

J.A. Brotons, M.F. Olea-Serrano, M. Villalobos, V. Pedraza and N. Olea, Environmental Health Perspectives, 1995, 103, 6, 608.

a.30

MAFF, Survey of BADGE epoxy monomer in canned foods, Food Surveillance Information Sheet, No 125, October, MAFF, London, UK, 1997.

a.31

A.H. Windle in Polymer Permeability, Ed., J. Comyn, Elsevier Applied Science, London, UK, 1985.

a.32

R.S. Garcia, P.P. Losada and C.P. Lamela, Chromatographia, 2003, 58, 5-6, 337.

a.33

N. Leepipatpiboon, O. Sae-Khow and S. Jayanta, Journal of Chromatography, A, 2005, 1073, 1-2, 331.

a.34

I. Jordakova, J. Dobias, M. Voldrich and J. Poustka, Czech Journal of Food Sciences, 2003, 21, 3, 85.

a.35

H. Ohno, M. Suzuki, T. Aomaya and K. Mitani, Shokuhin Eiseigaku Zasshi, 2003, 44, 6, 332.

a.36

MAFF, Survey of Chemical Migration from Can Coatings into Food and Beverages, 2. Epichlorohydrin, Food Surveillance Information Sheet, No 170, January, MAFF, London, UK, 1999.

Reference Books 1. T.A Turner, Canmaking: The Technology of Metal Protection and Decoration, Crown Cork and Seal, Blackie Academic and Professional, London, UK, 1997. 2. Manual for Resins for Surface Coatings, Volume 2, Eds., P. Oldring and G. Haywar, SITA Technology, London, UK, 1987. 3. T. Hutton, Food Manufacturing: An Overview, CCFRA, Chipping Camden, UK, 2001. 4. T. Hutton, Introduction to Food Hygiene in Food Processing, CCFRA, Chipping Camden, UK, 2007. 5. T.Hutton, Food Packaging, CCFRA, Chipping Camden, UK, 2003. 6. N. Anyadike, Introduction to Flexible Packaging, PIRA, Leatherhead, UK, 2003. 7. The Printing Ink Manual, 5th Edition, Eds., R.H Leach and R.J Pierce, Kluwer Academic Publishers, Dordrecht, The Netherlands, 2002. 8. P. Oittinen and H. Saarelma, Printing, Fapet Oy, Helsinka, Finland, 1998. 9. Lacquers, Varnishes and Coatings for Food and Drink Cans and for the Metal Decorating Industry, ICI Packaging Coatings, 2000.

a.37

ENDS Report, 2002, No.331, 31.

a.38

M. Huber, J. Ruiz and F. Chastellain, 2002, Food Additives and Contaminants, 2002, 19 Supplement 1, 221.

10. Chemical Migration and Food Contact Materials, Eds., K.A. Barnes, C.R. Sinclair and D.H. Watson, Woodhead Publishing, Cambridge, UK, 2006.

a.39

B. Aurela, T. Ohra-Aho and L. Soderhjelm, Packaging Technology and Science, 2001, 14, 2, 71.

11. Migration from Food Contact Materials, Ed., L.L. Katan, Blackie Academic and Professional, London, UK, 1996.

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Coatings and Inks for Food Contact Materials

12. Additives for Coatings, Ed., J. Bieleman, WileyVCH, Weinheim, Germany, 2000.

Professional, Research, Trade and Governmental Organisations

13. Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume II: Prepolymers and Reactive Diluents, Ed., G. Webster, John Wiley, Chichester, UK, 1997.

Council of Europe – Partial Agreement in the Social and Public Health Field, www.coe.int/soc-sp

14. J.P. Dowling, P. Pappas, B. Monroe and A. Carroy, Chemistry and Technology of UV and EB Formulation for Coatings, Inks & Paints, Volume V: Speciality Finishes, Wiley, Chichester, UK, 1997. 15. B. Thomson, Printing Materials: Science and Technology, PIRA International, Leatherhead, UK, 2004.

UK Food Standards Agency (FSA), www.foodstandards. gov.uk US Food and Drug Agency, www.fda.gov Bundesinstitut fur Risikobewertung (BfR) (German Federal Institute for Risk Assessment), www.bfr.bund.de The European Council of Paint, Printing Inks and Artists’ Colours Industry (CEPE), www.cepe.org

Reports 1. Food Standard Agency Reports Food Standard Agency/MAFF Projects on Food Contact Rubbers and Rubber Latex: A03043 – J. Haines et al., Assessment and quantification of latex protein (LP) transfer from LP-containing materials into food and drink products, 2004.

European Food Safety Association (EFSA), www.efsa. europa.eu Institute of Materials, Minerals and Mining (IOM3), www.iom3.org

A03038 – M.J. Forrest et al., Rubber Breakdown Products, 2005.

Leatherhead Food International, www.leatherheadfood.com

FS2248 – J.A. Sidwell et al., Further Migration Data on Food Contact Rubbers, 1997.

Central Science Laboratory, www.csl.gov.uk

FS2219 – J.A. Sidwell et al., Migration Data on Food Contact Rubbers, 1994.

PIRA International, www.pira.co.uk

M.J Forrest et al., Food Standards Agency Project A03046 – Chemical migration from silicones used in connection with food contact materials and articles, 2005. E. Bradley, Combined Food Standards Agency Projects FS2251 and A03022 – Overall Title : A systematic investigation into potential chemical migration from inks and associated coatings used on the food contact surface of packages, 2002. 2. British Coatings Federation, The BCF guide to printing inks for use on food wrappers and packages, Leatherhead, 2002. 3. C. Brede, I. Skjevrak and P. Fjeldal, SNT Arbeidsrapport, 2003, 3.

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European Printing Ink Manufacturers Association (EuPIA), www.eupia.org

Fraunhofer Institut Angewandte Polymerforschung, www.pioneers-in-polymers.com

Commercial Abstract Databases a) Rapra Abstracts (The Polymer Library) – Rapra Technology b) PIRA Abstracts – Pira International c) Chemical Abstracts – American Chemical Society d) World Surface Coatings Database – PRA Coatings Technology Centre

Coatings and Inks for Food Contact Materials

Acknowledgements The author would like to acknowledge the contribution made to this report by Dr Bryan Willoughby and Dr Ray Good. This arose out of the work that they were commissioned to do by Rapra Technology for the FSA Coatings and Ink project (Contract A03055). In particular, Dr Willoughby’s work been used in Chapters 2, 4 and 7 and Table 17, and Dr Good’s industry survey has been used as the basis for Chapter 3 and Tables 5 to 14.

Abbreviations

DRD

Draw redraw

DTA

Diethylene triamine

DWL

Drawn and wall ironed

EB

Electron beam

EFSA

European Food Safety Association

EFSA

European Food Safety Authority

EHDAB

2-Ethylhexyl-4-dimethylaminobenzoate

EOA

Ethylene diamine

EOE

Easy open end

EPDM

Ethylene-propylene-diene terpolymer

EU

European Union

EuPIA

European Printing Ink Manufacturers Association

ADI

Acceptable daily intake

BADGE

Bisphenol A diglycidyl ether

BCF

British Coatings Federation

BFDGE

Bisphenol F diglycidyl ether

EVA

Ethylene vinyl acetate

BHT

Butylated hydroxyl toluene

FOA

Food and Drugs Administration

bp

Boiling point

FOE

4´,4´ Diamino diphenyl-methane

BPA

Bisphenol A

FSA

Food Standards Agency

BPF

Bisphenol F

FSMD

Flat sheet metal decorating

CAB

Cellulose acetate butyrate

GC-MS

CEN

Comité Européen de Normalisation (European Committee for Standardisation)

Gas chromatography - mass spectrometry

GMP

Good manufacturing practice

GPTA

Propoxylated glyceryl triacrylate

HPLC

High performance liquid chromatography

IARC

International Agency for Research on Cancer

ITX

2-Isopropylthioxanthone

LC

Liquid chromatography

MAFF

Ministry of Agriculture, Fisheries and Food

CEPE CITPA

The European Council of Paint, Printing Inks and Artists’ Colours Industry International Confederation of Paper and Board Converters in Europe

CoE

Council of Europe

DEFRA

Department for Environmental, Food and Rural Affairs

DETX

2,4-Diethylthioxanthone

DICY

Dicyanidiamide

DMPA

2,2-Dimethoxy-2-phenylacetophenone

MS

Mass spectrometry

DNQ

Detected but not quantified

NC

Nitrocellulose

DPGDA

Dipropylene glycol diacrylate

Nd

Not detected by the method

59

Coatings and Inks for Food Contact Materials

N-ETSA

n-Ethyl-o/p-toluene-sulfonamide

QC

Quality control

NOGE

Novolal glycidyl ethers

QMA

NP

Nonyl Phenol

OML

Overall migration limit

Maximum permitted quantity of the substance in the finished material or article expressed as mg per 6 dm2 of the surface in contact with foodstuffs

PE

Polyethylene

QSAR

Quantitative structure-activity relationship.

PET

Polyethylene terephthalate REACH

PETA

Pentaerythritol tetra-acrylate

Registration, evaluation and authorisation of chemicals

PF

Phenol-formaldehyde

ROPP

Roll-on pilfer-proof

PP

Polypropylene

RTO

Regular twist off

ppb

Parts per billion

RTV

Room temperature vulcanising

ppm

Parts per million

SCF

PT

Press twist

Scientific Committee for Food (Pre EFSA)

PTFE

Polytetrafluoroethylene

SML

Specific migration limit(s)

PU

Polyurethane(s)

TDI

Tolerable daily intake

PVAc

Polyvinyl acetate

Tg

Glass transition temperature

PVB

Polyvinyl butyral(s)

UV

Ultra-violet

PVC

Polyvinyl chloride

VOC

Volatile organic compound(s)

PVOH

Polyvinyl alcohol

w/b

Water based

60

References and Abstracts

References from the Polymer Library Database Item 1 European Coatings Journal No.6, 2007, p.60-63 INTEGRATING THE PHOTOINITIATOR: SELFINITIATING RESINS PRODUCE UV COATINGS WITH FEW EXTRACTABLES Esselbrugge H Ashland The synthesis via the Michael reaction of self-initiating resins for UV coatings based on acrylate oligomers containing a photo-labile chromophore as a source of free radicals on exposure to UV irradiation is described. Films coated with the resins were subjected to extraction and migration tests with food simulants and the results are discussed in terms of potential food packaging applications. EUROPEAN COMMUNITY; EUROPEAN UNION; NETHERLANDS; WESTERN EUROPE

Accession no.998987 Item 2 Journal of Colloid And Interface Science 312, No.2, 2007, p.193-200 FLUORESCENCE PROBE TECHNIQUES TO MONITOR PROTEIN ADSORPTIONINDUCED CONFORMATION CHANGES ON BIODEGRADABLE POLYMERS Benesch J; Hungerford G; Suhling K; Tregidgo C; Mano J F; Reis R L Minho,Universidade; Portugal,Institute for Biotechnology and Bioengineering; King’s College The study of protein adsorption and any associated conformational changes on interaction with biomaterials is of great importance in the area of implants and tissue constructs. This study aimed to evaluate some fluorescent techniques to probe protein conformation on a selection of biodegradable polymers currently under investigation for biomedical applications. Because of the fluorescence emanating from the polymers, the use of monitoring intrinsic protein fluorescence was precluded. A highly solvatochromic fluorescent dye, Nile red, and a well-known protein label, fluorescein isothiocyanate, were employed to study the adsorption of serum albumin to polycaprolactone and to some extent also to two starch-containing polymer blends (SPCL and SEVA-C). A variety of fluorescence techniques, steady state, time resolved, and imaging were employed. Nile red was found to leach from the protein, while fluorescein isothiocyanate proved useful in elucidating a conformational change in the protein and the observation of protein aggregates adsorbed to the polymer surface. These effects were seen by making use of the phenomenon of energy migration between the fluorescent tags to monitor interprobe distance and

© Copyright 2007 Smithers Rapra Technology

the use of fluorescence lifetime imaging to ascertain the surface packing of the protein on polymer. 60 refs. Copyright (c) 2007 Elsevier Inc. EUROPEAN COMMUNITY; EUROPEAN UNION; PORTUGAL; UK; WESTERN EUROPE

Accession no.999065 Item 3 ANTEC 2007. Proceedings of the 65th SPE Annual conference held Cincinnati, Oh., 6th-11th May 2007. Brookfield, Ct., SPE, 2007, p.164-168, PDF 0214, CDROM, 012 ADVANCED TECHNOLOGIES FOR LASER MARKING OF PLASTICS Sabreen S R Sabreen Group Inc. (SPE) The newest generation of laser material science and hardware/software is driving strong industry demand for indelible, high speed laser marking processes to replace conventional ink printing. This paper presents a Ùtotal solutionsˆ methodology for achieving unprecedented marking contrast quality and colour laser marking of plastics via concomitant engineering of: 1) laser additive material science, 2) primary moulding operations, 3) laser/ software technology, and 4) systems integration. The first of its kind laser pigment to receive U.S. Food and Drug Administration (FDA) approval for use in laser processes is introduced as well as techniques to achieve high speed vector marking of alphanumeric text, graphics and product security codes. 4 refs. USA

Accession no.997413 Item 4 Applied Organometallic Chemistry 21, No.6, June 2007, p.412-424 DETERMINATION OF MIGRATION OF NBUTYLTINS AND N-OCTYLTINS TO FOOD SIMULANTS BY GAS CHROMATOGRAPHYMASS SPECTROMETRY Papaspyrou S D; Thomaidis; Lampi E N; Lioupis A Athens,University; Athens,General Chemistry State laboratory A simple gas chromatography/mass spectrometry method for the simultaneous determination of butyltin and octyltin compounds in water-based food simulants (water and 3% (w/v) acetic acid) is described and applied to various PVC samples (cling films, containers and water pipe. The method is based on one-step derivatisation/extraction with sodium tetraethyl borate directly in the aqueous phase in the presence of 1 ml of 0.05% (w/v) tropolone in hexane. Optimisation of the derivatisation conditions and

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References and Abstracts

calibration with mixed standard solutions of organotins are described. 51 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; GREECE; WESTERN EUROPE

Accession no.998245

char might only be considered as a potential for use as a co-fuel by relatively few industries. Juniper EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.995340 Item 5 Analytical Chemistry 79, No.8, 15th April 2007, p.3099-3104 MOLECULARLY IMPRINTED POLYMERIC FIBERS FOR SOLID-PHASE MICROEXTRACTION Turiel E; Tadeo J L; Martin-Esteban A Spain,Instituto Nacional de Investigacion y Tecnologia Agraria y Alimentaria A simple approach for the preparation of imprinted fibres, which involves the direct synthesis of the fibres using silica capillaries as moulds and the etching away of the silica after polymerisation. The method is demonstrated using the system propazine/methacrylic acid/ethylene glycol dimethacrylate as a model for the preparation of the fibres. The optimisation of variables affecting both polymer morphology and binding-elution conditions for target analytes is described and the performance of the imprinted fibres for the solid-phase microextraction of triazines from environmental and food samples evaluated. 15 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN; WESTERN EUROPE

Accession no.998248 Item 6 Banbury, Waste & Resources Action Programme, 2006, pp.47, ISBN, 30cm, 8(13). Online available from: http://www.wrap.org.uk/downloads/FINAL_Market_ Study_on_the_demand_for_char_11.01.07.f3e15db0.pdf (Accessed 11/06/07) MARKET STUDY ON THE DEMAND FOR CHAR FROM TYRE PYROLYSIS: PROJECT CODE: TYR020 Waste & Resources Action Programme This report focuses on the market opportunity for tyre derived char in the UK, and provides information on the potential magnitude of the opportunity for char derived from tyre pyrolysis, the potential market demand for char, and market accessibility. The study showed that there are two main potential opportunities to use tyre derived char in the near-term in the UK: using the material as a general low grade carbon black filler, and the possibility of using the char as a raw material for making pigments. The potential market for char as rubber filler is about 15,000-20,000 tonnes per year, and the possible demand in the carbon pigments industry is around 13,000-15,000 tonnes per year. Other end uses were investigated, but were found to have one or more technical, commercial, or regulatory issue. As a fuel,

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Item 7 New Scientist 194, No.2603, 12th May 2007, p.28-29 RECYCLED PLASTIC TO GET CLEAN BILL OF HEALTH Reilly M The techniques used to remove contaminants from plastic bottles before they can be recycled consume up to 2 litres of water per 500 grams of recycled material. This means plants cannot be built in areas where water is scarce. Waste from plants can also pollute local rivers. The plants typically earn around 1 cent per 500 grams of PETP they recycle, thanks to their high water and detergent bills, and to the low returns on selling the recycled plastic for industrial packaging. A new generation of plastics recycling plants will use technologies that reduce or even eliminate the need for water and produce plastics clean enough for food packaging, at a lower cost than existing techniques. Gary DeLaurentiis, now at ECO2 Plastics in California, has developed a system for stripping bottles before they are recycled that dispenses with water altogether. Shredded bottles are first immersed in the solvent ethyl lactate to clean them and then moved to a second chamber where they are blasted with liquid carbon dioxide to remove any remaining solvent. The evaporated solvent and carbon dioxide are captured so they can be reused. The distillate at the bottom of the stills, mostly left-over solvent and contaminants from the bottles, can be disposed of as solid waste. Since ethyl lactate is derived from beets and corn, it has been approved by the US FDA for use in cleaning food-preparation equipment. The solvent is said to be safe for preparing plastic for recycling into food and drink packaging. ECO2 EUROPE-GENERAL; USA

Accession no.995642 Item 8 Colloid and Polymer Science 285, No.2, Nov.2006, p.161-168 TAMARINDUS INDICA MUCILAGE AND ITS ACRYLAMIDE-GRAFTED COPOLYMER AS FLOCCULANTS FOR REMOVAL OF DYES Mishra A; Bajpai M; Pal S; Agrawal M; Pandey S Kanpur,Chhatrapati Shahu Ji Maharaj University Acrylamide was grafted onto a food-grade polysaccharide, tamarindus indica seed mucilage, by free-radical polymerisation using a ceric ion/nitric acid redox initiator and structurally characterised by FTIR spectroscopy. Both

© Copyright 2007 Smithers Rapra Technology

References and Abstracts

tamarindus indica seed mucilage and its copolymer with acrylamide were evaluated as flocculants for removing dyes from model textile wastewater containing azo, basic and reactive dyes. The effects of flocculant dose, dye concentration, contact time and pH on percent dye removal were investigated and the performance of the copolymer compared with that of the pure mucilage. 19 refs. INDIA

Accession no.996046 Item 9 Macromolecular Materials and Engineering 292, No.3, 12th March 2007, p.272-284 DIFFUSION OF MODEL CONTAMINANTS IN HIGH-DENSITY POLYETHYLENE Voultzatis I S; Papaspyrides C D; Tsenoglou C J; Roussis C Athens,National Technical University Four liquid solvents, 1,1,1-trichloroethane, toluene, chlorobenzene and octane, were used as model contaminants in sorption experiments in PE in order to study their diffusion behaviour between 40 and 70 deg.C and assess the plausibility of utilising recycled plastics as safe functional barriers in food packaging applications. A hybrid model that combined molecular and free volume theory elements was used to interpret the collected experimental data. This helped in evaluating microstructural characteristics pertaining to the penetrantpolymer systems tested, correlating these characteristics with the molecular properties of the solvent, and had an eventual role in predicting sorption and diffusivity in similar untested systems. 41 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; GREECE; WESTERN EUROPE

Accession no.996220

and binary mixtures of solvents and analysed using the e-nose and by GC-FID. The responses obtained from the e-nose were processed using principal component analysis and discriminate factorial analysis in order to identify the residual solvents. Partial least squares analysis was also used to quantify the amount of residual solvent and to correlate the e-nose results with gas chromatography, which is currently the standard method for determining residual VOCs in packaging films. There was good agreement between the e-nose responses and gas chromatography results for single solvents. The technique also worked for binary solvent mixtures. The electronic nose can be a viable alternative to traditional techniques while providing simplicity and objectivity, which would be extremely advantageous in routine quality control of residual solvents. 15 refs. USA

Accession no.994591 Item 11 Food Additives and Contaminants 24, No.4, April 2007, p.438-444 2- (2-ITX) IN FOOD AND FOOD PACKAGING MATERIALS ON THE GERMAN MARKET Rothenbacher T; Baumann M; Fuegel D Stuttgart,Chemisches und Veterinaruntersuchungsamt A fast and reliable method, based on HPLC coupled to a diode array and a fluorescence detector, for detecting the photoinitiator, 2-ITX, and also 2,4-diethylthioxanthone in food and food packaging materials is described and used to detect the presence of 2-ITX in a large number of food products packed in cartons, plastic cups and films. The method is shown to detect migration of 2-ITX from packaging materials into foodstuffs in 20% of samples. 15 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; WESTERN EUROPE

Item 10 Packaging Technology and Science 20, No.2, March-April 2007, p.99-112 DEVELOPMENT OF ELECTRONIC NOSE METHOD FOR EVALUATION OF RESIDUAL SOLVENTS IN LOW-DENSITY POLYETHYLENE FILMS Yuzay I E; Selke S Michigan,State University Flexible packaging films containing high levels of VOCs can alter the flavour and odour of packaged foods. Currently, a range of gas chromatographic techniques and sensor evaluations are used for assessing the residual VOCs in packaging films. An objective method for assessing the residual solvents from LDPE was developed using an Alpha MOS Fox 3000 electronic nose equipped with 12 metal oxide semiconductor sensors. Three VOCs, ethyl acetate, ethyl alcohol and toluene, were chosen as models for solvents of interest in flexible food packaging analysis. LDPE film samples were spiked with single

© Copyright 2007 Smithers Rapra Technology

Accession no.994005 Item 12 Plastics Technology 53, No.2, Feb.2007, p.60/75 EXTRUDING BIOPOLYMERS It is explained that plastics made from renewable carbon chain resources, rather than fossil carbon from oil or gas, are suddenly a firm commercial reality. The attraction is not just that they are marketed as environmentally friendly, but also that the prices are stable since they are not linked to petrochemicals. This article looks at the situation in detail, explains exactly what biopolymers are, and also highlights some of the bioplastic products available today. BASF AG; BASF Corp.; Novamont North America Inc.; DuPont; Stanelco plc; Wild Oats Markets; Sainsbury; Washington,Earth Policy Institute; Eastman Chemical Co.; BioBag; Huhtamaki; Wentus; Plantic Technologies Ltd.; Cereplast Inc.; Tate and Lyle Biopolymers;

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References and Abstracts

Mitsui Chemical; Shimadzu Chemical; Purac America; Galactic SA; Metabolix; Archer Daniels Midland Co.; Kaneka; Cargill; Dow Chemical; SRI Consulting; Anson Packaging; Wilkinson Industries Inc.; Wal-Mart; Plastic Suppliers Inc.; Coop Box; Sabert Corp.; Ex-Tech Plastics Inc.; Fabri-Kal Corp.; Parkinson Technologies Inc.; Marshall & Williams; BCC Research; Conair; Intertech-Pira; NatureWorks LLC; Plastic Engineering Associates Inc.; Polymer Process Communications; Spartech Corp.; Xaloy Inc.; Treofan Group AUSTRALIA; BELGIUM; CHINA; EU; EUROPE-GENERAL; EUROPEAN COMMUNITY; EUROPEAN ECONOMIC COMMUNITY; EUROPEAN UNION; FINLAND; GERMANY; ITALY; JAPAN; NETHERLANDS; NORWAY; SCANDINAVIA; UK; USA; WESTERN EUROPE; WESTERN EUROPE-GENERAL; WORLD

Accession no.994061 Item 13 Surface Coatings International 90, No.2, March 2007, p.68/75 PHOTOINITIATORS OLD AND NEW: FOOD FOR THOUGHT Green W A The history of the use of photoinitiators for UV-curable inks is discussed and type I photoinitiators, the aryl alkyl ketones, and type II photoinitiators, the aryl aryl ketones, are described. The possible migration of low molec.wt. initiators is examined and developments in polymeric and high molec.wt. photoinitiators, which exhibit reduced migration, are reported. The necessity for attempting to achieve zero risk is questioned and the advantages of the low molec.wt. ITX (a thioxanthone) over alternatives are described. Future developments in photoinitiators are considered. 11 refs. (Radcure Coatings and Inks: Cost and Performance, Manchester, UK, June 2006) EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.994095 Item 14 Pitture e Vernici 83, No.2, 1st-28th Feb.2007, p.65-72 English; Italian NOVEL DEFOAMERS AND REGULATORY COMPLIANCE FOR FOOD CONTACT PRINTING INKS AND OVER PRINT VARNISHES James V Dow Corning Ltd. The use of novel silicone-polyether copolymer defoamers, which meet the defoaming needs of manufacturers for printing inks and over print varnishes for indirect food contact while combating foam effectively and avoiding surface defects, such as craters and fish eyes, is discussed. The benefits of these defoamers over traditional PDMS technology are demonstrated and the use of 100% organomodified silicones for achieving greater formulation

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flexibility, lower use levels and stable performance on storage. 2 refs. (XXVIII Fatipec Congress, 12th-14th June, 2006, Budapest, Hungary) EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.992718 Item 15 Polymer International 56, No.4, April 2007, p.497-505 EFFECT OF CHEMICAL STRUCTURE AND COMPOSITION OF THE RESIN PHASE ON VINYL CONVERSION OF AMORPHOUS CALCIUM PHOSPHATE-FILLED COMPOSITES Skrtic D; Antonucci J M US,National Institute of Standards & Technology The effect of chemical structure and composition of the polymer matrix on the degree of vinyl conversion(DC) of copolymers (unfilled resins) and their amorphous calcium phosphate(ACP) composites attained upon photopolymerisation was studied. The DC could also be an indicator of the relative potential of these polymeric materials to leach out into the oral environment unreacted monomers that could adversely affect their biocompatibility. The following resins were examined: 2,2-bis(p-(2’-hydroxy3’-methacryloxypropoxy)phenyl)propane/triethylene glycol dimethacrylate(TEGDMA) (1:1 mass ratio; BT resin) combined with hydroxyethyl methacrylate(HEMA; BTH resin) and with HEMA and zirconyl dimethacrylate (BTHZ resin); urethane dimethacrylate(UDMA)/HEMA resins; and pyromellitic glycerol dimethacrylate(PMGDMA)/ TEGDMA (PT resin). To make composite specimens, resins were mixed with a mass fraction of 40% zirconiahybridised ACP. Copolymers and their composites were evaluated using near-IR spectroscopy for DC after 1 d and 28 d post-cure at 23 deg.C. Inclusion of HEMA into the BT and UDMA resins yielded copolymers and composites with the highest DCs. The significantly lower DCs of PT copolymers and their composites were attributed to the rigid aromatic core structure, tetravinyl functionality and limited methacrylate side-chain flexibility of the surface-active PMGDMA monomer. There was, however, an increase in the 28 d DC for the PT materials as there was for the BTHZ system. Surprisingly, the usual decrease observed in DC in going from unfilled polymer to composite was reversed for the PT system. 25 refs. USA

Accession no.992911 Item 16 Canadian Plastics 65, No.3, March 2007, p.10-13 NEW ADDITIVES: HANDFULS OF INNOVATION Stephen M Additives suppliers are unveiling a host of new formulations designed to improve processing and

© Copyright 2007 Smithers Rapra Technology

References and Abstracts

performance, provide brighter and longer lasting colours, and meet tougher safety and environmental regulations. This article outlines new nucleating/clarifying agents, chemical foaming additives, flame retardants, processing aids, internal mould release agents, UV stabilisers, pigments and colourants, and additives based on biodegradable carriers.

work are examined. The research is reported to allow a better evaluation of migration into foods by estimating the lowered diffusion in the foods, and by estimating the partitioning between the plastic materials and the real food. EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; WESTERN EUROPE

Accession no.989882

NORTH AMERICA

Accession no.991261 Item 17 Food Additives and Contaminants 24, No.3, March 2007, p.326-335 INVESTIGATION INTO THE MIGRATION POTENTIAL OF COATING MATERIALS FROM COOKWARE PRODUCTS Bradley E L; Read W A; Castle L UK,Dept.for the Environment,Food & Rural Affairs The migration potential of coating materials from cookware samples covering a wide variety of products, coating/metal types and food contact applications, and including polymer coatings such as poly(ether sulphone), poly(tetrafluoroethylene) and bisphenol A/epichlorohydrin was investigated by solvent extraction and by migration tests using food simulants. Analysis of the extracts was carried out using GC-MS and LC-MS to identify and quantify extracted species, and the migration of phthalates and bisphenol A is discussed. 14 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.991443 Item 18 Food Contact Polymers 2007. Proceedings of a conference held Brussels, Belgium, 21st-22nd Feb.2007. Shawbury, Rapra Technology, 2007, Paper 6, pp.4, ISBN 9781847350121, 29cm, 012 MODELLING MIGRATION FROM PLASTICS INTO FOODSTUFFS ˚ A NOVEL AND COST EFFICIENT APPROACH FOR COMPLIANCE EVALUATION AND CONSUMER EXPOSURE ESTIMATION Stoermer A; Franz R Freising,Fraunhofer Institut Verfahrenstechnik & Verpackung IVV (Rapra Technology) Migration modelling from plastics into food simulants is generally accepted as a tool for compliance evaluation of food contact materials according to Plastics Directive 2002/72/EC. However, the question is raised as to how migration modelling into food simulants compares to that with real foods. The European project known as Foodmigrosure attempted to fill this gap by carrying out systematic studies on mass transport from plastics into foodstuffs to derive a mathematical model for estimation of migration into foods. The first conclusions drawn from this

© Copyright 2007 Smithers Rapra Technology

Item 19 Food Contact Polymers 2007. Proceedings of a conference held Brussels, Belgium, 21st-22nd Feb.2007. Shawbury, Rapra Technology, 2007, Paper 10, pp. 4, ISBN 9781847350121, 29cm, 012 SILICONE ELASTOMERS FOR FOOD CONTACT APPLICATIONS Klaassen E Momentive Performance Materials Inc. (Rapra Technology) Silicone elastomers are particularly suitable for foodcontact applications since their basic chemistry allows for food-contact compliance. Their unique combination of properties includes elasticity, temperature resistance, chemical resistance, neutral odour and taste, and a nonstick surface. Key European regulations for food-contact and drinking water applications are examined. Typical applications are described, and include bakery moulds, ice cube trays, tubes for drinking water and coated sheets for use on conveyor belts used in the food industry. Product categories and processing technologies are described and regulatory compliance is discussed. EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; WESTERN EUROPE

Accession no.989886 Item 20 Plastic Packaging Innovation News 3, No.1, 20th March 2007, p.6 GLOWING TEMPERATURE-SENSITIVE FILM UNDER DEVELOPMENT It is briefly reported that a prototype of a new film that will show if food has been exposed to extremes of temperature is in development and should be ready at the end of 2008. Food wrapped in the intelligent film can be checked for temperature damage under long-range UV lamps, which usually make the film glow green, but cause a blue luminescence if the wrapper is damaged. The film is currently made with a food-grade dye and a biodegradable, but not food-grade polyester. Researchers at the University of Pisa say it will not be difficult to develop a food-grade polymer, providing the material can be melt-processable. In the future, it is intended to combine the film with selfrepairing technology. Pisa,University EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY; WESTERN EUROPE

Accession no.990159

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Item 21 Plastics Additives and Compounding 9, No.2, March-April 2007, p.14 CLARIFIER IMPROVES HAZE AND PROVIDES HIGHER STIFFNESS A new clarifier, developed by Adeka, is claimed to exhibit a higher crystallisation temperature and shorter crystallisation half-time resulting in alpha-form crystals, as well as a higher crystallisation rate and degree of crystallinity. Lower moulding temperatures are needed to maximise the clarifying ability of the new additive, ADK STAB NA-71, it is briefly reported. The clarifier improves haze effectively and provides excellent transparency even at low loading levels of around 0.1 wt.%, and exhibits superior clarity in thin-walled moulded articles. Use of the clarifier also results in higher stiffness, a 25% increase in flexural modulus. The product is claimed to be easy to use and offers an economically effective approach for clarified PP. Adeka Corp. USA

Accession no.989019 Item 22 Plastics Additives and Compounding 9, No.2, March-April 2007, p.32-35 STABILIZING POLYOLEFINS AND ENGINEERING RESINS TO MEET SPECIFIC APPLICATION NEEDS Markarian J Antioxidants and UV stabilisers are key additives for enabling performance of polyolefins and engineering resins in a wide range of applications. The global market for antioxidants in plastics, outside of heat stabilisers used in PVC, was about 326 thousand metric tons in 2006 and consumption is expected to grow at 4-5% AAGR. Antioxidant production is growing in the Middle East and Asia/Pacific to support expanding polymer production in these regions. Use of additive blends, with antioxidants and other additives premixed for compounding into the polymer as a single feedstream, has grown in the last decade. High temperature processes require specialised stabilisation. Chemtura’s Anox ProcessPlus stabiliser blends were designed for improved process stabilisation and colour under severe processing conditions, such as found in PP pipe, BOPP and thin wall injection moulding. The global market for UV stabilisers in plastics was 57 thousand metric tons in 2006, with about 60-65% going into polyolefin resins. UV stabilisers with application-specific advantages are being used in areas such as agricultural film and automotive parts. For example, Ciba Tinuvin NOR 371 hindered amine UV and thermal stabiliser protects greenhouse and mulch films in the presence of agrochemicals and harsh environmental conditions that can reduce the efficacy of standard HALS. WORLD

Accession no.989023

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Item 23 PETplanet insider 8, No.3, 2007, p.17 PET CATALYSTS AND THE ANTIMONY QUESTION Thiele U The current estimated world polyester production of about 42 million tonnes/year is more than 97% based on antimony catalysts, which represents some 8,970 tonnes of antimony. The increasing number of antimony catalyst producers, mainly those offering antimony trioxide, has resulted in growing product diversity and also uncertainty among catalyst users about product quality. However, driven by the needs of bottle grade PETP resin producers for the lowest lead and arsenic content in their antimony catalysts, products such as those offered by Arkema, Campine, Chan Long, Honeywell, J&M/Synetix, Mikuni or Yizheng have improved remarkably over the last 10 years. The currently established antimony limits for drinking water are presented. Scientific leaching tests indicate that the increase in antimony concentration caused by leaching into liquid foodstuffs packed in PETP bottles is an order of magnitude less than the limits set for US and EU drinking water standards. WORLD

Accession no.989045 Item 24 Journal of Applied Polymer Science 104, No.1, 5th April 2007, p.273-278 NOVEL POLY(VINYL ALCOHOL)TETRAETHOXYSILANE HYBRID MATRIX MEMBRANES AS OXYGEN BARRIERS Patil M B; Patil S A; Veerapur R S; Aminabhavi T M Karnatak University Synthesis of membranes which act as oxygen barriers by crosslinking polyvinyl alcohol using tetraethoxysilane, followed by solution casting and solvent evaporation is described. Membranes were characterised using Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and gas separation experiments. Oxygen permeability was measured for membranes of two different thicknesses, and was seen to vary with thickness and applied pressure. Films may be suitable for food packaging applications. 20 refs. INDIA

Accession no.989293 Item 25 Plastics Technology 52, No.11, Nov.2006, p.27 CLEAR NYLONS ARE CHEMICAL RESISTANT Nylon Corp. of America Inc. (Nycoa) has introduced a new line of clear transparent nylons, which targets applications involving exposure to harsh solvents - where

© Copyright 2007 Smithers Rapra Technology

References and Abstracts

polymers such as polycarbonate and polystyrene are not suitable. Brief details are given in this short article about the properties of the new “Nycotrans” resins. Nylon Corp.of America Inc.

unsaturated photoinitiators, which makes their use in medical applications possible. Food-contact applications are also mentioned. 10 refs.

USA

Accession no.989698

EASTERN EUROPE; POLAND

Accession no.989540 Item 26 Plastics Technology 52, No.12, Dec.2006, p.38-43 MORE FILLER, LESS RESIN It is explained that, in the world of T-shirt bags and can liners, where profit margins are razor thin and resin prices high, packaging film processors have, over the last year and a half, increased their loadings of calcium carbonate fillers by about ten percent. This article looks in detail at the market for fillers, and the consequences of using higher loadings. Section headings include: factors pushing fillers, concentrates improve, filler affects properties, how output increases, saving on additives, and, equipment modifications. Ampacet Corp.; Inteplast Group; Battenfeld Gloucester Engineering Co.; Bayshore Industrial Inc.; Heritage Plastics Inc.; Hosokawa Alpine America; Imerys Performance Minerals; Ingenia Polymers Group; Kiefel Inc.; Omya Inc.; Plastics Touchpoint Group Inc.; Reifenhauser Inc.; Hilex Poly Co.; Heritage Bag; Formosa Plastics Group; Chemical Market Associates Inc. CANADA; EUROPE-GENERAL; NORTH AMERICA; TAIWAN; THAILAND; USA; WORLD

Accession no.989599 Item 27 European Coatings Journal No.2, 2007, p.26-30 CHOOSING THE RIGHT INITIATOR. IMPROVED PERFORMANCE OF UVCROSSLINKING PRESSURE-SENSITIVE ADHESIVES Czech Z; Klementowska P; Drzycimska A Szczecin,University of Technology The use of UV light for crosslinking of adhesives is described and conventional and multifunctional photoinitiators are compared. The importance of the correct selection of photoinitiators for UV curing of pressure-sensitive adhesives is discussed. The results of experimental studies of the performance properties (tack, peel adhesion and shear strength) of solvent-borne, acrylic, pressure-sensitive adhesives, synthesised with different amounts of test acryloyloxy photoinitiators and applied onto a smooth polyester film, are presented. It is shown that there is a clear relationship between the performance of UV-crosslinked pressure-sensitive adhesives and the correct unsaturated photoinitiators and that very high shear strengths can be achieved using multifunctional

© Copyright 2007 Smithers Rapra Technology

Item 28 Chemical Migration and Food Contact Materials. Cambridge, Woodhead Publishing, 2007, p.64-83, ISBN 084939130X, 24cm, 938 TRACEABILITY AND FOOD CONTACT MATERIALS Dainelli D Sealed Air Corp.; European Plastics Converters Assn. Edited by: Barnes K A; Sinclair C R; Watson D H Tracing of all elements that contribute to a finished product is mainly needed to address quality defects. The good quality of food contact materials is not only a legal requirement, but it is in the industry’s interest to maintain a high level of control over its production, which can be achieved through suitable traceability systems. This chapter discusses the European regulations associated with the traceability of food contact materials, and provides industrial guidelines for this traceability. The limits of traceability systems in plastic processing are examined with respect to bulk storage of resins, reprocessed materials, and printing inks. 10 refs. BELGIUM; EU; EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.987608 Item 29 Chemical Migration and Food Contact Materials. Cambridge, Woodhead Publishing, 2007, p.87-121, ISBN 084939130X, 24cm, 938 COMPLIANCE TESTING OF CHEMICAL MIGRATION FROM FOOD CONTACT MATERIALS Veraart R; Coulier L TNO Quality of Life Edited by: Barnes K A; Sinclair C R; Watson D H In this chapter, the authors discuss how food contact materials can be tested for compliance with the relevant legislation in the European Union. Two complementary approaches to testing are examined. Conventional compliance testing is a target analysis of migrants, based on knowledge of the composition of the food contact material, and a nontarget approach for the non-intentionally added substances (NIASs). The main difference between them is that in conventional compliance testing, the investigation is focused on the ingredients (monomers, additives, etc.), used, and on how much of these ingredients are present and can potentially migrate into the food. In the non-target compliance approach all possible components that can migrate to the food are included, with the focus on components that were included in the polymer without the intention to be added. These

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References and Abstracts

include components such as oligomers, by-products, reaction products and impurities, etc. The methods of compliance testing are described, with details of relevant European test standards and procedures. 63 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; NETHERLANDS; WESTERN EUROPE; WESTERN EUROPEGENERAL

Accession no.987609 Item 30 Chemical Migration and Food Contact Materials. Cambridge, Woodhead Publishing, 2007, p.158-179, ISBN 084939130X, 24cm, 938 TOXICOLOGY AND RISK ASSESSMENT OF CHEMICAL MIGRANTS FROM FOOD CONTACT MATERIALS Arvidson K B; Cheeseman M A; McDougal A J US,Food & Drug Administration Edited by: Barnes K A; Sinclair C R; Watson D H In the US, components of food contact materials are regulated as food additives under the Federal Food, Drug, and Cosmetic Act (FFDCA). The FDA has the responsibility for the administration and enforcement of the FFDCA with regard to food contact materials. This chapter gives an overview of the FDA’s current approach to toxicology review and risk assessment for components of food contact materials. The regulatory framework is described, and methods for the safety assessment of food additives, including threshold approaches to safety assessment, are discussed. The carcinogenicity risk assessment for constituents of food additives is examined, together with the use of a structureactivity relationship analysis technique. 44 refs. USA

Accession no.987611

Item 32 Chemical Migration and Food Contact Materials. Cambridge, Woodhead Publishing, 2007, p.271-302, ISBN 084939130X, 24cm, 938 RUBBER AND CHEMICAL MIGRATION INTO FOOD Forrest M Rapra Technology Edited by: Barnes K A; Sinclair C R; Watson D H In contrast to plastics, rubbers are rarely used in the packaging of food products. Exceptions to this include the use of rubber in flip top seals on beer bottles and the seal that is present in food cans. However, in the food processing industry, a number of situations exist where significant contact between rubber and food can occur. Variations in contact conditions have an important effect on the potential of chemical species to migrate from the rubber components into the foodstuff, and in general, the contact times are usually short and the contact areas with the exception of hose and belting, are small. It is common for a rubber formulation to contain 10-15 ingredients, hence there is a large range of monomers, oligomers, processing aids and compounding ingredients to be taken into account when considering the potential for migration. This chapter lists the most important classes of rubbers used in the food industry, the main classes of additives used, and identifies typical food contact conditions. Current European and US regulations regarding the use of rubber as a food contact material are examined. Methods of assessing the safety of rubber as a food contact material are discussed in terms of migration testing, fingerprinting potential migrants, and determination of species in rubbers and migrants in food simulants and food products. 34 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; USA; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.987616 Item 31 Chemical Migration and Food Contact Materials. Cambridge, Woodhead Publishing, 2007, p.228-250, ISBN 084939130X, 24cm, 938 PLASTICS AND CHEMICAL MIGRATION INTO FOOD Cooper I Pira International Edited by: Barnes K A; Sinclair C R; Watson D H This chapter is primarily devoted to assessing the safety of food-contact materials. It includes a brief discussion on the different plastics used in the manufacture of food-contact materials, their key attributes and properties, composition and manufacture. The requirements of the EU Plastics Directive are examined, and shows how compliance with the legislation is demonstrated. Degradation products are reviewed, followed by a section on future trends in plastics materials, and source of further information. 21 refs.

Item 33 Chemical Migration and Food Contact Materials. Cambridge, Woodhead Publishing, 2007, p.302-319, ISBN 084939130X, 24cm, 938 FOOD PACKAGING INKS AND VARNISHES AND CHEMICAL MIGRATION INTO FOOD Aurela B; Soderhjelm L KCL Finland Edited by: Barnes K A; Sinclair C R; Watson D H This chapter deals with the use of printing inks and varnishes used on food packaging. It describes the processes and problems relating to printing on food packaging, dealing primarily with the components of ink and their possible migration into the packaged foodstuffs. Sensory (odour and taint) aspects and testing thereof is covered and statutory requirements are discussed. 12 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

EU; EUROPEAN COMMUNITY; EUROPEAN UNION; FINLAND; SCANDINAVIA; WESTERN EUROPE; WESTERN EUROPEGENERAL

Accession no.987614

Accession no.987617

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References and Abstracts

Item 34 Chemical Migration and Food Contact Materials. Cambridge, Woodhead Publishing, 2007, p. 320-332, ISBN 084939130X, 24cm, 938 FOOD PACKAGING ADHESIVES AND CHEMICAL MIGRATION INTO FOOD Bradley E; Castle L UK,Dept.for the Environment,Food & Rural Affairs; UK,Central Science Laboratory Edited by: Barnes K A; Sinclair C R; Watson D H The possibility of adhesive chemicals used in food packaging migrating into the foods is discussed. The many different types of adhesives and the wide variety of ways in which they can be used, influence the potential for migration of chemicals into the packaged food. The two main parameters considered therefore are the surface area of the adhesive used, and the residual content of low molecular weight substances. Examples are given of the adhesive types used in food packaging applications, and their typical application. For each type, details are given of the potential for chemical migration, and how the safety of these substances can be tested experimentally. The current regulatory situation in the EU and USA is also briefly discussed. 23 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; USA; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.987618 Item 35 Chemical Migration and Food Contact Materials. Cambridge, Woodhead Publishing, 2007, p.3476-370, ISBN 084939130X, 24cm, 938 CHEMICAL MIGRATION FROM MULTI-LAYER PACKAGING INTO FOOD Sidwell J Rapra Technology Edited by: Barnes K A; Sinclair C R; Watson D H The potential for chemical migration from multilayer packaging into food is discussed. Multilayer technology enables several materials to be combined in a laminated structure in order to optimise the properties of the packaging for a specific end use applications. This structure can be achieved by co-extrusion or by laminating films using adhesives. Potential chemical migration is influenced by the choice of materials and the additives used for the different layers, and whether the food-contact surface layers acts as a barrier to migratory species from underlying materials. Most migration research relates to the migration of species from laminating adhesives. Typical multilayer constructions and materials are described, with details of the adhesives commonly used, and their potential for chemical migration. 11 refs.

Item 36 Composites Science and Technology 67, No.3-4, 2007, p.399-405 SLIDING WEAR PERFORMANCE OF POLYAMIDE 6-CLAY NANOCOMPOSITES IN WATER Srinath G; Gnanamoorthy R Indian Institute of Technology Polyamide 6 (PA6) clay nanocomposites, a new class of specialty polymer, shows improved tribological properties under dry sliding conditions. In food and chemical industry, the polymeric materials are widely used in the machine elements due its excellent chemical inertness. Water, being a widely used solvent, tends to have contact with the machine elements and can either act as a lubricant or as a contaminant. Many factors such as the interaction of polymer with water, surface wettability, etc., play a major role on the friction and wear of polymers in aqueous conditions. This work reports the sliding wear performance of PA6 clay nanocomposites in water. Addition of clay affects the crystallinity of the nanocomposites, which in turn affects the plasticisation. Plasticisation of the surface by water causes increase in wear and decreases the coefficient of friction. 18 refs. INDIA

Accession no.987687 Item 37 Rubberchem 2006. Proceedings of a conference, held Munich, Germany, 5th-6th Dec.2006. Shawbury, Rapra Technology, 2006, Paper 2, pp.30, ISBN 1847350054, ISBN 9781847350053, 29cm, 012 BREAKDOWN PRODUCTS OF CURATIVES AND ANTIDEGRADANTS USED TO PRODUCE FOOD CONTACT ELASTOMERS Forrest M J; Coulier L; Willoughby B G; Thorn A Rapra Technology; TNO Nutrition & Food Research (Rapra Technology) A report is presented on an extensive research project carried out for the UK Food Standards Agency to obtain information on the breakdown and reaction products of curatives and antidegradants having the potential to migrate into food. The curatives and antidegradants targeted are those present in the inventory list contained within the Council of Europe Resolution on Rubber. The objectives of the project were to provide a comprehensive list of the breakdown products originating from the 161 curative and antidegradant compounds in the inventory list and to carry out a programme of work on test rubber compounds containing a selection of the curatives and antidegradants using both food simulants and food products to assess the potential of the breakdown products to migrate. Investigative techniques employed included headspace gas chromatography-mass spectroscopy and solvent extraction gas chromatography-mass spectroscopy. UK,Food Standards Agency

EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

EUROPEAN COMMUNITY; EUROPEAN UNION; NETHERLANDS; UK; WESTERN EUROPE

Accession no.987620

Accession no.988268

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References and Abstracts

Item 38 ANTEC 2006. Proceedings of the 64th SPE Annual conference held Charlotte, NC., 7th-11th May 2006. Brookfield, Ct., SPE, 2006, p.2660-4, PDF 103707, CDROM, 012 STRUCTURE AND PROPERTIES OF BIAXIALLY ORIENTED POLYPROPYLENES (BOPP) Dias P; Hiltner A; Baer E; Van Dun J; Chen H; Chum S P Case Western Reserve University; Dow Chemical Co. (SPE)

HIGH BARRIER SOLUTIONS FOR PLASTIC CONTAINERS USING FLUORINATION PROCESS Singh B Bloom Packaging Pvt.Ltd.

The solid-state structure, mechanical properties, and gas transport of biaxially oriented polypropylenes are investigated. Specifically, the effect of chain architecture on processing conditions and resulting properties of the oriented films is studied. Relationships between the process, solid state structure, and properties are described. 6 refs.

HDPE/PP rigid containers can be treated with fluorine gas to form high barrier fluorinated plastic containers. The fluorination process and theory of solvent permeation and barrier function are outlined. Fluorination treatment is quantified using FTIR. A table showing the conversion of % transmission ratio to level of fluorination is given. Permeation test data of fluorinated HDPE containers are also presented. Applications of fluorinated plastic containers include agrochemicals, flavours (food products) and fragrances (non-food products), automotive fuels and fuel additives, automotive fuel tanks, aromatic and non-polar chemicals, solvent based adhesives, and inks, paints and thinners.

USA

INDIA

Accession no.986417

Accession no.985858

Item 39 Addcon World 2006. Proceedings of the 12th International Plastics Additives and Modifiers Conference, held Cologne, Germany, 17th -18th Oct.2006. Shawbury, Rapra Technology, 2006, Paper 2, pp.14, ISBN 1847350038, ISBN 9781847350039, 29cm, 012 LEGISLATION AND TESTING OF FOOD CONTACT PLASTICS - AN UPDATE WITH RESPECT TO ADDITIVES Sidwell J Rapra Technology (Rapra Technology)

Item 41 ENDS Report No.384, Jan.2007, p.24-25 EXPERTS CONCERNED OVER HEALTH RISKS OF ORGANOTINS

This paper reviews the current regulatory position within the European Union with regard to the selection of additives and related substances for plastics in contact with foods. The European Commission is moving towards compiling a positive list of approved substances. Topical issues associated with the migration of several additives are discussed. These include: benzophenone and isopropyl thioxanthone photoinitiators in UV curable printing ink systems; epoxidised soyabean oil in PVC formulations; phthalate plasticisers; ethyl hexanoic acid; bisphenol A; bisphenol A diglycidyl ether (BADGE); and aromatic amines from laminating adhesives. Current research undertaken at Rapra to examine the migration of additives, including antioxidants, stabilisers and antistatic agents, using chromatographic techniques based on mass spectrometry, is reviewed. 15 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; WESTERN EUROPE-GENERAL

Accession no.985580 Item 40 Popular Plastics and Packaging 52, No.1, Jan.2007, p.84-89

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Organotins are used as pesticides, biocides, catalysts and stabilisers, but have immunotoxic and endocrine disrupting effects. They have also been linked to obesity. The European Commission has rejected a third draft risk assessment for underestimating the dangers. The biggest sources of human exposure to organotins are considered to be: food, particularly seafood which can be contaminated by organotins used in antifouling paint; indoor air and dust where PVC flooring and wall coverings contain organotins as stabilisers; skin absorption via clothing, where organotins may be present in PVC coatings or in textiles where they may be used as a biocide. The assessment does not consider exposure to organotins via PVC medical equipment, silicone breast implants or rubber pillows, and these need to be investigated. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; WESTERN EUROPE-GENERAL

Accession no.985877 Item 42 2004 PLACE Conference. Proceedings of a conference held Indianapolis, In., 29th Aug.-2nd Sept.2004. Atlanta, Ga., TAPPI Press, 2004, Paper 27, pp.7, CDROM, 012 FLEXIBLE PACKAGING ADHESIVES - THE BASICS Jopko L Rohm & Haas Co. (TAPPI) Flexible packaging adhesives, which are predominantly based on urethane and acrylic chemistry, are discussed with

© Copyright 2007 Smithers Rapra Technology

References and Abstracts

emphasis on basic chemistries, end-use performance levels and some chemical features that dictate performance. The general components of a PU adhesive are described, including polyol, backbone modifiers, isocyanate, and the creation of urethane is outlined. The advantages and disadvantages of solvent-based, 100% solids and PU dispersion adhesives are considered. Acrylic-based, polyvinylidene chloride-based and energy-cured adhesives (i.e. UV cured and electron beam cured) are also discussed. Accession no.986358 Item 43 2004 PLACE Conference. Proceedings of a conference held Indianapolis, In., 29th Aug.-2nd Sept.2004. Atlanta, Ga., TAPPI Press, 2004, Paper 47, pp.9, CDROM, 012 HIGH PERFORMANCE STRETCH HOOD PACKAGING FILMS USING METALLOCENE POLYETHYLENE Halle R W; Ohlsson S; Weisinger D R ExxonMobil Chemical (TAPPI) A stretch hood is a type of product protection system, commonly used to unitise and secure palletised products during shipping and storage. The use of a combination of a metallocene-catalysed PE with a new EVA copolymer (vinyl acetate content 7.5%, melt index 0.5) to produce a new high-performance stretch hood film is described. The coextruded film is shown to outperform both conventional monolayer and coextruded films in several different stretch hood and shrink hood applications. These applications include stretch hood films for building materials, heavy-duty sacks, empty PETP bottles, appliances, and beverages, food and bottled goods. Statistics are given on global stretch hood market growth and on market segment estimates for 2003 to 2010. 1 ref. ASIA; BELGIUM; EU; EUROPE-GENERAL; EUROPEAN COMMUNITY; EUROPEAN UNION; USA; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.986378 Item 44 2004 PLACE Conference. Proceedings of a conference held Indianapolis, In., 29th Aug.-2nd Sept.2004. Atlanta, Ga., TAPPI Press, 2004, Paper 54, pp.7, CDROM, 012 HOW TO APPLY AN OXYGEN BARRIER PRIMER WITH A ROLL COATER Cushing G; Ostness L Mica Corp.; Black Clawson Converting Machinery Inc. (TAPPI) A water-based primer was developed which imparted oxygen barrier properties and strong interlayer adhesion to film and metallised film substrates. Direct and reverse gravure coating techniques for achieving a smooth, level coating of the Mica M-2345 coating on oriented PETP

© Copyright 2007 Smithers Rapra Technology

film were investigated. Oxygen barrier performance was reported. The technology was developed for food, medical and industrial end uses. 3 refs. USA

Accession no.986385 Item 45 2004 PLACE Conference. Proceedings of a conference held Indianapolis, In., 29th Aug.-2nd Sept.2004. Atlanta, Ga., TAPPI Press, 2004, Paper 57, pp.6, CDROM, 012 EVALUATION OF LOW VOLTAGE ELECTRON BEAM PROCESSORS USING THIN FILM DOSIMETRY TECHNIQUES Rangwalla I Energy Sciences Inc. (TAPPI) Thin film dosimetry is described and the use of radiochromic nylon thin film from Far West Technologies is discussed. The dosimetric evaluation of low voltage electron beam accelerators used to cure coatings, inks and laminating adhesives, especially for food flexible packaging applications, is considered. The analysis of the performance of electron beam processors is examined with reference to yield measurements, beam uniformity, and depth dose. Future developments are mentioned. 5 refs. Far West Technologies USA

Accession no.986388 Item 46 2004 PLACE Conference. Proceedings of a conference held Indianapolis, In., 29th Aug.-2nd Sept.2004. Atlanta, Ga., TAPPI Press, 2004, Paper 58, pp.9, CDROM, 012 ADVANCING THE USE OF UV/EB MATERIALS IN FOOD PACKAGING ALLIANCE Golden R; Marrapese M Surface Specialties; Keller & Heckman LLP; Radtech International North America (TAPPI) The work of the RadTech Food Packaging Alliance, which is a self-funded group with the objective of serving as a catalyst for expanding the use of UV and electron beam(EB) materials in food packaging, is described. Particular attention is paid to the work of the Alliance aimed at accomplishing one or more successful Food Contact Notifications(FCNs) of UV/EB workhorse materials. The FCNs will establish a public baseline for what the FDA will accept in designing UV/EB formulations for food packaging uses. Migration studies are reported and substances cleared for use in paper coatings, can coatings, films, adhesives and printing inks in contact with foodstuffs are considered. RadTech Food Packaging Alliance; US,Food & Drug Administration USA

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Item 47 2004 PLACE Conference. Proceedings of a conference held Indianapolis, In., 29th Aug.-2nd Sept.2004. Atlanta, Ga., TAPPI Press, 2004, Paper 61, pp.12, CDROM, 012 NEW EVAL EVOH RESINS FOR FLEXIBLE PACKAGING Armstrong R B, EVAL Americas (USA) (TAPPI) The use of ethylene-vinyl alcohol copolymers(EVOHs) of varying mol % ethylene, including new grades of EVOH optimised for high-speed coextrusion coating and laminating, is discussed, with particular reference to basic properties and processability, gas, flavour and aroma barrier properties, and thermal stability. An overview of applications and structures is presented. 8 refs.

Item 50 Woodston, Recoup, 2006, pp.4, 30cm. Available from: www.recoup.org/design/docs/recycability_pet.pdf (Accessed 2nd October 2006) DESIGNING PET PACKAGING FOR RECYCLABILITY: A BRIEF GUIDE Reckitt Benckiser (Recoup) This guideline focuses on the design of PET bottles to facilitate recycling. It provides a summary of key considerations to make plastic packaging more recyclability. Advice is provided in the form of a set of general guidelines together with compatibility matrices for PET bottles materials.

USA

EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.986392

Accession no.982665

Item 48 Journal of Plastic Film and Sheeting 22, No.4, Oct.2006, p.265-274 COMPARATIVE PERFORMANCE AND BARRIER PROPERTIES OF BIODEGRADABLE THERMOPLASTICS AND NANOBIOCOMPOSITES VERSUS PET FOR FOOD PACKAGING APPLICATIONS Cava D; Gimenez E; Gavara R; Lagaron J M IATA; CSIC; Castellon,University; Nanobiomatters Ltd.

Item 51 Woodston, Recoup, 2006, pp.4, 30cm. Available from: www.recoup.org/design/docs/recycability_pvc.pdf (Accessed 2nd October 2006) DESIGNING PVC PACKAGING FOR RECYCLABILITY: A BRIEF GUIDE Reckitt Benckiser (Recoup)

The performance of packaging films made from biodegradable polylactic acid, amorphous polylactic acid, polycaprolactone, hydroxyalkanoate-valerate copolymer and their claycontaining nanocomposites is compared with those produced from PETP in terms of heat and retort resistance and permeability to water, aromas, oxygen and solvents. 10 refs. (SPE, ANTEC 2005, 1st-5th May, Boston, Massachusetts) EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN; WESTERN EUROPE

Accession no.985124 Item 49 Woodston, Recoup, 2006, pp.4, 30cm. Available from: www.recoup.org/design/docs/recycability_hdpe.pdf (Accessed 2nd October 2006) DESIGNING POLYETHYLENE PACKAGING FOR RECYCLABILITY: A BRIEF GUIDE Reckitt Benckiser (Recoup)

This guideline focuses on the design of PVC packaging to facilitate recycling. It provides a summary of key considerations to make plastic packaging more recyclability. Advice is provided in the form of a set of general guidelines together with compatibility matrices for PVC packaging materials. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.982666 Item 52 Woodston, Recoup, 2006, pp.4, 30cm. Available from: www.recoup.org/design/docs/recycability_ps.pdf (Accessed 2nd October 2006) DESIGNING POLYSTYRENE PACKAGING FOR RECYCLABILITY: A BRIEF GUIDE Reckitt Benckiser (Recoup)

This guideline focuses on the design of polyethylene plastic packaging to facilitate recycling. It provides a summary of key considerations to make plastic packaging more recyclability. Advice is provided in the form of a set of general guidelines together with compatibility matrices for polyethylene materials.

This guideline focuses on the design of polystyrene packaging to facilitate recycling. It provides a summary of key considerations to make plastic packaging more recyclability. Advice is provided in the form of a set of general guidelines together with compatibility matrices for polystyrene packaging materials.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.982664

Accession no.982667

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Item 53 Woodston, Recoup, 2006, pp.4, 30cm. Available from: www.recoup.org/design/docs/recycability_pp.pdf (Accessed 2nd October 2006) DESIGNING POLYPROPYLENE FOR RECYCLABILITY: A BRIEF GUIDE Reckitt Benckiser (Recoup) This guideline focuses on the design of polypropylene packaging to facilitate recycling. It provides a summary of key considerations to make plastic packaging more recyclability. Advice is provided in the form of a set of general guidelines together with compatibility matrices for polypropylene packaging materials. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.982668 Item 54 Journal of Applied Polymer Science 102, No.6, 15th Dec.2006 p.5841-5847 ANTIMICROBIAL POLY(N-VINYL-2PYRROLIDONE-ALT-MALEIC ANHYDRIDE)/ POLY(ETHYLENE IMINE) MACROCOMPLEXES Temiz A; Togay S O; Sener A; Guven G; Rzaev Z M O; Piskin E Hacettepe,University Preparation of antimicrobial polymer and polymer macro complexes of poly(vinyl pyrrolidone-alt-maleic anhydride), using radical alternating polymerisation initiated by azobisisobutyronitrile) in dioxane and interaction with polyethyleneimine (PEI) in aqueous solution, is described. Characterisation was carried out using elemental analysis, Fourier transform infrared and nuclear magnetic resonance spectroscopies, thermogravimetric analysis, differential scanning calorimetry, determination of nitrogen content and intrinsic viscosity measurements. Antimicrobial properties of both alternating copolymer and its PEI macrocomplexes were evaluated against gram-positive and gram-negative bacteria. Differences in behaviour to two gram-positive bacteria were discussed and explained. 49 refs. TURKEY

Accession no.982907 Item 55 Japan Chemical Week 47, No.2394, 30th Nov.2006, p.2 ADEKA MARKETS NEW, FAST-HARDENING POLYMER CEMENT It is briefly reported that Adeka has started marketing its new polymer cement as a floor material for kitchens and food and chemicals factories. The new cement is an improved version of the Adeka New Coat System, a floor material with high resistance to boiling water, acid and

© Copyright 2007 Smithers Rapra Technology

alkali. It is based on a modified polyol resin and two types of polyisocyanate hardening accelerators. Adeka Corp. JAPAN

Accession no.981671 Item 56 High Performance Plastics Aug.2006, p.8/9 BIODEGRADABLE PLASTIC THAT SOLIDIFIES IN SECONDS At the Tokyo Institute of Technology in Japan, scientists have now found a method of rapidly curing polylactic acid (PLA), in order to make biodegradable plastic for applications such as food containers. This small item reports very briefly on their research, which involves adding cyclodextrin microparticles to the PLA. Tokyo,Institute of Technology JAPAN

Accession no.982084 Item 57 Chemical Week 167, No.41, 30th Nov.-7th Dec.2005, p.42 RAD TECHNOLOGY Technology advances help UV/EB-curable adhesives expand into new applications. With a reduced level of VOCs, ease of handling, high performance and flow characteristics said to be better than solvent- and waterbased formulations, adhesives usage for radiation curing is sustaining double-digit growth. Laminating glues is by far the largest application, while pressure-sensitive adhesives is among the fastest-growing UV/EB end products. Cytec is focusing on developing the next generation of UVcurable waterborne resins for plastic and wood substrates, leading-edge UV/EB applications in coil coatings and auto refinish, and environmentally friendly, low-odour and lowextractable products for use in food packaging. RadTech International North America; Cytec USA

Accession no.954744 Item 58 ANTEC 2005. Proceedings of the 63rd SPE Annual conference held Boston, Ma., 1st-5th May. Brookfield, Ct., SPE, 2005, pp.7, PDF 101619, CDROM, 012 ADVANCED TECHNOLOGIES FOR HIGH CONTRAST & COLOR LASER MARKING OF PLASTICS Sabreen S R Sabreen Group Inc. (SPE) The newest generation of laser material science and hardware/ software is driving strong industry demand for indelible, high

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speed laser marking processes to replace conventional ink printing. This paper presents a “total solutions” methodology for achieving unprecedented marking contrast quality and colour laser marking of plastics via concomitant engineering of: 1) laser additive material science, 2) primary moulding operations, 3) laser/software technology, and 4) systems integration. The first of its kind laser pigment to receive U.S. Food and Drug Administration (FDA) approval for use in laser processes is introduced as well as techniques to achieve high speed vector marking of alphanumeric text, graphics and product security codes. 4 refs. USA

Accession no.955951 Item 59 Food Additives and Contaminants 22, No.10, Oct.2005, p.1012-22 NON-TARGETED MULTI-COMPONENT ANALYTICAL SURVEILLANCE OF PLASTIC FOOD CONTACT MATERIALS: IDENTIFICATION OF SUBSTANCES NOT INCLUDED IN EU POSITIVE LISTS AND THEIR RISK ASSESSMENT Skjevrak I; Brede C; Steffensen I-L; Mikalsen A; Alexander J; Fjeldal P; Herikstad H Norwegian Food Safety Authority; Norwegian Institute of Public Health A procedure used by the Norwegian Food Safety Authority for surveillance of contaminants from plastic food materials, based on GC-MS analysis of food simulants exposed to the plastic materials, is described. Migrants identified from polyolefin water bottles, electric kettles, polyamide cooking utensils and laminated food packaging included polymer degradation products and impurities, as well as extraneous materials such as adhesives, solvents and coatings. 36 refs. NORWAY; SCANDINAVIA; WESTERN EUROPE

Accession no.958019 Item 60 ANTEC 2005. Proceedings of the 63rd SPE Annual conference held Boston, Ma., 1st-5th May. Brookfield, Ct., SPE, 2005, pp.3, PDF 102096, CDROM, 012 IMPACT OF UV CURED INKS AND UV EXPOSURE ON PHYSICAL PROPERTIES OF BOPP FILMS Shrotri K; Upasani T; Williams S; Seung Kim; Kamaran Rab Rochester,Institute of Technology (SPE) Biaxially-oriented PP(BOPP) films are extensively used in the food packaging industry primarily because of their good barrier properties, machinability and printability. The effect of flexographic UV-cured acrylic inks on BOPP films was investigated with emphasis on permeability towards oxygen and moisture. The temperature dependence of the

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mechanical properties of the printed films was studied. Instron tensile strength, Mocon permeability test and thermodynamic results were obtained that suggested that there was no appreciable change in the physical properties when the films were printed with UV curing inks. 6 refs. USA

Accession no.958685 Item 61 Asian Plastics News Jan.-Feb.2006, p.14/7 BETTER LIVING THROUGH ADDITIVES Boi K End users from various industries are leveraging heavily on the latest developments in polymer additives to provide options for improving processing and for raising the quality of everyday products. BASF is positioning its Hexamoll DINCH as a choice non-phthalate plasticiser for sensitive human contact applications in toys and childcare articles, as well as food contact and medical applications. Chemtura’s Anox No Dust Blends of antioxidants include Anox FiberPlus for the process stabilisation of PP fibre grades and Anox ProcessPlus for process stabilisation of PP and HDPE. Hyperform HPN-68L nucleating agent from Milliken is developed as a new class of nucleators that offer improvements over the conventional and advanced nucleation technologies used for PP. In nanocomposite developments, PolyOne is investigating the use of its Nanoblend concentrates for large injection moulded parts, replacing traditional mineral or glass reinforcements and flame-retardant additives in a wide variety of resin compounds. WORLD

Accession no.959514 Item 62 Progress in Rubber, Plastics and Recycling Technology 22, No.1, 2006, p.1-21 CONTAMINANTS AND THEIR LEVELS OF RETENTION IN EXTRUDED, RECYCLED POLY(ETHYLENE TEREPHTHALATE) FROM CURBSIDE COLLECTION. PART 1: EXTRACTION KINETICS AND PARTICLE SIZE EFFECTS Konkol L M; Cross R F; Harding I H; Kosior E Swinburne,University of Technology; Visy Technical Centre Extruded recycled poly(ethylene terephthalate)(PET) from kerbside collections was subjected to solvent extraction and GC-MS analysis as particles after annealing and grinding to determine contaminants and their levels. The effects of particle size on the extraction and analysis process were investigated, and the results are discussed in terms of food contact applications of the recycled PET. 13 refs. AUSTRALIA

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References and Abstracts

Item 63 China Chemical Reporter 17, No.4-5, 6th-16th Feb.2006, p.22-3 MALEIC ANHYDRIDE CAPACITY IS SERIOUS SURPLUS Maleic anhydride is an important organic chemical raw material and fine chemical product mainly used in the production of unsaturated polyester and alkyd resin, and also in pesticides, pharmaceuticals, coatings, ink, lubricants, food additives and surfactants. The total capacity of maleic anhydride in China is more than 420,000 t/y, with an output of 236,000 tons in 2004. Capacity is concentrated in the north and the market is already saturated. East China and South China, however, are the major producing areas of UPR and there is a supply shortage of maleic anhydride. Several units are to be constructed or expanded in the near future. If these projects can start production on schedule, capacity of maleic anhydride in China will be more than 500,000 t/y in 2010. Demand was around 227,000 tons in 2004 and will reach 393,000 tons in 2010. CHINA

Accession no.960278 Item 64 Plastics and Rubber Weekly 24th Feb.2006, p.11 PLASTICS PACKAGING, YES PLEASE According to a new report from Frost & Sullivan, market revenues for flexible food packaging in western Europe will increase from Euro1.491bn in 2005 to Euro1.926bn by 2012. Greater demand for processed foods by consumers is supporting the need for plastic packaging, with emphasis on multilayer structures and vacuum packaging. Lowweight stand-up pouches are replacing alternatives such as cans and glass jars. Improvements in the properties of PE, achieved by new synthesis methods, will contribute to the polymer’s sustained growth. PP producers are investing in R&D efforts for catalysis development, aiming at commercialising new grades, which are expected to reach the market by 2006-07. Frost & Sullivan WESTERN EUROPE-GENERAL

Accession no.960295 Item 65 Injection Moulding 2005. Proceedings of a conference held Copenhagen, Denmark, 1st.-2nd. March 2005.. Copenhagen, Hexagon Holdings Aps, 2005, Paper 10, pp.12, CD-ROM, 012 TAILORED MOULD RELEASE FOR OPTIMUM OUTPUT Read M Croda Polymer Additives (Hexagon Holdings Aps) Details are given of the IncroMold range of additives which aid in the injection moulding process at various

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stages in the moulding cycle. The additives are mixed with the polymer prior to melting in the injection extruder. Since the additive works internally, it works automatically within the polymer during the moulding cycle to effect many benefits. These include effective mould release, and post-moulding benefits such as torque release, a reduction in surface friction, scratch and scuff resistance, post-moulding part assembly, and pigment dispersion. Improvements to cycle time are also examined. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.961389 Item 66 China Chemical Reporter 17, No.7, 6th March 2006, p.15 WHAT IS LEADING FLEXIBLE PACKAGE MATERIAL TO GROW Wang D China has over 5,000 flexible packaging producers with a total capacity of more than 1.8 million t/y. Film manufacturers such as DuPont, Dow and Shell have been active suppliers of BOPP and BOPETP in China’s market, while the OPS thermal shrink film market is controlled by Japanese companies. PVDC, EVOH, high-insulating aluminium foil film and modified PVA coating film will be the future development direction in China’s flexible packaging market. In inks, chlori-PP ink holds a 60% market share in China and polyamide ink a 30% market share. Water-based adhesives and alcohol-based ink have entered a good development period in China. Currently, 90% of flexible packaging adhesives are solvent-based, but water-based acrylic adhesives, mainly sold by Rohm & Haas, and PU adhesives are gaining more market share in China. CHINA

Accession no.961486 Item 67 Brookfield, Ct., SPE, 2005, 18 papers, 30cm, 012 4TH EUROPEAN ADDITIVES AND COLORS CONFERENCE. PROCEEDINGS OF A CONFERENCE HELD AACHEN, GERMANY, 16TH-17TH MARCH 2005 (SPE,Additives & Color Europe Div.) Eighteen papers are published following this 2 day conference focusing on the modification and colouration of plastics and polymers in Europe. Papers include: additives for improved optical appearance of plastics, low warping pigments for colouration of moulded articles, wetting agents for pigment dispersion: advantages and disadvantages, nano clay additives for oxygen and humidity barrier of polymers. EUROPE-GENERAL; EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; WESTERN EUROPE

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Item 68 POLYOLEFINS 2005. Proceedings of a conference held Houston, Tx., 27th. Feb. - 2nd. March 2005. Brookfield, Ct., SPE, 2005, Paper 3, pp.10, CD-ROM, 012 METALLOCENE-CATALYZED POLYETHYLENES FOR THE GLOBAL LLDPE MARKET Farley J M; Davey C R; Kolb R Univation Technologies (SPE,South Texas Section; SPE,Thermoplastic Materials & Foams Div.; SPE,Polymer Modifiers & Additives Div.; Society of Plastics Engineers) A description is given of next generation metallocenecatalysed linear, low density polyethylenes. Advances in catalyst and process technologies have allowed the production of polymers with tailored microstructures using a single, gas-phase reactor. The comonomer and molecular weight distributions are determiners of the ultimate balance of properties. Both can be controlled by the choice of catalyst system and reactor process conditions. This ability to tune polymer properties allows the resin producer to optimise grades for specific applications. In addition, the converter can further optimise the balance of film properties by adjusting the fabrication process. Commodity grades such as liners or stretch film as well as value-added grades for food packaging can be produced without a catalyst transition. The enhanced polymer performance combined with the attractive economics of the Unipol gas-phase reactor are claimed to make this new technology widely applicable to the global LLDPE market. Market trends and recent developments at Univation Technologies are discussed.

phase process ethylene-hexene resin. The resins were characterised to evaluate their behaviour under processing conditions and their overall performance in injection moulding applications. 4 refs. USA

Accession no.962389 Item 70 Brand 5, No.2, Jan.-Feb.2006, p.34-9 LET THERE BE LIGHT Vine K Pira In today’s market, point of purchase decisions are all important and there is an increasing market trend for the use of transparent packaging. However, the disadvantage of using clear packaging is that it lets in unfiltered light, which has a detrimental effect on food and drink, particularly dairy, meats and fresh juices. As well as discolouration, more serious effects include reducing shelf-life, effect on product flavour and reduction of nutritional content. The quest is on to develop packaging films and containers with high clarity and high barrier to sun and artificial light. Research has shown that the main cause of the damaging effects of light on food and drink products is the process of photooxidation. To an extent, products can be protected from the effects of light by reducing exposure to oxygen. The number of factors that influence the effects of light makes it very difficult to provide a universal packaging structure. WORLD

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USA

Accession no.962363 Item 69 POLYOLEFINS 2005. Proceedings of a conference held Houston, Tx., 27th. Feb. - 2nd. March 2005. Brookfield, Ct., SPE, 2005, Paper 29, pp.13, CD-ROM, 012 A NEW APPROACH TO ENHANCING POLYETHYLENE PRODUCT PERFORMANCE FOR RIGID THIN WALL LIDS USED FOR FOOD PACKAGING (SPE,South Texas Section; SPE,Thermoplastic Materials & Foams Div.; SPE,Polymer Modifiers & Additives Div.; Society of Plastics Engineers) A new linear low density polyethylene has been developed for thin walled lids used in rigid food packaging applications. The resin Surpass IFs932-A from Nova Chemicals Corp. is claimed to combine outstanding processability with excellent physical properties and part aesthetics. It is a single-site based ethylene-octene copolymer which is produced using Nova Chemical’s advanced Sclairtech technology and patented singlesite catalyst. It is compared to a Ziegler-Natta solution process ethylene-butene resin and a Ziegler-Natta gas

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Item 71 Flexible 4, No.5, Jan.-Feb.2006, p.40/8 SOLUBLE ISSUES Preston N Polyvinyl alcohol is the most commonly used watersoluble film and dissolves within about one minute when immersed in water. The first soluble packaging application on the consumer market was for the packaging of premeasured pouches of laundry detergents. In Europe alone, 15% of the laundry detergent market is accounted for by PVAL unit-dose products. The personal care sector, including body wash, shampoo and conditioner, is the next big area expected to be hit by the soluble film phenomenon. Sanitary items are another growth area, with significant potential for soluble films for tampon packages that the consumer can flush down the toilet. Edible, food-based films represent an alternative to PVAL and have obvious application in food packaging. The US Agricultural Research Service has developed food-based films that can be used as food wrap or straws, but also dissolve in liquid so that they can be eaten too. WORLD

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References and Abstracts

Item 72 High Performance Plastics Aug.2005, p.4 POLYESTER ELASTOMERS WITH BETTER THERMAL PROPERTIES Ticona, the US engineering thermoplastics company, has recently introduced a series of thermoplastic copolyester elastomers that offer enhanced thermal properties. This short article provides us with brief details of the five new grades, which are known as “Riteflex 425”, “Riteflex 430”, “Riteflex 435”, “Riteflex 440”, and “Riteflex 447”. Ticona; US,Food & Drug Administration USA

Accession no.962970 Item 73 Plastics Technology 51, No.8, Aug.2005, p.52/9 BARRIER BOTTLE TECHNOLOGIES SQUARE OFF Grande J A Single-serve packaging containers are raising shelf life demands, so packaging producers are looking for the barrier with the best cost-performance for PETP bottles. This article discusses in detail the latest developments in multilayer barrier solutions, as well as monolayer, coating, and oxygen-scavenging technologies. Advanced Plastics Technologies; Amcor PET Packaging; Business Development Associates; Colormatrix Corp.; DevTech Labs; Futura Polyesters; Honeywell Specialty Polymers; Husky Injection Molding Systems Ltd.; Coca-Cola Co.; Germany,Institute of Plastics Processing; Invista; Kortec Inc.; M and G Polymers; Mitsubishi Gas Chemical America Inc.; Nanocor Inc.; Schoenwald Consulting; Sidel Inc.; SIG Corpoplast; SIPA Inc.; Valspar Corp.; Wellman Inc.; SBA-CCI WorldPET; Martens; Coors Brewing Co.; Anheuser-Busch; Hite Brewery Co.; Hyosong Corp.; Oriental Brewing; Graham Packaging; Schott Hicotec; Shell Chemical; Kosa; US,Food & Drug Administration; Rexam; Foroya Bjor; Honeywell Performance Products ASIA; BELGIUM; CANADA; DENMARK; EU; EUROPEGENERAL; EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; INDIA; KOREA; NORTH AMERICA; RUSSIA; SCANDINAVIA; SOUTH KOREA; UK; UKRAINE; USA; WESTERN EUROPE; WESTERN EUROPE-GENERAL; WORLD

Accession no.963005 Item 74 Plastics Technology 51, No.8, Aug.2005, p.67 COLOR MATCHING GOES ONLINE This short article informs us that a new subscription-based service for formulating custom colours on the Internet (aimed at smaller companies that do not have their own

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colour-matching system and database) was launched in July 2005. It is called Matchmycolor.com. Brief details are given. Matchmycolor.com; SpecialChem; Ciba Specialty Chemicals; DuPont Titanium Technologies; X-Rite; Nelli Rodi TrendLab EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; WESTERN EUROPE

Accession no.963006 Item 75 Polimeri 26, No.3, 2005, p.128-32 Croatian SUSPENSION GRADE POLY(VINYL CHLORIDE) AND HAZARDS OF ITS PRODUCTION Kovacic T; Andricic B Split,University In suspension polymerisation of PVC, the monomer, liquid vinyl chloride(VC), is mechanically dispersed in water and polymerised by monomer-soluble initiator in the presence of protective colloid. The process is carried out in a batch reactor, in a closed system. From the environmental viewpoint, modern suspension polymerisation exhibits a relatively small number of problems. Among them, the most important is monomer carcinogenicity, as demonstrated in 1973. Technologists, physicians and scientists were soon engaged and new technological solutions were found, which eliminated monomer emission during the technological process, exposure of workers to VC, as well as the danger of high residual monomer concentration in the polymer. The maximum allowed concentrations of VC were also defined. Modern technology, using degassing and recovery of excess VC, removal of monomer from the polymer suspension, wastewater treatment and good process control, are shown to enable safe plant operation and use of PVC in the food and pharmaceutical industries and in medicine. 11 refs. CROATIA

Accession no.965084 Item 76 Plastics Additives and Compounding 8, No.2, March-April 2006, p.40-2 STABILIZERS: SOME RECENT DEVELOPMENTS Ferro has introduced five environmentally-friendly nonlead mixed-metal heat stabilisers that offer improved performance compared to currently available alternatives to lead stabilisers. Therm-Chek 7208P is a calciumzinc powder stabiliser for high temperature cable and automotive wire applications. Chemtura’s Mark OBS Organic Based Stabilizers for rigid and flexible PVC are heavy-metal-free alternatives to traditional lead, Ba/Zn and Ca/Zn stabilisers. To meet the growing need for a high performance UV screener for the PETP packaging

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industry, Cytec has introduced Cyasorb 3638F light stabiliser. Another product, Cyasorb 3808PP5 light stabiliser, is said to provide outstanding weatherability in interior and exterior automotive TPO. Cytec is also introducing CEC 350, a light stabiliser product for twoand three-year greenhouse film applications. WORLD

Accession no.965451 Item 77 New Scientist 190, No.2549, 29th April 2006, p.25 DISAPPEARING TATTOO It is briefly reported that new tattoo inks that are safer to use and far easier to remove are set to be launched next year. Freedom-2 is planning to introduce a range of dyes that have already been approved by the FDA for use in cosmetics, food, drugs and medical devices. To prevent the dyes being absorbed by the body, they are encapsulated in protective polymer beads just 1-3 micrometres in diameter. This is small enough to allow them to be injected into the skin and absorbed by skin cells to form a tattoo. The pigment can be removed by a single laser treatment which splits the beads open, dumping the dye into cells where it is absorbed. Freedom-2 USA

Accession no.965474 Item 78 Journal of Macromolecular Science A A43, No.2, 2006, p.315-26 GRAFT COPOLYMERIZATION OF POLYACRYLAMIDE ONTO TAMARIND MUCILAGE Mishra A; Bajpai M Kanpur,Chhatrapati Shahu Ji Maharaj University The graft copolymerisation of polyacrylamide onto a watersoluble food grade polysaccharide, Tamarind mucilage, initiated by ceric ion, and characterisation of the products by viscosity, FTIR, SEM, DSC, TGA and biodegradation studies is described. The effects of monomer concentration, initiator concentration, reaction time and temperature on grafting efficiency and degree of grafting were investigated and the results are discussed. 15 refs.

DETERMINE TRANSPORT PROPERTIES AND INTERACTIONS IN FOOD PACKAGING FILMS Cava D; Cabedo L; Gimenez E; Gavara R; Lagaron J M CSIC; Jaume I,Universitat A simultaneous analysis of the transport properties of water through extruded food packaging films made of ethylenevinyl alcohol copolymers with various ethylene contents (26 to 48 mol %) and of water/polymer interactions was carried out using FTIR spectroscopy. A characterisation of solvent uptake (water sorption isotherms), diffusion and permeability coefficients as a function of ethylene content and relative humidity was performed across the above composition range. From the results, a previously unreported Langmuir contribution was found at low relative humidity conditions for the copolymers, which could be responsible for the unusual trend in oxygen permeability reported earlier for these materials. Furthermore, a distribution of water molecules with different hydrogen bonding strengths and different diffusion rates was encountered, which suggested that the interaction and transport properties of moisture in these polymers was not a simple and homogeneous process. 14 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN; WESTERN EUROPE

Accession no.966205 Item 80 Package Print and Converting International May-June 2006, p.8 HIGH PERFORMANCE PHTHALATE-FREE WATER-BASED COATING In recent years, phthalate ester emissions have become a major environmental and health concern. Food packaging concerns have been focused on the use of phthalate plasticisers in inks and coatings, and some packaging films, as there is a risk that the phthalates may migrate into foods. A new generation of water-based coatings available from Starna Industries, which is free from phthalates such as DINP, DIDP, DNOP, BBP and DEHP, is Curecoat. Not only is Curecoat free from phthalates, the formulae is also free from VOCs and HAPs. Application is via flexo, gravure or roller coater and drying is via hot air or infrared. Curecoat can be used as a primer on coated and non-coated papers, foils and fabrics and offers users the possibility as a primer on metallised films and papers. Starna Industries

INDIA

EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

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Item 79 Polymer Testing 25, No.2, 2006, p.254-61 EFFECT OF ETHYLENE CONTENT ON THE INTERACTION BETWEEN ETHYLENE-VINYL ALCOHOL COPOLYMERS AND WATER. I. APPLICATION OF FT-IR SPECTROSCOPY TO

Item 81 Brand 5, No.3, March-April 2006, p.42-8 OIL CHANGE Vine K

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In March 2006, for the first time, biopolymers and oil-based polymers have reached the same price by weight. This

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References and Abstracts

removes one of the main barriers to the use of bioplastics, material costs. Biopackaging refers to packaging that is either biodegradable (it will break down or compost) or sustainable (it is made from a renewable resource). There are three main forms of renewable biopackaging: polylactic acid, polyhydroxyalkanoates and thermoplastic starch. Despite the fact that the use of biopackaging is on the increase, applications are still relatively few and it remains a niche market. This article looks at whether biopackaging will ever be able to move into the mainstream packaging market. It examines the main drivers for the biopackaging industry and how these differ between different global markets, the types of biopackaging being used by retailers and brand owners, and the downsides to biopackaging that are holding the market back. WORLD

Accession no.967425 Item 82 Shawbury, Smithers Rapra Ltd., 2006, pp.viii, 280, ISBN 1859575277, 25cm, 6P ASSESSING FOOD SAFETY OF POLYMER PACKAGING Vergnaud, J; Rosca I (Rapra Technology) This book is designed to help current and prospective researchers in the field of food safety in plastic packaging. The book is divided into 7 chapters. Chapter 1 is devoted to a theoretical discussion of the process of diffusion through a sheet. Chapter 2 is concerned with the transfer of the contaminants taking place in packages before they are in contact with food. Chapter 3 is devoted to the problems caused by the process of co-extrusion or co-moulding of the films or of the packages. Chapter 4 is the chapter in which some applications of the theoretical considerations established in Chapters 1 to 3 are developed further. Chapter 5 considers the future, when use of active packaging will be widespread. Chapter 6 discusses the misconceptions arising from the processes or misuse of equations. Chapter 7 details the conclusions arising from the book. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.967542 Item 83 Analytica Chimica Acta 566, No.1, 27th April 2006, p.60-8 PREDICTING THE PERFORMANCE OF MOLECULARLY IMPRINTED POLYMERS: SELECTIVE EXTRACTION OF CAFFEINE BY MOLECULARLY IMPRINTED SOLID PHASE EXTRACTION Farrington K; Magner E; Regan F Dublin,City University; Limerick,University The design and synthesis of a molecularly imprinted polymer capable of extracting caffeine as template from a

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standard solution and from food samples was investigated. The use of NMR titration experiments and molecular modelling in determining the relative ratios of template to functional monomer, and in the choice of solvent as porogen and the amount used is discussed. A stepwise procedure for the development and testing of a molecularly imprinted polymer is proposed. EUROPEAN COMMUNITY; EUROPEAN UNION; IRELAND; WESTERN EUROPE

Accession no.967738 Item 84 Shawbury, Rapra Technology, 2006, pp. 148, 29 cm. Rapra Review Rept. No. 182, vol. 16, No. 2, 2006 FOOD CONTACT RUBBERS 2 - PRODUCTS, MIGRATION AND REGULATION Forrest M J Rapra Technology Edited by: Humphreys S (Rapra Technology) Rapra Review Report No.182 This review report gives a comprehensive overview of the use of rubber as a food contact material. It includes information on the types of rubber and rubber products used in the industry, formulations, contact regulations and migration testing regimes. Also included are details of on-going research to improve its safety, and future trends. Some major research projects carried out in the UK are discussed, and a comprehensive survey of the available migration data is included. 257 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; WESTERN EUROPE-GENERAL

Accession no.969308 Item 85 Rubber and Plastics News 35, No.24, 26th June 2006, p.14-16 REVIEWING SCIENCE OF COLORING RUBBER COMPOUNDS Stewart W M Excel Polymers LLC Colour science is often misunderstood. Rubber technologists spend years learning how to compound and develop excellent compound properties, yet few truly understand the importance of colour selection and dispersion to overall compound properties. This paper reviews the science of colour and appearance then focuses upon pigment selection and several types of pigment incorporation technologies. Different light sources can lead to metamerism and surface texture may dramatically affect the appearance of the colour. The basics of colour science and some different methods for introducing colourants into production batches are examined. Looking beyond the initial raw material cost allows the evaluation of various methods for lower total production cost. It is important to review the costs associated with scrap, cleanup and

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efficiency of manufacturing process. Knowledge, quality, consistency and innovation are important characteristics to look for in colour suppliers. USA

Accession no.970315 Item 86 Plastics Additives and Compounding 8, No.3, May-June 2006, p.9 EUPOLEN PE BLUE RECEIVES FDA APPROVAL BASF’s pigment preparation Eupolen PE Blue 69-1501 has received Food Contact Notification approval from the American FDA, it is briefly reported. As a result, the product can be used in concentrations up to 2% in plastic items that come into contact with food, including closures for drinks bottles, crates for fruit and vegetables, freezer boxes, drinks cans, plastic cups and packaging films. Eupolen PE Blue 69-1501 is a highly concentrated polyolefin-based, dispersed mono-pigment concentrate. High colour strength, good fastness to light and weathering, constant colouristic properties, good metering properties and a low-dust physical form are the characteristics of Eupolen PE Blue 69-1501. BASF USA

Accession no.970380 Item 87 Plastic Packaging Innovation News 2, No.8, 13th June 2006, p.7-8 RESEARCHERS DISCOVER COLOURANT THAT DOESN’T STAIN It is briefly reported that researchers have discovered a natural yellow pigment that will not stain plastic packaging. The pigment, called phloridzine oxidation product (POP), a by-product of the cider industry, could provide a natural alternative to existing yellow pigments such as tartrazine and carotene. POP is completely water soluble and can be used in both the food and cosmetics industries. INRA EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; WESTERN EUROPE

Accession no.970426 Item 88 LCGC Europe 19, No.7, Suppl., July 2006, p.41 ANALYSIS OF POLYDIMETHYL SILOXANE BY GPC VISCOMETRY Saunders G Polymer Laboratories Ltd. Polydimethyl siloxane or PDMS is a non-toxic, nonflammable silicon-based polymeric material noted for its unusual rheological behaviour. PDMS is a viscoelastic material, which with long flow times or at high temperatures behaves similar to a liquid. However, with

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short flow times or at low temperatures, it behaves in the same way as rubber. This application note describes the analysis of PDMS by GPC using the PL-GPC 50 integrated GPC instrument. Due to the importance of the viscometric properties of the material in many final applications, a PLBV 400 viscometer was included in the PL-GPC 50 as well as the standard refractive index detector. This combination of detectors also allows analysis of the material by the Universal Calibration method, giving accurate molecular weights which are not reliant on the chemistry of the standards used for calibration. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.970438 Item 89 Plastic Packaging Innovation News 2, No.9, 27th June 2006, p.8 BASF RECEIVES FOOD CONTACT APPROVAL FOR BLUE PIGMENT It is briefly reported that BASF’s new pigment preparation could be used in plastic packaging within weeks. Although the pigment is already on the market, BASF only received approval for food contact use from the US FDA in March 2006. The pigment preparation, Eupolen PE Blue 69-1501, can now be used in concentrations of up to 2% in plastic packaging that comes into contact with food, such as closures for drinks bottles, plastic cups or packaging films. The pigment is also suited for use in all kinds of injection moulding applications such as flatware, plates or closures. BASF USA

Accession no.970443 Item 90 Food Additives and Contaminants 23, No.7, July 2006, p.726-737 EXAMINATION OF STYRENEDIVINYLBENZENE ION-EXCHANGE RESINS, USED IN CONTACT WITH FOOD, FOR POTENTIAL MIGRANTS Sidwell J A; Willoughby B G Rapra Technology Ltd. The nature of extractable substances from various styrenedivinylbenzene ion exchange resins, including strong acid cation resins, strong and weak base anion resins and an active carbon replacement resin (macroporous crosslinked PS based Macronet with a very high internal surface area) was investigated by means of electrospray liquid chromatography-mass spectroscopy- and gas chromatography-mass spectroscopy techniques. Volatile species were detected and the possible implications of the data obtained on food safety briefly discussed. 7 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.971848

© Copyright 2007 Smithers Rapra Technology

References and Abstracts

Item 91 Food Additives and Contaminants 23, No.7, July 2006, p.738-746 DIFFUSION OF LIMONENE IN POLYETHYLENE Limm W; Begley T H; Lickly T; Hentges S G US,Food & Drug Administration; Dow Chemical Co.; American Plastics Council Diffusion coefficients of limonene in various LLDPEs, HDPEs and LDPEs were determined from sorption data by TGA and the effects of comonomers, catalysts and processing methods on the barrier properties of the polyethylenes at 30C investigated using limonene as the probe sorbent. Absorption and desorption tests were also carried out on heat-pressed films made from the resins, the results of which indicated that the diffusion coefficients of limonene did not change substantially. 31 refs. USA

Accession no.971849 Item 92 Campus Datasheet CAMPUS DATASHEET FOR MINLON EFE6096 GY090A, A MINERAL-FILLED POLYAMIDE-6,6 FROM DUPONT ENGINEERING POLYMERS DuPont Engineering Polymers (M-Base Engineering and Software GmbH) CAMPUS datasheet for an impact-modified, heatstabilised, 15% mineral-filled polyamide-6,6 for injection moulding applications. It exhibits very low warpage and improved impact resistance. It contains grey pigment. Identification: ISO 1043: PA66-IMD15. ISO 3795 / FMVSS 302 burning rate: < 100 mm/min. Specific certification is available on request. This grade is not compliant with European food contact requirements. Applications include wheel covers. This datasheet is one in a range of datasheets provided by Materials Data Center from the CAMPUS (Computer Aided Material Preselection By Uniform Standards) database. All data is measured according to strict CAMPUS ISO standards, thus ensuring a high standard of data comparability across different manufacturer’s datasets. For an indication of properties given on the datasheet, please see the list of keywords below. If appropriate, this datasheet PDF is updated at 3 monthly intervals. For subscription information regarding the Materials Data Center, please follow the link on the Rapra Polymer Library home page http://www.polymerlibrary.com EU; EUROPEAN COMMUNITY; EUROPEAN UNION; WESTERN EUROPE-GENERAL

Accession no.972268 Item 93 Campus Datasheet CAMPUS DATASHEET FOR MINLON EFE6091 BK375, A GLASS FIBRE AND MINERAL

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REINFORCED A POLYAMIDE-6,6 FROM DUPONT ENGINEERING POLYMERS DuPont Engineering Polymers (M-Base Engineering and Software GmbH) CAMPUS datasheet for a heat-stabilised, 25% glass fibre, 15% mineral reinforced polyamide-6,6 for injection moulding applications. It exhibits very low warpage, and improved mechanical strength and temperature resistance. It contains black pigment. Identification: ISO 1043: PA66-(GF+MD)40. ISO 3795 / FMVSS 302 burning rate: B51 mm/min. Specific certification is available on request. This grade is not compliant with European food contact requirements. Applications include automotive fan shrouds. This datasheet is one in a range of datasheets provided by Materials Data Center from the CAMPUS (Computer Aided Material Preselection By Uniform Standards) database. All data is measured according to strict CAMPUS ISO standards, thus ensuring a high standard of data comparability across different manufacturer’s datasets. For an indication of properties given on the datasheet, please see the list of keywords below. If appropriate, this datasheet PDF is updated at 3 monthly intervals. For subscription information regarding the Materials Data Center, please follow the link on the Rapra Polymer Library home page http://www. polymerlibrary.com EU; EUROPEAN COMMUNITY; EUROPEAN UNION; WESTERN EUROPE-GENERAL

Accession no.972269 Item 94 Food Additives and Contaminants 23, No.8, Aug.2006, p.854-860 MIGRATION OF DEHYDROABIETIC AND ABIETIC ACIDS FROM PAPER AND PAPERBOARD FOOD PACKAGING INTO FOODSIMULATING SOLVENTS AND TENAX TA Asako Ozaki; Tomoko Ooshima; Yoshiaki Mori Osaka,City Institute of Public Health and Environmental Sciences An investigation was undertaken to establish the concentration in paper products of dehydroabietic(DHA) and abietic(AA) resin acids, present in rosin, which are major toxicants of pulp- and paper-mill effluent. Their migration was studied from paper and paperboard products into various food-simulating solvents and the substitute fatty food simulant Tenax TA (modified polyphenylene oxide). DHA and AA were detected in 5 of 10 virgin paper products and in all 10 recycled paperboard products for food-contact use at concentrations of 14-500 and 110-1200 microgram/g, respectively. In virgin paper products, the highest migration was into 95% ethanol or heptane, with negligible or no migration into other solvents. In recycled paperboard products, migration was highest into 95% ethanol, but was also observed into 20% ethanol, water and heptane. Migration to Tenax TA was also observed and the migration level increased with time. The maximum

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migration levels of DHA and AA into food simulants were 0.853 and 3.14 microgram/g, respectively. The results suggested that, in the worst case, the daily intake of DHA and AA from paper and paperboard products was 50 times lower than the tolerable daily intake of rosin. 21 refs. JAPAN

Accession no.975308 Item 95 Plastics Additives and Compounding 8, No.4, July-Aug.2006, p.40-43 SETTING NEW STANDARDS FOR THE ANALYSIS OF ADDITIVES IN POLYETHYLENE Van Der Maten T PANalytical BV The analysis of additives in polymers is an essential part of the production process. Recent advances in Xray fluorescence spectroscopy have provided polymer and plastics manufacturers with better process control, higher cost efficiency and a much clearer overview of their environmental impact. The data presented clearly demonstrates that the new PANalytical XRF spectrometer, Axios-Poly, with ADPOL calibration standards delivers the accurate and repeatable measurement that is required in the industry today. The combination offers a highly effective method of measuring sub-ppm levels for a wide range of important elements. EUROPEAN COMMUNITY; EUROPEAN UNION; NETHERLANDS; WESTERN EUROPE

Accession no.975912

in PP resins subjected to multiple heat histories. The materials are expected to find applications in end-uses such as pharmaceuticals, infant products and some food packaging, allowing processors to benefit from the technical and physical properties of clarified PP without sacrificing clarity and transparency. Several grades in the PProTint range are now FDA compliant. This abstract includes all the information contained in the original article. PolyOne USA

Accession no.976953 Item 98 Plastic Packaging Innovation News 2, No.16, 3rd Oct.2006, p.6-7 POLYVAL PUSHES SOLUBLE BAGS AT FRESH FOOD INDUSTRY It is briefly reported that Polyval is looking to supply its PVAL film to the packaging industry for fresh produce. Although the bags are made from fossil fuels, they dissolve in water within a few hours and then fully degrade into water and carbon dioxide after 12 weeks. Polyval has food contact approval for the film, but the major limitation is that it can only be used to package dry foods. One of the main advantages of the film over PE is that it is impervious to gases, but it allows water vapour to be transmitted, preventing condensation from forming on the inside of a package. Other potential applications of the dissolvable material are laundry bags and cement bags. Polyval plc EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Item 96 Woodston, UK, Recoup, 2006, 30cm, pp.39, Available online from http://www.recoup.org/design/docs/ Recyclability_40page.pdf (Accessed on 22/09/06) PLASTICS PACKAGING: RECYCLABILITY BY DESIGN Reckitt Benckiser (Recoup)

Accession no.977006

The objective of this guide was to produce definitive guidance to designers and specifiers on the design of plastic packaging to facilitate recycling. The guide is divided into the following main sections: aims, general guidelines, and material specific guidelines for containers and film. Nestle waters; SPI

According to Fasson Roll North America, the largest film markets for narrow web include home and personal care, beer and beverage, security and food labelling. The company expects 3-5% growth for films in the home and personal care industry and double digit growth in the beer and beverage industry. One of the largest growth areas for film is the use of pressure sensitive labels in the beverage market with some notable key users switching to PP-based PS labels, primarily in the beer sector. Plastic Suppliers manufactures EarthFirst PLA film which is used in the flexible packaging, labelling, shrink sleeve labelling, tamper evident and windowing markets. Working with films poses different challenges for converters than working with papers. Surface treatment of most films is important for adhesion of inks, toner and adhesives.

EU; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.976040 Item 97 European Plastics News 33, No.9, Oct.2006, p.33 CUTTING THE HAZE IN PP RESINS PolyOne’s OnColor PProTint and PProTintPlus are two new products designed to mask the haze that develops

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Item 99 LNW Label and Narrow Web 11, No.6, Sept.2006, p.50/57 FILM LABEL ADVANCEMENTS Sartor M

USA

Accession no.977020

© Copyright 2007 Smithers Rapra Technology

References and Abstracts

Item 100 2005 PLACE Conference. Proceedings of a conference held Las Vegas, Nv., 27th-29th Sept.2005. Atlanta, Ga., TAPPI Press, 2005, Paper 23, pp.23, CDROM, 012 THE EFFECTS OF RETORT CONDITIONS ON CLEAR HIGH BARRIER LAMINATED STRUCTURES Mueller T R Rohm & Haas Co. (TAPPI) The performance of solventless and solvent-based adhesives in retort structures was evaluated. Tests were conducted on pouches made from four ply PETP laminations with and without aluminium foil, which were filled with water and retorted at 121 deg.C for one hour, 132 deg.C for 30 minutes or 132 deg.C for 30 minutes and water quenched. The barrier properties and interlaminar bond strengths before and after retort were assessed and compared with those of conventional foil structures. USA

Accession no.977614 Item 101 High Performance Plastics May 2006, p.4 METALLIZED POLYESTER FILM A new thermal silver-metallised PETP film has been introduced by GBC Films Group Europe of the Netherlands, it is reported here. The film, known as “7100 Metallized PET”, is geared at applications in food and retail packaging. Brief details are given in this little item. GBC Films Group Europe; Acco Brands Corp. EUROPE-GENERAL; EUROPEAN COMMUNITY; EUROPEAN UNION; NETHERLANDS; USA; WESTERN EUROPE

Accession no.977751 Item 102 Modern Plastics World Encyclopedia 2006, p.87-88 MULTIPLE USES MEAN PP SPANS COMMODITIES TO VALUE-ADDED PRODUCTS Herrgard G Borealis Polymers Oy The ability of polypropylene to be used in a variety of applications is discussed with reference to market trends and material developments. PP is the world’s third most popular polymer after polyethylene and polyester. Its production is estimated to be 44.38 million tonnes in 2005. demand for PP in mature areas of application is being stimulated by improved resin performance. Injection moulding, pipe, automotive and some film applications have growth rates above the average. Technology developments in these areas are described, and include products providing a stiffness/impact balance, grater stiffness, achieved by means of multimodal polymerisation using high isotacticity catalysts, and flexural moduli

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reaching 2500 MPa in future. Other developments include impact resistance grades for food packaging and durable goods, improved melt flow rates to meet the demands of complex mouldings, and heat resistant, scratch resistant and paintable products for automotive applications. Film and pipe applications are also examined. EUROPEAN UNION; FINLAND; SCANDINAVIA; WESTERN EUROPE; WORLD

Accession no.977989 Item 103 Flexible 5, No.2, July-Aug.2006, p.10-17 ASIAN FILMS This article discusses the prospects for Asia’s flexible packaging industry. China is developing the world’s largest packaging industry, which is expected to grow by 12% annually through to 2010. The main end-users of flexible packaging are ranked as pharmaceutical, fast food, pet food and personal care and hygiene. In India flexible packaging is the most common packaging format, with many traditional rigid pack formats being replaced with flexible versions. For many years, India has been exporting unconverted BOPP, PETP and PE films, and more recently converted products. Vietnam has been growing at a rate of 7% annually and its emerging flexible packaging industry has been experiencing extraordinary growth rates. ASIA

Accession no.978244 Item 104 Flexible 5, No.2, July-Aug.2006, p.18/27 FLEXED FOR GROWTH With the increasing demand volume of flexible packaging in each end-user market, the annual output of the Chinese flexible packaging plants is surging. In 2004, shipments of flexible packaging in China amounted to 3.09 million tonnes, with the market growing at an annual rate of more than 10%. This article gives an overall description of the raw materials market, focusing on the main properties of the materials and their application status in the Chinese flexible packaging plants. Films include PE, BOPP, CPP, EVOH, metallised film, PA/BOPA, PVC, PVDC, PETP/ BOPETP and metallocene polymers. Adhesive, ink and heat/cold seal coatings are also examined. CHINA

Accession no.978245 Item 105 Plastic Packaging Innovation News 2, No.17, 17th Oct.2006, p.5 PACKAGING STICKS According to a 2006 Pira market report, the global market for adhesives in flexible packaging in 2004 was almost 245

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million kg. It was expected to increase by 8.4% in 2005 and by a further 13.2% between 2005 and 2010. Growth is expected to continue across all main end use markets between 2005 and 2010, with the exception of cosmetics and toiletries, where a slight decline is noted. The largest rise in demand is anticipated in the meat, fish and poultry, pet food and savoury snacks product sectors as these markets evolve in developing economies. Technological developments are being driven by legislation as well as cost-reduction considerations. In the coming years, there is likely to be a significant improvement in the range of laminating adhesives available, involving the use of new and improved chemistry, films and resins. Broad changes are anticipated in the use of adhesives, reflecting a move away from solvent-based adhesives towards more environmentally friendly products such as water-based adhesives. Pira International WORLD

Accession no.978345 Item 106 Polymers Paint Colour Journal 196, No.4504, Sept.2006, p.48/50 FOOD FOR THOUGHT James V Dow Corning Ltd. U.S. Food and Drug Administration and Council of Europe food packaging regulations which could severely limit material choice for the ink and varnish industries are discussed. It is shown that with expertise in modifying the architecture of silicone-polyether copolymer technology, structures can be designed which can achieve good foam control and film quality in the manufacture and application of waterborne inks and varnishes while, most importantly, allowing compliance with food packaging legislation in place to protect the public. 2 refs. US,Food & Drug Administration; Council of Europe EUROPE-GENERAL; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; USA; WESTERN EUROPE

Accession no.979151 Item 107 ANTEC 2006. Proceedings of the 64th SPE Annual conference held Charlotte, NC., 7th-11th May 2006. Brookfield, Ct., SPE, 2006, p.92-7, PDF 103578, CDROM, 012 WORKING WITH ORGANIC PIGMENTS IN YELLOW COLOR SPACE Cole D T; Reinicker R A Ciba Specialty Chemicals Corp. (SPE) Formulators colouring plastics and synthetic fibres can select from a variety of organic colorants in order to achieve a final desired colour. The choices can be confusing unless the colorants are previously specified

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or are well known to the formulator. This paper will deal with a subset of the colorants in yellow colour space while clarifying the selection process with respect to some of the most important properties of the colorants for plastics and fibres. 4 refs. USA

Accession no.979210 Item 108 Silicone Elastomers 2006. Proceedings of a conference held Frankfurt, Germany, 19th-20th Sept. 2006. Shawbury, Rapra Technology, 2006, Paper 3, pp.24, 29 cm, 012 THE USE OF GCXGC-TOFMS AND LC-MS FOR THE DETERMINATION OF MIGRANTS FROM SILICONE RUBBERS INTO FOOD SIMULANTS AND FOOD PRODUCTS Forrest M J; Holding S R; Howells D; Eardley M Rapra Technology (Rapra Technology) The aim of this work is to demonstrate how the enhanced capabilities of GC-GCxTOFMS and LC-MS can be used to generate migration data on silicone rubbers in contact with both aqueous and fatty food simulants and foods, that would not be possible using standard GC-MS and HPLC instruments. Specific migration experiments were carried out using both food simulants (distilled water and 95% ethanol), and a number of food products (carbonated water, white wine and olive oil). The results obtained from the analysis of these samples by GCxGC-TOFMS and LC-MS showed that the principal species of interest were siloxane oligomers. 4 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.979244 Item 109 Przemyst Chemiczny 85, No.7, July 2006, p.471-477 Polish THE TRENDS IN INDUSTRIAL APPLICATIONS OF REACTIVE POLYMERS ON THE EXAMPLE OF ROHM AND HAAS COMPANY’S PRODUCTS Kociolek-Balawejder E; Surowiec J Wroclaw,Academy of Economics; Rohm & Haas France SAS A review is presented on ion exchange resins for the treatment of industrial water, potable water, polymeric catalysts and resins for food purification, environmental protection and pharmaceutical and medical diagnostic applications. 16 refs. EASTERN EUROPE; EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; POLAND; WESTERN EUROPE

Accession no.980073

© Copyright 2007 Smithers Rapra Technology

References and Abstracts

Item 110 European Coatings Journal No. 10, 2004, p.31/6 UV SYSTEM HAS STICKING POWER Tonnoir O SICPA Adhesion issues relating to UV ink technology in converting applications are discussed, and an alternative UV technology is presented which is claimed to provide outstanding adhesion. This involves the use of new resins based on chemically-modified epoxy acrylate, and a dual curing mechanism. The modification results in an isocyanate prepolymer which can be cured under UV light. When the film is cured under UV light, it becomes a part of the substrate, linked by a strong molecular bonding within the ink film and between the film and substrate. The technique is reported to be able to address the continuous problem of how to achieve a good printability without altering adhesion, and is proposed as an economic alternative to expensive technical solutions to the adhesion problem. 3 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.926596

materials with optimised and enhanced agricultural and food packaging performances. Microhardness measurements are used to analyse the mechanical response of the materials in order to obtain information about the dispersion of the two immiscible components. Good versatility is achieved although properties may be improved by addition of a compatibilising agent. 23 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.927180 Item 113 Popular Plastics and Packaging 49, No.10, Oct.2004, p.100-2 LATEST DEVELOPMENTS IN PLASTICS PACKAGING Kulshreshtha A K Indian Petrochemical Corp.Ltd. This article discusses the latest developments in active packaging, including oxygen scavengers, antimicrobial films and intelligent films. INDIA

Accession no.927262 Item 111 Modern Plastics International 34, No.11, Nov.2004, p.52 HIGH-PERFORMANCE PE TARGETS THINWALLED PARTS A new grade of Surpass single-site catalyst-produced PE, IFs932A, targets thin-wall injection moulding applications, it is briefly reported. This material has low viscosity to allow easier mould fills with high cavitation tools, shorter cycle times, high clarity and energy savings due to lower barrel temperatures. It has a balance of toughness and stiffness. The organoleptic properties are said to be superior to other PE grades on the market, making it ideal for food packaging applications such as lids and closures. Nova Chemicals CANADA

Accession no.926682

Item 114 Plastics News(USA) 16, No.39, 29th Nov.2004, p.4 TORAY EXPANDS PET, PP FILMS Pryweller J It is briefly reported that Toray Plastics (America) is expanding into PETP film packaging applications in North America. The company has introduced a coextruded, chemically treated film that offers good adhesion to waterand solvent-based inks and a one-sided, heat-sealable film for wrapping portable foods. The company has also launched a heat-sealable oriented PP film for food packets and stand-up pouches. To make the films, the company will shift production in North Kingston, R.I., away from the manufacture of PETP tape films for the video market. Toray Plastics (America) Inc. NORTH AMERICA

Item 112 Journal of Polymer Science: Polymer Physics Edition 42, No.20, Oct. 2004, p.3766-74 OXYGEN PERMEABILITY IN BLENDS OF A VINYL ALCOHOL/ETHYLENE COPOLYMER AND A METALLOCENIC ETHYLENE/1-OCTENE COPOLYMER Laguna M F; Cerrada M L; Benavente R; Perez E Instituto de Ciencia y Tecnologia de Polimeros The preparation, morphological characterisation and oxygen permeability of blends of a vinyl alcohol-ethylene (VAE) copolymer with a metallocenic ethylene-1-octene copolymer (CEO) are presented. The study aims to design

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Accession no.927265 Item 115 Polymers Paint Colour Journal 194, No.4482, Nov.2004, p.15-6 PACKAGING INKS GO GREEN Ivory N Sun Chemical Ltd. Problems experienced in the application of cationicallycured printing inks to non-food contact packaging resulting from the by-products of photolysis of the photoinitiators causing odour or taint and the potential for migration of chemical species into food, are reviewed.

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The commercial development of new cationic initiators to overcome these problems is described. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.927672 Item 116 European Plastics News 32, No.1, Jan.2005, p.10 BIOPOLYMERS KEEP GROWING Proctor & Gamble is continuing its research into bio-based biodegradable aliphatic polyester (PHA). Although there has been progress towards commercialisation, there are still performance and design barriers to be addressed. In blow and injection moulding the challenges are cycle time and impact resistance. However, one tableware application already looks attractive for P&G in Nodax PHA, painted tableware, where Nodax provides not only an enhancement over the conventionally used PP materials in terms of strong adhesion without using a primer coat, but cost savings as well. Italian packaging company Alcas has released a range of ice-cream cups made from NatureWorks PLA. In film, Dutch fresh produce distribution company The Greenery plans to produce its first produce packed in biopolymer film. WORLD

Accession no.928478 Item 117 Macromolecular Bioscience 4, No.11, 20th Nov.2004, p.1053-60 PHYSICAL CHARACTERIZATION OF COUPLED POLY(LACTIC ACID)/STARCH/ MALEIC ANHYDRIDE BLENDS PLASTICIZED BY ACETYL TRIETHYL CITRATE Zhang J-F; Sun X Kansas State University The effects of acetyl triethyl citrate as plasticiser on the properties of blends of poly(lactic acid) with starch, compatibilised with maleic anhydride using 2,5-bis(tertbutylperoxy)-2,5-dimethylhexane as initiator, were investigated by tensile testing, water absorption, DSC and SEM. Migration and leaching of the plasticiser into water is discussed in terms of potential food-contact applications of the blends. 31 refs. USA

Accession no.929443 Item 118 Food Additives and Contaminants 21, No.10, Oct.2004, p.1007-14 MIGRATION OF A UV STABILIZER FROM POLYETHYLENE TEREPHTHALATE(PET) INTO FOOD SIMULANT Begley T H; Biles J E; Cunningham C; Piringer O

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US,Food & Drug Administration; Fabes GmbH The migration of Tinuvin 234 (2-(2H-benzotriazol-2-yl)4,6-bis(1-methyl-1-phenylethyl)phenol) into food simulants from PETP was measured using high-performance liquid chromatography with UV detection. Ethanol/water, isooctane and a fractionated coconut oil simulant (Miglyol) were used as food simulating solvents. The migration characteristics were measured at temperatures in the range 40 to 70C. Diffusion coefficients were determined. At 40C, the amount of migration into 95% ethanol after 10 days was 2 microgram/sq dm. Isooctane was found to be a good fatty food simulant which provided similar results for PETP to those of fatty foods. 12 refs. Ciba Specialty Chemicals Corp. USA

Accession no.929906 Item 119 Plastics Additives and Compounding 6, No.6, Nov.-Dec.2004, p.11 RECYCLABLE PRODUCTS BENEFIT FROM YELLOW PIGMENT It is briefly reported that Shepherd Color has introduced a chrome-free yellow pigment which the company says can be used in products that need to meet recycling and food contact legislation. The pigment, Yellow 20P296, is part of the company’s Artic infrared reflecting pigment line and is a clean, red, buff shade. Because it is heavy metal free, it can be used in an variety of products that fall under environment or food contact legislation. These include applications in the automotive and electrical markets where materials are often recycled at the end of the product life. Shepherd Color Co. USA

Accession no.930311 Item 120 Plastic Packaging Innovation News 1, No.1, 16th Dec.2004, p.7 ROHM AND HAAS GETS STUCK INTO WATERBASED ADHESIVES Rohm & Haas has revealed it is developing a water-based adhesive for foods that are challenging to pack because of their moisture content, such as cheese, meat and coffee. The company plans to have an improved version of its Robond L, an acrylic water-based adhesive for dry bond lamination applications, commercialised during 2005. The advanced version of Robond L will have improved product resistance for use with fat, vinegar, oil and fruit juice and temperature resistance for withstanding the high temperatures during pasteurisation. Rohm & Haas Co. USA

Accession no.930367

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References and Abstracts

Item 121 Patent Number: EP 1475425 A1 20041110 THERMAL PROCESS FOR THE MANUFACTURE OF A LAMINATE AND APPARATUS THEREFOR Narumiya T; Asano I; Kasahara H; Tanaka R Nakamoto Packs Co.Ltd.; Nissei Chemical Co.Ltd. The manufacturing method involves laminating a first substrate film layer and a second substrate film layer through an adhesive resin layer, integrating the adhesive resin layer with the first substrate film layer, heating the surface of the adhesive resin layer by heat rays in the presence of oxygen to induce functional groups which contribute to adhesion and superimposing the second substrate film layer on the adhesive resin layer to be bonded thereto with pressure. The thermal laminate is strong without the need for solvent and is safe and hygienic in contact with food. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; JAPAN; WESTERN EUROPE-GENERAL

Accession no.930660 Item 122 British Plastics and Rubber Jan.2005, p.22-3 RINGING THE CHANGES ON ENGINEERING THERMOPLASTICS Cyclics Corporation is planning to double the size of its 2,500 t/y plant at Schwarzeheide, Germany, towards the end of this year and has started planning for a second plant of 25-50,000 t/y capacity which could be on-line by 2009. Cyclics makes cyclic PBTP, CBT, a low viscosity form of PBTP. CBT has particular potential in processes where its water-like viscosity can be used to advantage, such as rotational moulding, casting and infusing fibre reinforcements. CBT has an inherent high gloss surface and for Class A applications can also be painted. Mechanically and thermally it outperforms PE, so can achieve high stiffness at lower wall thicknesses with lower part weight. Cyclics has signed up with Ahlstrom Glassfibre to supply CBT resins for Ahlstrom to combine with its glass fibre reinforcements to produce composite systems for wind turbine and marine applications. Cyclics Corp. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; WESTERN EUROPE; WESTERN EUROPEGENERAL

Accession no.931332 Item 123 Japan Chemical Week 46, No.2304, 3rd Feb.2005, p.4 MITSUI CHEM INTRODUCES PROPYLENEBASED PERFORMANCE ELASTOMERS It is briefly reported that Mitsui Chemicals has used metallocene catalysis in the development of a new series of

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propylene-based performance elastomers, the Tafmer XM Series, which feature greatly enhanced homogeneity. When used in blends in the heat sealing layer of a PP film, the new series will allow heat sealing at a temperature 20C lower compared to the existing conventional propylene-based Tafmer, thereby significantly enhancing the efficiency of the food packaging process. Furthermore, the series can be expected to improve efficiency in the OPP film coating process, and also to make inroads into a wide variety of applications in addition to resin modifiers, such as automotive. Mitsui Chemicals JAPAN

Accession no.932496 Item 124 Japan Chemical Week 46, No.2305, 10th Feb.2005, p.2 DAINICHI BARES 100% BIODEGRADABLE ANTIMICROBIAL SHEET Dainichiseika Color & Chemicals has developed a totally biodegradable lunch box sheet, it is briefly reported. Not only the sheet itself, but also the ink and adhesive are biodegradable and after use the sheet can be disposed of in compost. The antimicrobial sheet, Wasapearl, comprises a laminate of polylactic acid film, made from corn, and paper from rayon pulp, impregnated with an extract of natural wasabi (Japanese horseradish) and mustard possessing bacteriostatic activity. Dainichiseika Color & Chemicals Mfg.Co. JAPAN

Accession no.932543 Item 125 Brussels, Cefic, 2004, pp.2, 30 cm, 3/3/05 MIGRATION OF STYRENE FROM UNSATURATED POLYESTER RESINS Cefic; PIRA; APME The migration of styrene from unsaturated polyester resins was tested in four commercially available resins subjected to a number of post cure conditions. Styrene migration into three food stimulants, 3% acetic acid, 10% ethanol, and olive oil, was determined using single sided migration cells. The exposure conditions for the migration measurements were 2 hours at 70 deg.C and 40 days at 40 deg.C. The residual styrene levels for all samples were measured to assess the possible correlation between migration of styrene into the stimulants and the residual styrene content in the material. The materials tested were SMC, solid surface materials, gel coated flat sheeting, and flat sheeting, and GRP pipe with a resin-rich liner. Apart from the pipe sample, the correlation between styrene migration and residual styrene content is claimed to be sufficiently encouraging to speculate that by simply measuring the residual styrene level of food contact products manufactured from unsaturated polyester resin,

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an assessment of an acceptable styrene migration level can be made. WESTERN EUROPE

Accession no.933574 Item 126 European Polymer Journal 41, No.4, April 2005, p.707-14 FTIR INVESTIGATION OF THE SPECIFIC MIGRATION OF ADDITIVES FROM RIGID POLY(VINYL CHLORIDE) Atek D; Belhaneche-Bensemra N Algiers,Ecole Nationale Polytechnique The migration of additives from rigid poly(vinyl chloride) (PVC) containing epoxidised sunflower oil as an organic costabiliser, zinc and calcium stearates as primary stabilisers, and stearic acid as a lubricant was examined by using sunflower oil and 15% (v/v) aqueous ethanol as models for foods. Circular samples of the rigid PVC were immersed in a known volume of the model food for 12 days at 40 deg C. Samples of the polymer and the food model were removed each day for analysis by Fourier-transform IR spectroscopy. The direct analysis of the model foods was complicated by the overlap of bands in the additives. However, an analysis of the PVC films obtained by dissolution of the circular samples in tetrahydrofuran and evaporation of the solvent was more conclusive. Although some migration of the additives was detected, the level of migration was less than that legally permitted for foodcontact materials (10 mg/sq dm). 11 refs. ALGERIA

Accession no.934921 Item 127 Additives for Polymers Dec.2004, p.9 BASF GREEN PIGMENT RECEIVES FDA APPROVAL BASF has been granted approval from the US Food & Drug Administration for its phthalocyanine pigment, known as “Heliogen Green K 9360”, for food-contact applications. Brief details are given in this very short article. BASF; US,FOOD & DRUG ADMINISTRATION USA

Accession no.935359 Item 128 Hot Colors, Cool Plastics 2004. Proceedings of a SPE Retec conference held Marco Island, Fl., 20th.-21st. Sept.2004. Brookfield, Ct., SPE, 2004, p.51-9, CD-ROM, 012 GOING GREEN WITH ULTRAMARINE BLUE Calvert D Holliday Pigments Ltd. (SPE,Color & Appearance Div.)

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The pigment ultramarine blue is examined with respect to its environmental impacts, health hazards and safety. Whilst the pigment has a favourable toxicity profile and a long history of application in sensitive applications such as cosmetics and in food-contact applications, in order to meet the requirements of discerning customers practice sustainable procurement and look for products with a beneficial life cycle analysis. This paper, therefore, outlines the results of a study which shows how a commitment to sustainable manufacture is an essential addition to the favourable toxicity profile. Areas for improvement are recognised and options for renewable energy resources are discussed. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.935629 Item 129 Plastics and Rubber Asia 20, No.132, March 2005, p.18 BASELL’S FILM DEVELOPMENTS Basell has introduced a family of Ziegler catalysts that are designed for use in gas phase PE technologies, it is briefly reported. Known as Avant Z230, the catalysts are said to be able to produce narrow molecular weight for film, injection moulding and rotomoulding grades of LLDPE, MDPE and HDPE. Basell has also developed a new generation PP copolymer, Clyrell RC1314. Based on the Spherizone technology, Clyrell is said to have better optical, stiffness and sealing properties as well as low odours. Designed for use in side layers, processors have reported that Clyrell displays no visible crystallisation line. Potential applications include retort food pouches, hygiene product packaging and large-size bags for animal feed. Basell EU; EUROPEAN COMMUNITY; EUROPEAN UNION; NETHERLANDS; WESTERN EUROPE; WESTERN EUROPEGENERAL

Accession no.935930 Item 130 Food Additives and Contaminants 21, No.12, Dec.2004, p.1179-85 METHOD OF TEST AND SURVEY OF CAPROLACTAM MIGRATION INTO FOODS PACKAGED IN NYLON-6 Bradley E L; Speck D R; Read W A; Castle L UK,Dept.of Environment,Food & Rural Affairs An analytical method for determining residual caprolactam content in foods is described and applied to an analysis of 50 retail foodstuffs in polyamide-6 packaging. The method entails extraction of the foodstuff with ethanol/water containing caprolactam as internal standard, defatting of the extract with hexane and analysis of the defatted extract by liquid chromatography combined with mass spectrometry. 14 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE; WESTERN EUROPE-GENERAL

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References and Abstracts

Item 131 Paint and Coatings Industry 21, No.4, April 2005, p.38/44 CHECKMATE FOR MICROBES Zeren S; Preuss A; Konig B Ciba Specialty Chemicals Inc. Paints that repel microorganisms are increasingly in demand, and biocides based on silver ions are suitable for this purpose. In this study, a silver glass and a silver zeolite were used as biocide additives. Two different powder coating systems were used, namely a clear coat, based on PU for use in the health and hospital sector, and a white pigmented powder coating, based on a hybrid for the foodprocessing industry. In order to characterise the overall antimicrobial additive effectiveness in combating bacteria and fungus on the powder coating surface, the following tests were carried out to determine the bactericidal and fungicidal activity at the surface: determination of the lowest concentration of the A1-type biocide additive necessary in the PU clear coat to repel all three types of organisms; repeat testing of the antimicrobial effect on the surfaces after a rinsing and light exposure test, allowing the long-term effect of biocide additives to be monitored; and characterisation of the surfaces of the powder coatings by means of colour, gloss and haze measurements. 4 refs. SWITZERLAND; WESTERN EUROPE

Accession no.938061 Item 132 Paper Film and Foil Converter 79, No.4, April 2005, p.12 FDA OKS BASF PIGMENT BASF has been granted approval from the US FDA for its phthalocyanine pigment Heliogen Green K 9360 under the Food Contact Notification programme. BASF claims it is the only supplier of a pigment with this Color Index number (Pigment Green 36) to have been granted approval. The pigment is approved for use as a food-contact substance in all types of polymers. The coloured polymers may be used according to the conditions of use C-G, table 2 of 21 CFR 176.170(c), and not to exceed temperatures of 70C. Users are subject to the provisions of 21 CFR 178.3297. This abstract includes all the information contained in the original article. BASF Corp. USA

Accession no.939074 Item 133 Plastics Engineering Europe 3, No.1, Spring 2005, p.36-8 PLASTICS ADDITIVES ROUNDUP Pritchard G Rapra Technology Ltd. This article examines some of the important technology developments, economic issues and regulatory concerns

© Copyright 2007 Smithers Rapra Technology

affecting the additives industry. About 75% of all additives measured by tonnage and 60% by value are used in just one polymer, PVC. PVC is the target destination for almost all heat stabilisers and about 86% of all plasticisers by volume, together with rather more than three-quarters of all impact modifiers, over 60% of antimicrobial additives and more than half of all chemical blowing or foaming agents. Over 90% of all antiblock and slip agents by volume go into polyolefins, together with well over 60% of light stabilisers and antioxidants and more than half of all nucleating and clarifying agents. In the building and construction sector, there are likely to be higher fire resistance standards in future, offering opportunities for increased consumption of flame retardants. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.940102 Item 134 Modern Plastics Worldwide 82, No.5, May 2005, p.23 REGULATORY SHOWDOWN? Deligio T According to the US FDA, substances that are not expected to become a component of a food stuff, or those that do not pose a health risk, are cleared using analytical chemistry data and extrapolation to show they pose no toxicological concern. In Europe, however, all materials present must be cleared using relatively exhaustive toxicological evaluations, regardless of the amount or likelihood of migration. As the European Union works towards a Super-Regulation, differences that require reconciliation seem likely, especially for companies looking to employ one packaging platform across continents. One current point of contention is migration, where, unlike the EU, the FDA offers some exemptions. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; USA; WESTERN EUROPE-GENERAL

Accession no.941117 Item 135 British Plastics and Rubber May 2005, p.16 FOOD CONTACT APPROVAL FOR LIGHT STABILISER It is briefly reported that BASF’s Uvinul 5050 H light stabiliser for polyolefins has been given a Food Contact Notification by the US FDA. This enables its use in applications such as woven tape bags like big bags for flour and grain, packaging films and milk containers when the requirements and definitions laid down in 21 CFR 177.1520 of FDA are observed. Uvinul 5050 H is a sterically hindered amine which prevents plastics from degrading by scavenging the free radicals that are formed when plastics are exposed to UV light. BASF USA

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Item 136 Brand 4, No.4, May-June 2005, p.36-41 TINY MIRACLES For the packaging industry, nanoparticles in the form of nanoclays have gone into nanocomposites used in thinfilm barriers and rigid packaging to improve gas barrier protection. These improved gas barriers increase the shelf life of food and beverages. Nanoparticles are currently made from a wide variety of materials, with the most common of the new generation being ceramics. The big story for nanotechnology in packaging applications may be to enable low-cost devices that sense their environment and process information. The two relevant areas are sensing technologies, or smart dust, and radio frequency identification. RFID technology has so far provided merely self-identification in the form of bar codes, but through nanotechnology it could have much greater functionality, such as detecting when food has gone bad. Nanotechnology in printing is also discussed. WORLD

Accession no.942227 Item 137 Canadian Plastics 63, No.4, April 2005, p.13/6 SPECIAL ADVANTAGE LeGault M The US FDA recently approved Shepherd Color’s StarLight FL 105 for use as a colourant in all types of food-contact applications. The pigment is designed to create sparkling effects in items such as plastic tumblers, dinnerware and packaging for food and cosmetics. EMD Chemicals’ line of Iriodin WMD pearlescent special effects pigments is produced using a new process that makes the pigment easier to use, with improved throughput. Teknor Color has launched a line of microbead colour concentrates designed to create striking sparkling effects in PETP beverage bottles. Clariant Masterbatches has expanded its Soft-Touch special effects line, previously limited to blow moulded containers, to injection-moulded products such as caps and closures. Soft-Touch uses a soft-textured resin compound in combination with a masterbatch colourant system to provide a soft matte finish. NORTH AMERICA

Accession no.942345 Item 138 Food Additives and Contaminants 22, No.3, March 2005, p.245-50 DETERMINATION OF ETHYLENETHIOUREA (ETU) AND PROPYLENETHIOUREA (PTU) IN FOODS BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY-ATMOSPHERIC PRESSURE CHEMICAL IONISATION-MEDIUMRESOLUTION MASS SPECTROMETRY

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Startin J R; Hird S J; Sykes M D UK,Central Science Laboratory A novel method for determining ETU and PTU in food is described. It involves extraction of ETU and PTU by blending with dichloromethane in the presence of sodium sulphate, sodium carbonate, thiourea and ascorbic acid, removal of dichloromethane by rotary evaporation after filtration, redissolving the extract in water, analysis by reversed phase liquid chromatography and detection by means of atmospheric pressure chemical ionisation-mass spectrometry using a double focusing mass spectrometer. 27 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.942989 Item 139 Food Additives and Contaminants 22, No.3, March 2005, p.280-8 DIETARY EXPOSURE ASSESSMENT OF INFANTS TO BISPHENOL A FROM THE USE OF POLYCARBONATE BABY MILK BOTTLES Kwok Onn Wong; Lay Woon Leo; Huay Leng Seah Singapore,Agri-Food and Veterinary Authority A study was made of residual Bisphenol A content in various polycarbonate baby milk bottles available on the Singapore market. The potential migration of Bisphenol A from each bottle was also determined under more severe temperatures than usual using food-simulating solvents and time conditions recommended by the US,Food & Drug Administration. It was established that the dietary exposure of Bisphenol A from the bottles was below the oral Reference Dose laid down by the US,Environmental Protection Agency and that there was no health risk to infants from use of the bottles. 17 refs. US,Food & Drug Administration; US,Environmental Protection Agency SINGAPORE

Accession no.942990 Item 140 Journal of Membrane Science 253, No.1-2, 5th May 2005, p.139-47 WATER AND HEXANE PERMEATE FLUX THROUGH ORGANIC AND CERAMIC MEMBRANES. EFFECT OF PRETREATMENT ON HEXANE PERMEATE FLUX Garcia A; Alvarez S; Riera F; Alvarez R; Coca J Oviedo,University; Valencia,Polytechnical University The behaviour of several organic and inorganic membranes in the presence of organic solvents (hexane) for application in edible oil processing was studied. Ceramic membrane with a zirconia filtration layer and molec.wt. cut-offs(MWCO) of 1000 and 5000 g/mol and polyethersulphone(PES) membranes with MWCO of 4000 and 9000 g/mol were tested in pilot-plant scale equipment. The effect

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References and Abstracts

of pretreatment, consisting of soaking the membranes in mixtures of solvents of decreasing polarity, on the performance of both types of membranes was evaluated. The pretreatment was very effective for PES membranes, but ineffective for zirconia membranes. Hexane flux was higher through pretreated PES membranes than through ceramic membranes with higher MWCO. The results obtained could be explained by the different hydrophilicity of PES and ceramic membranes. The Hagen-Poiseuille equation was not able to predict the results on permeate flux, which indicated that other parameters apart from viscosity should be taken into account, e.g. surface tension, hydrophobicity.

dimensional gas chromatography(GC) with time-of-flight mass spectroscopy(MS) are examined. The principles and practice of the technique are described and results of analyses of compounds based on nitrile rubber, fluorocarbon rubber, acrylic rubber, epichlorohydrin rubber and butyl rubber are presented and discussed. Comparison is made between data generated by this two-dimensional GC-MS technique and by conventional GC-MS. The main applications of the new analysis technique are discussed, including reverse engineering of unknown rubber samples, extractables testing and food migration testing.

EU; EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.944177

Accession no.943107 Item 141 Kunststoffe Plast Europe 95, No.4, 2005, p.102-5 NICKEL AND CHROMIUM RUTILE YELLOW - PIGMENT CLASS WITH LOW RISK Endriss H; Fischer R BASF AG; Deutscher Verband der Mineralfarbenindustrie A risk assessment of nickel and chromium yellow pigments is presented. It is shown that, although these pigments contain heavy metals, they exhibit virtually inert behaviour, as the metals are not bioavailable. Studies undertaken as part of the OECD High Production Volume Programme, which confirm that these yellow pigments have only low hazard potential, are described. The use of rutile pigments in food packaging is discussed. The colouration of plastics with this class of pigments can be regarded as being more or less harmless from a toxicological and ecological perspective. 4 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; WESTERN EUROPE; WESTERN EUROPEGENERAL

Accession no.944171 Item 142 High Performance and Speciality Elastomers 2005. Proceedings of a conference held Geneva, Switzerland, 20th-21st April 2005. Shawbury, Rapra Technology Ltd., 2005, Paper 2, pp.17, 29cm, 012 USE OF TWO-DIMENSIONAL GC-MS FOR THE IDENTIFICATION AND QUANTIFICATION OF LOW MOLECULAR WEIGHT COMPOUNDS FROM HIGH PERFORMANCE ELASTOMERS Forrest M; Holding S; Howells D Rapra Technology Ltd. (Rapra Technology Ltd.) The practical implications for the compositional analysis of the low molec.wt. compounds in rubber using two-

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EU; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Item 143 Food Additives and Contaminants 22, No.5, May 2005, p.490-502 TEST METHOD FOR MEASURING NONVISIBLE SET-OFF FROM INKS AND LACQUERS ON THE FOOD-CONTACT SURFACE OF PRINTED PACKAGING MATERIALS Bradley E L; Castle L; Dines T J; Fitzgerald A G; Gonzalez Tunon P; Jickells S M; Johns S M; Layfield E S; Mountfort K A; Onoh H; Ramsay I A UK,Dept.for the Environment,Food & Rural Affairs; Dundee,University; Laser Installations Ltd. The development of a test method to measure invisible set-off of inks and lacquers based on various resins such as acrylics or polyurethanes on the food-contact surface of food-packaging materials such as polyethylene is described. A method using luminescence was found to meet the requirements of sensitivity, together with low cost, ease of use, non-destructive testing and a clear pass or fail indication. 20 refs. EU; EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.945764 Item 144 Plastics Technology 51, No.3, March 2005, p.61 ONLINE SERVICE HELPS MEET EU PACKAGING SPECS French company SpecialChem has launched a new on-line calculation service called “MigraPass”, to help manufacturers comply with the 2002 European Union regulations on the migration of hazardous substances in food packaging applications. Brief details are offered in this concise article. SPECIALCHEM; FABES GMBH RESEARCH CO.; PIRA INTERNATIONAL EU; EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; GERMANY; UK; WESTERN EUROPE; WESTERN EUROPEGENERAL

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Item 145 High Performance Plastics April 2005, p.3 HOMOGENEOUS PROPYLENE-BASED ELASTOMERS FOR FOOD PACKAGING

when exposed to ultraviolet light by scavenging free radicals, has been granted a Food Contact Notification by the US Food & Drug Administration, it is reported in this small article.

Japanese company Mitsui Chemicals Inc. has launched a series of propylene-based elastomers intended for food packaging applications, it is announced in this small article. Brief details are given of the new series, which is known as “Tafmer XM”.

EU; EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; USA; WESTERN EUROPE; WESTERN EUROPEGENERAL

MITSUI CHEMICALS INC. JAPAN

Accession no.946168 Item 146 High Performance Plastics April 2005, p.8/9 STABILIZER MIGRATES INTO FOOD A study was carried out at the US Food & Drug Administration to measure the migration of the commonlyused UV stabiliser “Tinuvin 234” from a PETP sample into food simulants, using high-performance liquid chromatography with UV detection. Brief details are presented in this short article. US,FOOD & DRUG ADMINISTRATION USA

Accession no.946177 Item 147 Adhesives and Sealants Industry 12, No.8, Aug.2005, p.22/5 FORMULATING CONCEPTS OF ENERGYCURABLE LAMINATING ADHESIVES Des Roches S RAHN USA Corp. Over the past decade, laminating adhesives have become a relevant sector of energy-curable technology. Recent development work into the realm of food packaging has begun to build profitable businesses for those using this technology. RAHN is a supplier of energy-curable raw materials used in finished formulated products. The company has formulated four laminating adhesives with different end properties to suit industry needs. T-peel properties, viscosity and reactivity are discussed. USA

BASF AG; US,FOOD & DRUG ADMINISTRATION

Accession no.948316 Item 149 High Performance Plastics June 2005, p.3 SOLVENT-FREE POLYESTER FILMS In this short article two new coated PETP films from ExxonMobil Chemical Co. of the USA are briefly introduced to us. The films, designated “XPET 700” and “XPET 800”, are water-based and are intended for the packaging of fresh food. EXXONMOBIL CHEMICAL CO. USA

Accession no.948321 Item 150 PETplanet insider 6, No.9, 2005, p.12/4 BEER IN PET: RECYCLING CONSIDERATIONS As a global leader in bottle-to-bottle production, Amcor PET Packaging takes a keen interest in the impact of coated and multilayer beer bottles on the bottle-to-bottle recycling chain. At the company’s recycling plant in Beaune, France, state-of-the-art technology produces food grade resin ready to be reused in drinks bottles. The recycling facility is able to handle coloured bottles, multilayer bottles, coloured multilayer bottles and even coloured coated bottles. There is no need for pre-sorting. Beaune can produce 24,000 tonnes of resin pellets from over 30,000 tonnes of postconsumer PETP, equivalent to approximately 700 million PETP bottles. Around 17,000 tonnes of the resin produced is of food grade quality, known as Amcor SuperCycle, while the remaining 7,000 tonnes of NuCycle is used for non-food applications. Amcor recommends a 25% content of SuperCycle resin in new multilayer beer bottles. Amcor PET Packaging EU; EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; WESTERN EUROPE; WESTERN EUROPE-GENERAL

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Accession no.948783

Item 148 Additives for Polymers May 2005, p.8 BASF LIGHT STABILIZER RECEIVES FDA APPROVAL

Item 151 China Chemical Reporter 16, No.25, 6th Sept.2005, p.8 OPPORTUNITY OF ENVIRONMENTAL FRIENDLY FLEXIBLE PACKAGING ADHESIVES IN CHINA Wang D

BASF AG’s “Uvinul 5050 H” sterically hindered amine light stabiliser, which prevents plastics from degrading

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References and Abstracts

Vinyl acetate- and toluene-borne two-component PU adhesives are still the main varieties used in the flexible packaging market in China. However, reports of solvent residue problems in packaging and cost pressures from upstream products such as crude oil, are pushing the flexible packaging adhesive market towards more environmentally friendly and healthy products. Waterborne flexible adhesive producer Rohm & Haas sponsored two flexible packaging seminars in China in 2002 and 2004 to promote “green” adhesive and ink. The company is now the largest water-borne flexible adhesive player in China. Henkel is also promoting its solvent-free adhesive in China, but the development is very slow compared with water-based adhesive as it needs new investment in lamination machines. CHINA

Accession no.950659 Item 152 Italia Imballaggio No.10, Oct.2005, p.132-3 Italian; English ENVIRONMENTALLY TESTED The commitment of Italian converter Gerosa Group to sustainable development is seen in the adoption of waterbased adhesives, replacing solvent-based ones, for the production of laminated film for use with cold sealers. Rohm & Haas supplied the innovative water-based Robond L acrylic adhesives for dry bond laminating. These adhesives have high solids formulations, so less water evaporation is needed compared to other water-based systems. Laminations cure quickly and exhibit high green bonds, improving productivity. Rohm & Haas; Gerosa EU; EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.951641 Item 153 Journal of Applied Polymer Science 98, No.3, 5th Nov.2005, p.1186-91 SYNTHESIS AND CHARACTERIZATION OF POLYACRYLAMIDE GRAFTED COPOLYMERS OF KUNDOOR MUCILAGE Mishra A; Bajpai M Kanpur,Chhatrapati Shahu Ji Maharaj University Details are given of the grafting of acrylamide onto watersoluble food-grade polysaccharide Kundoor mucilage initiated by ceric ion in aqueous medium. The effect of monomer concentration, initiator concentration, reaction time, and temperature in terms of grafting efficiency and percent of grafting were investigated. The graft copolymers were characterised by FTIR, DSC, SEM, and X-ray diffraction. 25 refs. INDIA

Accession no.952096

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Item 154 Addcon World 2005. Proceedings of the 11th International Plastics Additives and Modifiers Conference, held Hamburg, 21st-22nd Sept.2005. Shawbury, Rapra Technology Ltd., 2005, Paper 12, pp.4, 29cm, 012 ANTIMICROBIALS IN FOOD-CONTACT APPLICATIONS IN THE EU - A REGULATORY PUZZLE Gergely A Keller & Heckman LLP (Rapra Technology Ltd.) The regulations concerning additives with antimicrobial activity used in plastics in direct contact with foodstuffs are discussed and an examination is made of the use conditions and possible migration of the additive into food to define whether the use of the additive in the intended application complies with the regulations governing that application. BELGIUM; EU; EUROPEAN COMMUNITY; EUROPEAN UNION; WESTERN EUROPE; WESTERN EUROPE-GENERAL

Accession no.952278 Item 155 Addcon World 2005. Proceedings of the 11th International Plastics Additives and Modifiers Conference, held Hamburg, 21st-22nd Sept.2005. Shawbury, Rapra Technology Ltd., 2005, Paper 13, pp.4, 29cm, 012 IMPACT OF SILVER GLASS CERAMIC ANTIMICROBIAL ACTIVE INGREDIENT ON COLD TOLERANT GERMS ON REFRIGERATOR INTERIORS Studer H Sanitized AG (Rapra Technology Ltd.) Data are presented showing the effectiveness of Sanitized Silver, an antimicrobial containing silver as active ingredient, for reducing cold-tolerating listeria on the surfaces of refrigerator interiors made from plastics and coated with the silver compound. 3 refs. SWITZERLAND; WESTERN EUROPE

Accession no.952279 Item 156 Asian Plastics News Nov.2005, p.7 MITSUI CHEMICALS LAUNCHES NEW ELASTOMER BRAND It is briefly reported that Mitsui Chemicals is launching a new line of alpha-olefin-based elastomers based on its proprietary metallocene catalyst technology, with the crystalline structure being controlled in nano-order. By being able to control its structure in nano order, the Notio elastomer achieves better performance balance in terms of transparency, heat resistance, flexibility and rubber

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elasticity. Notio applications will be as the protection films of electronic and optical parts, as well as for a variety of sealing materials. When used as an impact modifier for PP, Notio blends have impact resistance and scratch resistance at high levels without impairing transparency. Mitsui Chemicals JAPAN

Accession no.952746 Item 157 Additives for Polymers Feb.2004, p.2 BASF INTRODUCES ADVANCED SILVER PIGMENT FOR PLASTICS COLORATION Germany’s BASF AG has introduced a new silver pigment for colouring plastics, which is known as “Variocrom Magic Silver K 1000”. This concise article provides us with brief details about the new pigment’s special properties and intended applications. BASF AG EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; WESTERN EUROPE

Accession no.904520 Item 158 Flexible 2, No.5, Jan.-Feb.2004, p.40/8 ATOMIC EXPLOSION Anyadike N After a rapid increase in its adoption outside packaging, nanotechnology has demonstrated its significant longterm commercial potential. This article reviews current developments and assesses the value of bringing this technology into the packaging environment. The US is the world leader in nanoscale science research with well over 400 US domestic companies involved. The industry’s holy grail is to turn clay particles into smart materials by combining them with functional organic molecules to form hybrid materials. By doing this, a whole new spectrum of materials can be developed that will respond in a particular way in a particular environment. A team at Strathclyde University is currently developing intelligent packaging, using nanoparticles that change colour if there has been any oxidation of food inside the packaging. WORLD

Accession no.906457 Item 159 Package Print and Converting International Jan.-Feb.2004, p.46-7 EB CURING OF SOLVENTLESS ADHESIVES AND OVERPRINT VARNISHES Wild L Edlon Machinery Ltd. The platform technology used to develop the low voltage, low cost electron beam curing equipment type EZCure,

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manufactured by Energy Sciences, is now further optimised to meet the broader needs of the film packaging material converter. Through these optimisations, smaller, lower cost, energy efficient, second generation (EZCure 2) EB equipment has been developed. The cost effective and environmentally friendly electron beam curing process could be the future curing/drying method of choice given certain restrictions and problems which face the converter today, particularly in the field of solventless laminating adhesives and solvent based adhesives and lacquers. Electron beam chemistry is 100% solids, not unlike UV, but does not require the photoinitiator catalyst of UV and therefore presents a much more viable case for use in food packaging. ENERGY SCIENCES INC. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.906427 Item 160 Chemical and Engineering News 82, No.6, 9th Feb.2004, p.25-9 BIOCATALYSIS IN POLYMER SCIENCE Freemantle M Biocatalysis in polymer science is a highly interdisciplinary area. Much of the research in this area has focused on the use of enzymes for the synthesis of novel monomers and polymers, for the catalysis of polymer modification reactions and for polymer degradation. Researchers at Hercules have used biocatalysis to modify and improve the properties of polymeric materials. One such material is Kymene G3-X, a water-soluble polymer manufactured by Hercules that is used to make paper products stronger when wet. Researchers at the University of Maryland Biotechnology Institute are looking into the use of enzymes to create functionally useful biopolymer-based materials that would be difficult to obtain by alternative synthetic routes. Nijmegen University is developing techniques for the “smart” assembly of hybrid biopolymers. The work has potential applications for protein purification and in the biosensor field, for protein recognition. WORLD

Accession no.906376 Item 161 Brand 3, No.2, Jan.-Feb.2004, p.42-8 CHALLENGING FILMS Anyadike N Intelligent packaging is set to take off as technologies to manufacture films improve. The market for intelligent packaging is forecast to double in value between 2002-07 to reach a total of Euro493.3m. Intelligent breathable films, aimed at enhancing freshness, is one area of packaging technology that is growing rapidly. A definition of intelligent packaging is the kind of packaging that uses devices within the pack or as part of the package itself to sense and register

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References and Abstracts

certain changes in the pack and its contents. For example, labels or films that change colour to signal an external or internal temperature change. In intelligent packaging, the package function is able to switch itself on and off in response to changing external and/or internal conditions. Active packaging systems consist of a matrix polymer, such as PETP, plus an oxygen scavenging/absorbing component and a catalyst. Antimicrobial technologies also have the potential to extend the shelf life of perishable foods. WORLD

Accession no.907122

Several new products which have been launched by Atofina are drawn to our attention in this article. The company has introduced “Plastistrength 770”, a high-performance processing aid for rigid PVC packaging applications, “Thermolite 140” and “Thermolite 179” heat stabilisers for PVC building products, “Finaclear 636” and “Finaclear 609” impact modifiers for PS, and also “Finaclear 540” and “Finaclear 550” impact modifiers aimed at film and sheet extrusion-thermoforming applications for food packaging. ATOFINA CHEMICALS INC. EUROPE-GENERAL; EUROPEAN COMMUNITY; EUROPEAN UNION; NETHERLANDS; USA; WESTERN EUROPE

Item 162 Chemical Week 166, No.8, 10th March 2004, p.4 FULLER ACQUIRES ADHESIVES AND RESINS BUSINESS IN PORTUGAL It is briefly reported that H.B. Fuller has acquired the adhesives and resins operations of Probos (Oporto, Portugal). The acquired business consists of waterbased, hot melt, reactive and solvent-based adhesives, and emulsions for paints, textiles and food products. It has sales of approximately 30m US dollars/year. Probos manufactures Fuller’s Rakoll-brand woodworking adhesives under a long-term contract. Fuller H.B.; Probos SA EUROPEAN COMMUNITY; EUROPEAN UNION; PORTUGAL; WESTERN EUROPE

Accession no.907161

Accession no.907903 Item 165 High Performance Plastics Feb.2004, p.5/6 DAINIPPON AND ASAHI KASEI IN PS SHEET DEAL In Japan, Asahi Kasei Corp. and Dainippon Ink & Chemicals Inc. are planning to integrate their PS sheet business into a 50:50 joint venture. The new company will become Japan’s largest supplier of PS sheet, a product which is widely used in transparent food containers. Brief details of the companies’ plans are given. DAINIPPON INK & CHEMICALS INC.; ASAHI KASEI CORP.; ASAHI KASEI LIFE & LIVING CORP.; MITSUBISHI CHEMICAL JAPAN

Item 163 Chemical Market Reporter 265, No.10, 8th March 2004, p.3 H.B. FULLER ACQUIRES ADHESIVES AND RESINS BUSINESS H.B. Fuller has purchased the adhesives and resins businesses of Probos SA, based in Oporto, Portugal, it is briefly reported. The Probos businesses have combined annual sales of roughly 30m US dollars and primarily serve the Iberian peninsula. The acquired product lines include water-based, hot melt, reactive and solvent-based adhesives for the assembly, woodworking, footwear and converting industries, and emulsions for the paints, textiles and food product industries. For several years, Probos has been the exclusive licensee of Fuller’s Rakoll woodworking brand for the Portuguese market. FULLER H.B.,CO.; PROBOS SA EUROPEAN COMMUNITY; EUROPEAN UNION; PORTUGAL; WESTERN EUROPE

Accession no.907213 Item 164 Additives for Polymers Jan.2004, p.2/3 ATOFINA LAUNCHES NEW PROCESS AID AND IMPACT MODIFIERS

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Accession no.909177 Item 166 Chemical Market Reporter 265, No.14, 5th April 2004, p.FR8-9 INDUSTRY GEARS UP FOR INDUSTRIAL BIOTECHNOLOGY WAVE Mirasol F Although still far from being a well-established and wellaccepted sector, industrial biotechnology has already set roots in a wide variety of practical applications. These include the use of biofeedstocks such as sugars and biomass to replace fossil oil and gas, the use of bioprocesses such as fermentation and biocatalysis for production of vitamins and active pharmaceutical ingredients, and the production of bio-based products such as biopolymers and enzymes. Cargill Dow is leading the way in the biopolymer revolution with the rapid success of its biology-based technology. A year ago the company launched Ingeo, a natural fibre akin to cotton manufactured from its NatureWorks polylactic acid. Last July, Metabolix and BASF AG formed a research collaboration for developing plastics from renewable resources. Metabolix is expected to produce polyester plastics from sugar using fermentation technology, supplying BASF with pilotscale sample quantities. In turn, BASF is investigating

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the materials technology and processing the properties of the products. WORLD

Accession no.909701 Item 167 New Scientist 182, No.2444, 24th April 2004, p.26 WRAPPERS SMARTEN UP TO PROTECT FOOD Kleiner K While conventional packaging simply acts as a barrier that protects food, active packaging can do a lot more. The French Monoprix supermarket chain is using a device called a time temperature indicator on a number of fresh foods. The TTI is a label that tracks the temperature a package has been kept at and for how long. The bullseyelike label has a central ring containing a chemical which polymerises, changing colour as it does so from clear to dark. Increasing the temperature speeds up the polymerisation. The National Center for Toxicological Research has developed a plastic disc impregnated with a dye that sits inside food packaging and changes colour if telltale gases produced by decay are present. Landec has developed a membrane wrapper which changes its permeability as the temperature changes in a way that keeps different products at their optimal oxygen/carbon dioxide concentrations. WORLD

Accession no.909789 Item 168 Shawbury, Rapra Technology Ltd., 2004, pp. 164, 29 cm. Rapra Review Rept. No. 171, vol. 15, No. 3, 2004. NALOAN PVC COMPOUNDS AND PROCESSING Patrick S Edited by: Humphreys S (Rapra Technology Ltd.) Rapra Review Report No.171 This review of PVC compounds and processing techniques includes information on health and environmental aspects, and recycling and waste management of PVC. An overview is given of the PVC industry, with an outline of PVC resin producers and compounders, and details of the global market by application. Key additives are identified and specific consideration is given to heat stabilisers, plasticisers, multifunctional additives, property modifiers, lubricants, fillers, flame retardants, pigments, biocides, blowing agents, antioxidants, and light stabilisers. Compounding and processing technology is reviewed, with reference to dry blend mixing, melt compounding, liquid PVC blending, gelation, extrusion, injection moulding, extrusion blow moulding, orientation, calendaring and moulding processes for plastisols and pastes. 466 refs. WORLD

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Item 169 Materials World 12, No.5, May 2004, p.30-2 PERFECT PITCH Inditherm is a Rotherham-based company that has developed a material of the same name that looks like a clothing textile, but that conducts low-voltage electricity to provide an evenly heated surface for virtually any purpose, from sports physiotherapy and warm steering wheels to concrete structures and football pitches. The essential ingredients of Inditherm are carbon black and an elastomeric polymer. Unlike other heating solutions, which are prone to hot and cold spots, Inditherm’s flexible carbon-based polymer conducts electricity, in the range of 6v to 48v, to provide a consistently heated surface that can be controlled and monitored up to 120C in ambient conditions as low as -40C. Inditherm EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.910917 Item 170 Flexible 2, No.6, March-April 2004, p.5 EXXONMOBIL CHEMICAL INTRODUCES NEW WAVE OF METALLOCENE POLYPROPYLENES Building upon its Exxpol technology that produced the first metallocene-catalysed PP in 1995, ExxonMobil Chemical is introducing a new wave of Achieve metallocene PP following the development of an additional catalyst platform. The new Achieve lines have applications across a range of markets, beginning with nonwovens, but also set to include both flexible and rigid packaging applications. Achieve TM 6936G1 is the first mPP designed for meltblown applications. It has the high-melt flow rate and narrow molecular weight distribution needed to reach the next level of performance in meltblown processes. Tests have shown that nonwoven fabrics made from Achieve TM 6936G1 offer increased barrier properties, increased comfort from reduced weight and greater air flow, reduced spray impact penetration and FDA compliance for use as articles or components of articles intended for food contact. ExxonMobil Chemical Co. USA

Accession no.910948 Item 171 Flexible 2, No.6, March-April 2004, p.18/25 ADOPTION PROCESS Ver-Bruggen S Cryovac’s oxygen scavenging film can be used in rigid and flexible packaging with both high-moisture content foods and dry products. The oxygen scavenger is

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References and Abstracts

activated by light from a special UV lamp, supplied by Cryovac and fixed to the packaging line. Wipak claims its oxygen scavenging film, which has almost clear visibility, is gaining interest on the continent. The film uses a moisture-triggering technology that does not require additional preparation or equipment to activate the scavengers. However, for the foreseeable future, sachets, even with the additional cost of inserting them into packs, are much cheaper to use than film. Antibacterial films have traditionally courted controversy because they may be used to package foods that are going bad, even if they are stifling the growth of microbes. Active flexible packaging and active films are still very much in the development stage and will only begin to thrive in Europe once the revised food contact materials council directive is implemented. WORLD

Accession no.910952 Item 172 Flexible 2, No.6, March-April 2004, p.42-8 FAST CURES Anyadike N The world market for laminated food packaging materials is growing at an annual average rate of approximately 45%. There is growing interest in low-cost electron beam curing technology in the flexible packaging industry, with interest sparked by the recent availability of lower-cost EB units. EB is seen as a more food packaging friendly alternative to UV-curable technology. Today there are around 150 different PUR laminating adhesives that can realistically be substituted by UV or EB cure adhesives. However, in order for this to happen, a considerable amount of testing would need to be done. Therefore, a cure primer, which accelerates the cure of well-proven laminating adhesives is a much simpler and more costeffective technology approach. WORLD

technical Bisphenol A diglycidyl ether with solvents and phenols are employed to confirm the identification of migrants and the method is validated using several epoxy coatings applied to tinplate strips. (Pt.2, ibid, p.377-89) 35 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; WESTERN EUROPE

Accession no.911080 Item 174 2003 PLACE Conference and the Global Hot Melt Symposium. Proceedings of a Conference held Orlando, Fl., 3rd-7th Aug. 2003. Atlanta, Ga., TAPPI Press, 2003, Paper 27-2, 30 cm. 012 EMBRACING EB/UV CURABLE TECHNOLOGY FOR FOOD PACKAGING END-USED THROUGH FDA COMPLIANCE SELF-CERTIFICATION PROCESS Lin A; Wind G; Wornick F Sovereign Specialty Chemicals Inc. (TAPPI) The development of a comprehensive testing protocol employing cell extraction and liquid chromatography with a mass selective spectrometer for UV/electron beam curable, acrylated coatings/adhesives/inks is described. FDA compliance of UV/electron beam curable chemistry can be determined with the aid of this testing protocol through support of the No Migration/ No Food Additive statutory exemptions under FDA regulations. Possible commercial applications of this technology are indicated as are the steps necessary to ensure continuous FDA compliance of food packaging materials using UV/electron beam curable chemistry. 14 refs. US,Federal Drugs Administration USA

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Accession no.910955 Item 173 Food Additives and Contaminants 21, No.4, April 2004, p.390-405 MIGRATION FROM CAN COATINGS: PART 3. SYNTHESIS, IDENTIFICATION AND QUANTIFICATION OF MIGRATING EPOXYBASED SUBSTANCES BELOW 1000 DA Schaefer A; Simat T J Hamburg,University; Dresden,Technische Universitat A report is presented on the development of a method for identifying and quantifying Bisphenol A-diglycidyl etherrelated substances below 1000 Da migrating from epoxybased can coatings. The analysis is performed using HPLC coupled with UV light, fluorescence and electrospray ionisation-mass selective detection. Microreactions of

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Item 175 Canadian Plastics 62, No.5, May 2004, p.22 OPTIMIZING USE OF TPES RTP has introduced a new series of TPE compounds formulated for specific properties and optimised performance. RTP 6002 and RTP 6003 have been specifically developed for improved bonding in two-shot or insert overmoulded applications. Bayer Polymers is expanding its line of aromatic Desmopan thermoplastic PUs with four new highly transparent grades. These are primarily targeted for ski boots and sports and leisure footwear, applications for which good abrasion resistance is required. NORTH AMERICA

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Item 176 European Plastics News 31, No.7, July-Aug.2004, p.15 L/LDPE HINTS AT RECOVERY Platt D According to Nexant Chem Systems, Western European consumption of LDPE fell 2.2% to 4.8 million tonnes in 2003, reflecting a poor economic performance in major European economies. At the same time, LLDPE consumption increased 4.6% to 2.6 million tonnes. While LDPE tends to remain fairly stable, LLDPE takes most of the growth in the market because it costs less and is a tougher material. Nexant is predicting around 1%/year growth for LDPE consumption during the next five years, while LLDPE demand is expected to grow by 7.6%. Film accounted for around 72% of total LDPE and 80% of LLDPE consumption in 2003. Growth in demand is being driven primarily by the increasing use of plastic for food packaging. The consultancy expects very limited additional LLDPE capacity to come onstream in Europe during the next five years. As such, most of the growth in European LLDPE demand will be taken up by imports. In 2009, it is projected that over a million tonnes of LLDPE will come into Europe from the Middle East. Nexant Chem Systems WESTERN EUROPE-GENERAL

Accession no.914398 Item 177 Brand 3, No.4, May-June 2004, p.22-7 DIVINE COMBINATION Ver-Bruggen S Within the diagnostic packaging sector, most investment and research is directed into developing time-temperature indicators and wireless time-temperature labels. However, another hot area is the work being done by various institutes to develop non-invasive oxygen sensors. Oxygen scavengers provide the second biggest market for active packaging, after moisture scavengers. Packaging which extends product shelf life by either removing oxygen through absorption or displacing the oxygen with other gases, as in the case with MAP, is becoming the industry’s preferred method of preserving fresh produce. The Acosic project, funded by the EU, aims to develop combined indicator and scavenger systems, which can absorb oxygen, whilst indicating the functionality of the scavenger and whether the pack has any leaks. VTT Technical Research Centre of Finland is working on improving the properties of its oxygen sensor so that it can be printed as an ink onto packaging. WORLD

Accession no.914434 Item 178 European Chemical News 81, No.2108, 12th-18th July 2004, p.16

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PROPYLENE GLYCOL The major outlet for propylene glycol (PG) is the production of unsaturated polyester resins, which are used in surface coatings and GRP. The second largest consumer is antifreeze where it is replacing ethylene glycol in deicing aircraft and as a coolant in the food industry. The PG market is currently well balanced to tight due to various production problems in Spain and scheduled outages in France and Germany. Demand in Europe is said to be relatively healthy and in line with expectations. Overall, the market in western Europe was up by 6% last year on 2002, but exports were down because of the weak dollar. Future demand growth in Europe is forecast at GDP rates. Asia is the fastest growing market and consumption here is predicted to grow between 6-10%. WORLD

Accession no.915123 Item 179 Shawbury, Rapra Technology Ltd., 2004, pp. 120, 29 cm. Rapra Review Rept. No. 173, vol. 15, No. 5, 2004. NALOAN REGULATION OF FOOD PACKAGING IN EUROPE AND THE USA Knight D J; Creighton L A Safepharm Laboratories Ltd. Edited by: Humphreys S (Rapra Technology Ltd.) Rapra Review Report No.173 This report updates Rapra Review Report 61, and covers food packaging regulations in the EU, the general framework Directive and the main ‘daughter’ Directive on plastics. This is followed by a brief description of the national legislation relating to food packaging for most of the important European countries. Consideration is given to the safety of food packaging, whose absence from EU or national regulation, means that this is assessed largely from CoE Recommendations, draft Recommendations, other European national approvals, (in particular from Germany), or US approval. Safety evaluation of food packaging includes exposure assessments, toxicology testing and risk assessment. Future developments relating to food packing in the EU are discussed, and include the use of active and intelligent packaging materials, and the disposal and recycling of plastics, and control of migration is also addressed. 449 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; USA; WESTERN EUROPE

Accession no.916375 Item 180 Chemical Week 166, No.24, 21st-28th July 2004, p.31-2 UV/EB IS FUTURE FORCE TO BE RECKONED WITH Valero G

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RadTech International North America reports the use of UV/EB formulated products reached 82,800 metric tons in 2003, up 8% over 2001. Graphic arts applications and the wood finishes industry continue to be the largest market segments with a combined 45% share. Because UV-cured coatings provide the durability required by automotive coatings, industry observers say it has opened the door for expanded developments by OEM paint manufacturers and peaked the interest of auto makers. UV-cured powder coatings is another market with vast growth potential. Performance issues surrounding the use of photoinitiators in UV curing are being overcome by the development of new raw materials that are inherently photoreactive, enabling no-odour coatings and inks that are potentially usable in food packaging. NORTH AMERICA

Accession no.917844 Item 181 Journal of Applied Polymer Science 92, No.5, 5th June 2004, p.2845-58 FUNCTIONAL BARRIERS IN PET RECYCLED BOTTLES. PART I. DETERMINATION OF DIFFUSION COEFFICIENTS IN BIORIENTED PET WITH AND WITHOUT CONTACT WITH FOOD SIMULANTS Pennarun P Y; Dole P; Feigenbaum A Reims,Institut National de la Recherches Agronomiques The presence of a layer of virgin polymer (a functional barrier) intercalated between a layer of recycled polymer and foodstuff in order to prevent the migration of contaminants of the recycled polymer into the food was studied. Diffusion coefficients of a large set of model pollutants (surrogates) at low concentrations in PETP were measured under various conditions. A solid-to-solid diffusion test was devised to avoid the use of a solvent which may have plasticising and partitioning effects. The diffusion coefficients obtained for the surrogates agreed with published data for gases measured by permeation experiments where no plasticisation occurred. Migration from PETP into food simulants was then studied. Migration into an aqueous medium was largely influenced by the solubility of the surrogates. Less soluble ones were not detected, despite high diffusion coefficient values. With ethanol there were no partitioning effects and the high plasticisation effect of PETP by ethanol considerably increased the apparent diffusion coefficients. The larger the molecular weight of the surrogate, the more important was the plasticisation effect on the diffusion coefficients. 28 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; WESTERN EUROPE

Accession no.920738 Item 182 Journal of Applied Polymer Science 92, No.5, 5th June 2004, p.2961-9

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COLORANTS BASED ON RENEWABLE RESOURCES AND FOOD-GRADE COLORANTS FOR APPLICATIONS IN THERMOPLASTICS van den Oever M J A; Boeriu C G; Blaauw R; van Haveren J Agrotechnology & Food Innovations BV Colourants based on renewable resources and food grade colourants covering most of the colour spectrum were evaluated for use in PP and PVC. Most of them could be processed in PP at 200C or even 260C while retaining good colour intensity and colour brightness. In PP, the light stability of alizarin (red), carmine (red), indigo (blue), purpurin (red), quinizarin (red) and the aluminium lakes of quinoline yellow and indigo carmine (blue) was close to the requirements for indoor applications. A few colourants showed bleeding from PP but this was reduced to a large extent by bonding these colourants to the reactive carrier maleic anhydride grafted PP. After processing in PVC at 200C, good colour intensity and saturation was maintained. Quinizarin (a structural analogue of alizarin and purpurin) showed a light stability which was close to that of commercial lead chromate/molybdate orange-based colourants. The best performing natural colourants were suitable for applications such as underground PVC water drainage pipes and indoor PP applications where moderate heat resistance and UV light stability are required. 27 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; NETHERLANDS; WESTERN EUROPE

Accession no.920749 Item 183 High Performance Plastics June 2004, p.3 ALLOY POLYMER SHEETS In the USA, Spartech Corp. has recently introduced a range of new products: “Acrylloy XLB” (acrylic film), “EnviroGuard AM” (acrylic/ABS sheet), “Laser Pro” (olefin-based additive), “Millennium V” (polycarbonate/ABS alloy sheet), “Packalloy LTO” (olefin-based sheet and rollstock), “Polyshield CR” (transparent cell-cast sheet), “StatPro SD” (colour concentrate), “SoundX Plus” (mineral-filled polymer sheet), “Solarex SV” (copolyester sheet), and “WeatherPro S” (coextruded ABS sheet). Brief details of each are supplied here. SPARTECH CORP. USA

Accession no.920804 Item 184 Flexible 3, No.3, Sept.-Oct.2004, p.16/24 BRAND NEW BARRIER Anyadike N Cyclic olefin copolymers (COCs) are produced by polymerising ethylene and norbornene using metallocene

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catalyst technology. They have a better water vapour barrier than PP or PE, although the oxygen barrier is similar to both PP and PE. The major difference is in their mechanical characteristics. They are considerably stiffer than LDPE, but with the same layer thickness, making it possible to maintain film stiffness in much thinner coextruded materials. Applications for COCs are as a discrete layer in a multilayer structure, either by coextrusion or extrusion coating, and as a blend with PE. Ticona is by far the most prominent supplier of COCs and recently launched a range of proprietary COCs marketed under the Topas name. They are approved for food-contact applications such as flexible packaging in both Europe and the US. Blister packs represent an area of major potential for COCs. Medical-grade blister packs must be designed in such a way as to protect the contents from moisture and other environmental factors. WORLD

Accession no.921290

solvent-free polyurethane laminating adhesives with smart cure for compliance with food packaging regulations is discussed. EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; WESTERN EUROPE

Accession no.922631 Item 187 Plastics Technology 50, No.9, Sept.2004, p.41-2 ANTIOXIDANTS FOR OLEFINS, PVC Several large chemical additive companies will introduce new polymer antioxidants at the K 2004 show to be held in Dusseldorf in Germany. This short article provides a brief overview of what is to be unveiled at the show, including “Anox ProcessPlus” from Great Lakes Chemical Corp., and a new environmentally-friendly antioxidant for PVC from Ciba Specialty Chemicals, called “Irgastab PVC 11 EM”.

Item 185 Polymer Engineering plus No.74, 9th-15th Sept.2004, p.6 FDA APPROVAL FOR STARLIGHT PIGMENT

GREAT LAKES CHEMICAL CORP.; CIBA SPECIALTY CHEMICALS; CROMPTON CORP.; GE SPECIALTY CHEMICALS

StarLight FL 105 pigment has been approved by the US FDA for use as a colourant in all types of food-contact polymers. Approval will allow the pigment to be used in items such as plastic tumblers, dinnerware and packaging for food and cosmetics. The product line has been developed using innovative MicroMirror technology to obtain a brilliance and sparkle in a variety of different applications. With StarLight, the edges are coated, making the effect visible at any orientation. The sparkle can be created at low pigment levels, even as low as 500ppm and can even be achieved with opaque pigments. StarLight pigments are compatible with most polymers, blends and alloys and can be processed at high temperatures without problem. Shepherd Color Co.

Accession no.925189

USA

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; USA; WESTERN EUROPE

Accession no.921331

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; USA; WESTERN EUROPE

Item 188 Plastics Technology 50, No.9, Sept.2004, p.43 NON-WARPING PIGMENTS Ciba Specialty Chemicals, BASF Corp., and Lanxess will all be introducing new polymer non-warping pigments at the K 2004 show, which is shortly to be held in Dusseldorf, in Germany. This small article briefly highlights for us the new pigments they will be exhibiting, and their advantageous properties. CIBA SPECIALTY CHEMICALS; BASF CORP.; LANXESS CORP.; BAYER AG

Accession no.925192 Item 186 Adhasion Kleben und Dichten 48, No.9, Suppl.(within original), 2004, p.24/8 German; English TRENDS IN PACKAGING - A CHALLENGE FOR PACKAGING ADHESIVES Onusseit H Henkel KGaA Developments in the field of packaging adhesives, initiated by new materials, new production processes and additional requirements to be met by packaging, are reviewed in terms of application methods, bonding of more sophisticated coated and printed packaging materials and high speed production lines. The development of solvent-based and

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Item 189 Plastics Technology 50, No.9, Sept.2004, p.91 SPECIALTY PE RESINS Two new families of polyethylenes (PEs) made with a single-site catalyst by Borealis are to be launched by the company at the forthcoming K 2004 exhibition in October, we are informed in this small article. The new developments are briefly introduced here. BOREALIS COMPOUNDS LLC EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; USA; WESTERN EUROPE

Accession no.925203

© Copyright 2007 Smithers Rapra Technology

References and Abstracts

Item 190 Flexible 2, No.2, July-Aug.2003, p.34/41 ADDED FLAVOUR Anyadike N The market for films and coatings that have the ability to interact with the packaged product or act as a barrier is growing. In the area of food packaging it is important for films to function as a flavour, odour and fragrance barrier, and it is also important from a point of preventing contamination that there be no unwanted migration from the packaging to the product. Active packaging involves plastics designed to increase shelf life of specific products. It is vital that food remains stable in terms of aroma concentration and composition during the shelf life of the product. WORLD

Accession no.902321 Item 191 Packaging Technology and Science 16, No.5, Sept.-Oct.2003, p.209-20 SAFETY AND QUALITY OF PLASTIC FOOD CONTACT MATERIALS. OPTIMIZATION OF EXTRACTION TIME AND EXTRACTION YIELD, BASED ON ARITHMETIC RULES DERIVED FROM MATHEMATICAL DESCRIPTION OF DIFFUSION. APPLICATION TO CONTROL STRATEGIES Scholler D; Vergnaud J M; Bouquant J; Vergallen H; Feigenbaum A Institut National de la Recherche Agronomique Migration of packaging constituents into food may raise concerns about food safety. This paper describes the conclusions of a EU research project aiming to facilitate the introduction of migration control into good manufacturing practice and into enforcement policies. The first part describes a re-evaluation of analytical approaches to extract and identify potential migrants released by plastic materials, viz. comparison of analytical methods, choice of extraction solvents and of fat simulants. The study focuses on the extraction time needed to achieve a given extraction yield. By correlating these parameters with simple and practical equations, it is possible to design alternative tests for control of compliance of packaging plastics. Using a reference experiment, it is possible to calculate the percentage of extraction which can be achieved in a given time, or the time necessary to reach a target extraction level for other polymer/solvent combinations. A global control scheme is proposed, which indicates whether and when calculation and testing should be applied. Guidelines are proposed and can be adapted to both industrial control and to enforcement laboratories. 11 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; WESTERN EUROPE

Accession no.900965

© Copyright 2007 Smithers Rapra Technology

Item 192 Packaging Technology and Science 16, No.3, May-June 2003, p.99-106 WIDE-SPECTRUM ANTIMICROBIAL PACKAGING MATERIALS INCORPORATING NISIN AND CHITOSAN IN THE COATING Lee C H; An D S; Park H J; Lee D S Kyungnam,University; Korea,University Nisin and/or chitosan were coated, in 3% concentrations, onto paper with a binder medium of EVA to provide antimicrobial activity for use in food packaging. The combined use of nisin and chitosan in the coating was an attempt to give a wide antimicrobial spectrum that could inhibit the growth of several food spoilage and poisonous microorganisms. The migration of the preservative from the coatings to water was evaluated at 10C and related to the suppressed microbial growth in the water and microbial medium. The paper coated with nisin was more effective than the chitosan-coated paper in inhibiting the Grampositive bacterium, Listeria monocytogenes, whereas the latter was more effective against Escherichia coli O157: H7. Combined inclusion of nisin and chitosan in the coating gave antimicrobial activity against both bacterial strains and could improve the microbial stability of milk and orange juice stored at 10C. 24 refs. SOUTH KOREA

Accession no.895898 Item 193 Food Additives and Contaminants 20, No.6, June 2003, p.607-18 BENZOPHENONE IN CARTONBOARD PACKAGING MATERIALS AND THE FACTORS THAT INFLUENCE ITS MIGRATION INTO FOOD Anderson W A C; Castle L UK,Dept.for the Environment,Food & Rural Affairs A method is described to test for benzophenone in cartonboard packaging materials and to test for migration levels in foodstuffs. The extracts were analysed by gas chromatography-mass spectrometry. 11 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.891699 Item 194 ENDS Report No.339, April 2003, p.32 BOOTS REMOVES BISPHENOL A FROM FOOD JAR LIDS Boots has become the latest member of a small band of retailers to have produced strategies for managing the health, environmental and reputational risks posed by chemicals in products. The strategy includes plans to phase out the use of lacquers containing bisphenol A in food jar lids and to encourage suppliers to seek alternatives

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to phthalates. Three years ago, Boots was potentially the prime target of a campaign by Friends of the Earth to persuade retailers to stop using hazardous chemicals and to post information about the chemicals they did use on their websites. Due to potential public opinion, the company has become one of the initial group of retailers - also including Marks & Spencer, the Co-op, B&Q and the Early Learning Centre - to sign up to FoE’s ‘risky chemical pledge’ in 2002. This has committed them to identify known or suspected endocrine disrupters or bioaccumulative substances, and to aim to phase them out within five years. Details are given. BOOTS CO.PLC; FRIENDS OF THE EARTH EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.889235 Item 195 Shawbury, Rapra Technology Ltd., 2003, p.viii, 244, ISBN 1859573746, 25cm, 123-921T AIR MONITORING IN THE RUBBER AND PLASTICS INDUSTRIES Willoughby B G This book examines the types of chemicals found in the polymer industry and the potential hazards. It goes on to explain the common chemical reactions of concern to health and safety. Monitoring methods are described in some detail together with their limitations. This book is divided into the following seven chapters: Chapter 1 - What to look for - What’s there at the start; Chapter 2 - What to look for - What’s created during processing; Chapter 3 - Air monitoring strategies; Chapter 4 - Indirect methods - Trapping species from air; Chapter 5 - Indirect methods - Laboratory analysis; Chapter 6 - Indirect methods - Data Analysis; Chapter 7 - Direct methods EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.888365 Item 196 2002 PLACE Conference. Proceedings of a conference held Boston, Ma., 9th-12th Sept. 2002. Atlanta, GA, TAPPI Press, 2002, Session 16 Paper 58, pp.14, CD Rom, 012 ESTABLISHING A SUITABLE FDA STATUS FOR COATINGS AND ADHESIVES Baughan J S Keller & Heckman LLP (TAPPI) This powerpoint presentation discusses the establishment of a suitable FDA status for coatings and adhesives used in the food industry or in food-contact applications, with respect to the FDA’s definitions of a food additive or a food contact substance. The latter is defined as any substance intended for use as a component of materials used in manufacturing, packing, packaging, transporting or holding food if such use

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is not intended to have a technical effect in food. Options for establishing FDA status are examined. USA

Accession no.883522 Item 197 2002 PLACE Conference. Proceedings of a conference held Boston, Ma., 9th-12th Sept. 2002. Atlanta, GA, TAPPI Press, 2002, Session 13, Paper 48, pp.27, CD Rom, 012 RECENT ADVANCEMENTS IN TESTING PROTOCOLS FOR FDA COMPLIANT EB COATINGS AND ADHESIVES Lin A; Gao H; Wind G; Wornick F Sovereign Specialty Chemicals Inc. (TAPPI) A comprehensive testing protocol utilising cell extraction method and liquid chromatography with a mass selective spectrometer has been developed for testing UV/EB curable, acrylated coatings, adhesives and inks, in order to determine the suitability of the chemistry as part of the food packaging materials. The testing protocol helps to determine FDA compliance of the UV/EB curable chemistry by supporting the ‘no migration’/ ‘no food additive’ statutory exemptions under FDA regulations. Examples are described, which demonstrate the suitability, advantages and selectivity of LC-MS/LC-MS-MS detection methods over the GC-MS method. Also demonstrated is the possibility of achieving FDA compliance with EB curable, acrylated chemistry, and to be able to maintain the same compliance with normal process variation, e.g. coat weight, curing voltage, curing dosage. A powerpoint version of this paper is also included. 6 refs. USA

Accession no.883512 Item 198 Packaging Technology and Science 15, No.5, Sept.-Oct.2002, p.247-54 PROPERTIES OF NISIN-INCORPORATED POLYMER COATINGS AS ANTIMICROBIAL PACKAGING MATERIALS Young-Min Kim Kyungnam,University Nisin was incorporated into binder solutions of acrylic polymer and EVA and then coated onto paper. Diffusive migration of incorporated nisin and the antimicrobial activity of the polymer coatings were investigated in order to understand the way of controlling nisin migration and the extent of microbial suppression by the coated paper. EVA exhibited faster rate and higher degree of migration into aqueous food simulant solutions compared to acrylic polymers, and also exhibited a higher degree of suppression against Micrococcus flavus ATCC 10240 inoculated into the microbial medium. 28 refs. SOUTH KOREA

Accession no.879348

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References and Abstracts

Item 199 Paper Film and Foil Converter 77, No.2, Feb.2003, p.22 CONCERN OVER “PHTHALATES” IN FOOD PACKAGING Podhajny R M Plasticisers are used extensively to soften plastics, building products, blood bags, cosmetics and personal care products, as well as packaging inks and coatings. The majority of plasticisers fall into a broad class of chemicals called esters. In recent years, phthalate esters emissions have become a major environmental and health concern. Phthalate esters vary in their toxicity, but the most widely used phthalate, DEHP, has been labelled as a probable human carcinogen. Food packaging concerns have been focused recently on the use of phthalate plasticisers in many inks, coatings and packaging films, as phthalates can migrate into food from these products. WORLD

Because additives have been around for decades, they have never diminished from research focus in formulations. Even though additives represent a minor portion of a formulator’s paint or milk formula, without them surface defects can be significant. In particular, silicone additives bring to the coatings’ table a range of surface-modifying and enhancing properties. As a result of the increasing pressure to reduce VOCs, UV-curable technology is experiencing a significant growth in the market. The technological advancements of silicone additives are examined as they have progressed through simple polyether modification, which have helped overcome incompatibilities in coatings formulations. The more reactive functional modifications that silicones are heading towards still help to maintain compatibility but offer more permanent results. Typical coating film defects such as cratering and orange peel are avoided, and the negative effects of floating can be suppressed. Furthermore, these additives provide smooth surfaces as well as improving the gloss and allowing the coating to be more scratch resistant. 4 refs.

Accession no.879267

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY; USA; WESTERN EUROPE

Item 200 Plastics in Contact with Foodstuffs. Proceedings of a conference held London, 12th Dec. 2000. Leatherhead, Pira International, 2000, Paper 8, pp.8, 31 cm, 012 DETERMINATION OF BADGE, BFDGE AND NOGE IN FOODS, FOOD SIMULANTS AND COATINGS Rijk R; Bas R TNO Nutrition & Food Research (Pira International)

Accession no.878217

In order to enforce the draft EU directive which intends to exclude the use of Novolac diglycidyl ethers (BADGE) as a hydrogen chloride scavenger in organosol based coatings, analytical methods are required. TNO has been working for several years on the development of a suitable analytical method to determine both BADGE, NOGE (Novolac diglycidyl ethers), and BFDGE, (the smallest molecule in the series of NOGE) including their derivatives in food simulants, foodstuffs and coatings.. Details are given of the development of an analytical method and a confirmation procedure for the determination of the epoxides and their reaction products. EUROPEAN COMMUNITY; EUROPEAN UNION; NETHERLANDS; UK; WESTERN EUROPE

Item 202 Adhesives Age 45, No.11, Nov.2002, p.22-5 LIGHTING IT UP Lin A Sovereign Specialty Chemicals Inc. More and more flexible packaging applications including adhesives, coatings and inks have been drawn to electron beam and UV curable chemistry for many obvious reasons. These reasons include zero or very low VOC and HAPS, space saving, increase in productivity and lower energy consumption. However, the applications in food packaging segments have been limited, especially the food use flexible packaging area. Some of the common concerns from the converters, in the past, have been related to odour, potential migration, lack of proper testing protocols, lack of a simple and secure cure monitoring mechanism and lack of understanding regarding FDA status/regulations of the chemistry. This article discusses the advancements that have been made in the industry to address these concerns. USA

Accession no.874611

Accession no.878454 Item 201 Surface Coatings International Part B 85, No.B4, Nov.2002, p.309-12 ORGANIC-MODIFIED POLYDIMETHYLSILOXANES FOR UVCURABLE COATINGS Stalker D L; Sandmeyer F Wacker Silicones Corp.; Wacker-Chemie GmbH

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Item 203 Hygenic Coatings. Proceedings of a conference held Brussels, Belgium, 8th-9th July 2002. Teddington, Paint Research Association, 2002, Paper 8, p.1-7, 29cm, 012 THE NEED TO IMPROVE HYGIENE IN FOOD PROCESSING PLANTS Notermans S; Hoornstra E TNO Nutrition & Food Research

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References and Abstracts

(Paint Research Association) Food-borne disease statistics and data on endemic bacteria in food processing plants are presented and discussed. Factors contributing to the outbreak of disease and related to inadequate handling are considered and a new strategy for improving hygiene in food processing plants is proposed. The results of experiments carried out using UVdisinfection to inactivate microorganisms on a conveyor belt (Ammaraal Nonex) are also reported. 6 refs. BELGIUM; EUROPE-GENERAL; EUROPEAN COMMUNITY; EUROPEAN UNION; NETHERLANDS; USA; WESTERN EUROPE; WORLD

Accession no.873118 Item 204 Paper Film and Foil Converter 76, No.8, Aug.2002, p.18 REDEFINING PLASTICIZERS IN INKS AND COATINGS Podhajny R M Plasticisers are chemicals that can soften binders used in ink and coatings, improving their flexibility. Most plasticisers are high boiling liquids that partially “dissolve” the polymer framework of select binders. These plasticisers effectively reduce the softening point of the ink or coating binder. One of the undesirable effects of using plasticisers is they can raise the COF by making the ink or coating formulation “softer”. Not only is this effect evident in the ink and coating surface, but some plasticisers can migrate from front to back of the film within the roll. Higher temperature and pressure will increase the rate of migration. As a rule of thumb, if the COF of a printed or coated film rises with time, plasticiser migration would be suspected. USA

Accession no.865441 Item 205 Polymers Paint Colour Journal 192, No.4454, July 2002, p.21-2 INKS FOR NEW MARKETS Sime K Ink formulation relies heavily upon the end use requirement. A growth area is in the food packaging industry, where solvent-based inks are frowned upon due to the VOCs present. There are several classes of ink grades from direct contact with the food, e.g. printing onto eggs, all the way through to exterior packaging. Direct contact with food obviously has the most stringent parameters to fulfil in safety terms. Food packaging that will not come into direct contact with the food item has less stringent rules and much of the testing is done inhouse. Often, for historical reasons, an ink is used with no testing, simply relying on the fact that it has ‘always been used’ and ‘everybody else uses it’. Very little is understood about the possible migration of materials through food packaging, especially in the areas

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of uncured monomers. Several barrier layers are often employed to minimise migration, but long-term effects are only estimated, as information is often gathered through simulated accelerated age testing. Despite these issues, UV curing inks are growing in usage because of their durability and gloss. Aspects covered include formulation with UV, applications and personalisation. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.863726 Item 206 Food Additives and Contaminants 19, No.2, Feb.2002, p.184-201 SAFETY AND QUALITY OF FOOD CONTACT MATERIALS. I. EVALUATION OF ANALYTICAL STRATEGIES TO INTRODUCE MIGRATION TESTING INTO GOOD MANUFACTURING PRACTICE Feigenbaum A; Scholler D; Bouquant J; Brigot G; Ferrier D; Franz R; Lillemark L; Riquet A M; Petersen J H; van Lierop B; Yagoubi N Institut National de la Recherche Agronomique; Reims,University; Paris II,Universite; Denmark’Veterinary & Food Administration; Keuringdients van Waren Results of a research project (EU AUR Research Programme CT94-1025) aimed at introduction of control of migration into good manufacturing practice and into enforcement work are reported. Representative classes of polymer were defined on the basis of chemical structure, technological function, migration behaviour and market share. These classes were characterised by analytical methods. High-temp. gas chromatography was shown to be a powerful method for identification of potential migrants and PMR provided a convenient fingerprint of plastics materials. Volatile compounds were characterised by headspace techniques, in which it was shown to be essential to differentiate volatile compounds desorbed from those generated during the thermal desorption itself. For metal trace analysis, microwave mineralisation followed by atomic absorption was employed. These different techniques were introduced into a systematic testing scheme that was envisaged as being suitable both for industrial control and for enforcement laboratories. 24 refs. DENMARK; EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; GERMANY; NETHERLANDS; SCANDINAVIA; WESTERN EUROPE

Accession no.863624 Item 207 Food Additives and Contaminants 19, No.2, Feb.2002, p.168-75 ANALYSIS OF FOOD PACKAGING UV INKS FOR CHEMICALS WITH POTENTIAL TO MIGRATE INTO FOOD SIMULANTS

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References and Abstracts

Papilloud S; Baudraz D Sicpa Printing Inks Chromatographic methods developed for analysis of the level of ink ingredients potentially available to migrate into food simulants are described and results obtained by application of gas chromatography/mass spectrometry to quantification of the levels of photoinitiators and acrylates are presented and discussed. It is shown that these methods can be used to assess the quality of printing inks intended for primary food packaging to ensure that the release of chemicals is negligible. 10 refs. SWITZERLAND; WESTERN EUROPE

Accession no.863622 Item 208 Food Additives and Contaminants Vol.19, Suppl., 2002, p.185-91 COMPREHENSIVE ANALYSIS OF MIGRATES FROM FOOD-PACKAGING MATERIALS: A CHALLENGE Grob K Zurich Canton,Official Food Control Authority It is suggested that present European regulation of food packaging materials does not provide the assessment for safety corresponding to the opinion of toxicologists that migrants ingested in amounts exceeding a threshold of 1.5 microgram/day should be identified and evaluated toxicologically. Many substances that migrate are neither starting point materials nor obvious derivatives thereof and are, therefore, not covered by existing systems based on positive lists. Safety presupposes the comprehensive analysis of the migrating substances, ultimately to the limits in terms of concentration and molec.wt. considered to be of toxicological concern. Expected problems with this analytical challenge are considered, leading to the conclusion that it will be difficult to achieve comprehensive analysis down to the concentrations presently considered safe, but that systematic work should start to define the possibilities and limitations of analytical chemistry for a migrate-oriented coating legislation. 12 refs. (2nd International Symposium on ‘Food Packaging: Ensuring the Safety and Quality of Foods, Vienna, Austria, Nov.2000) SWITZERLAND; WESTERN EUROPE

Accession no.863618 Item 209 Food Additives and Contaminants Vol.19, Suppl., 2002, p.73-8 TIME-TEMPERATURE STUDY OF THE KINETICS OF MIGRATION OF BADGE (BISPHENOL-A-DIGLYCIDYL-ETHER) INTO A FATTY MEDIUM Simoneau C; Theobald A; Roncari P; Hannaert P; Anklam E European Commission

© Copyright 2007 Smithers Rapra Technology

The migration kinetics of BADGE from processed and non-processed model cans with epoxy resin-based lacquers into vegetable oil were investigated as a function of the process treatment and the temp. of storage. Aliquots from the samples were taken at regular intervals for more than a year. Samples were analysed for BADGE by high-performance liquid chromatography with fluorescence detection. The results showed that heat processing had the greatest effect on migration of BADGE. Storage temp. also significantly influenced migration from non-processed cans, particularly at higher storage temps. such as 60C. Some samples were subjected to 60C storage after an initial period at 20C and an effect on migration was also noted, although to a lesser extent than from processing. The results of migration at higher temps. were also correlated with the potential degradation of BADGE from oxidation products. 15 refs. (2nd International Symposium on ‘Food Packaging: Ensuring the Safety and Quality of Foods, Vienna, Austria, Nov.2000) EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY; WESTERN EUROPE

Accession no.863610 Item 210 Epoxy Technologies for Ambient Cure Protective Coatings. Conference proceedings. Brussels, 12th-14th May 1997, paper 23 INFLUENCE OF THE BENZYL ALCOHOL ON THE REACTIVITY RATIO, SECONDARY AMINE/PRIMARY AMINE, IN THE CURE OF EPOXY AMINE. CASE APPLICATION: COATING FOR DRINKING WATER Paz-Abuin S; Lopez-Quintela A; Pazos M; Prendes P; Varela M; Paseito P Gairesa (Paint Research Association) Based on a kinetic model proposed, the ratio of rate constants (R), secondary amine (k2) to primary amine (k1) is directly obtained by evaluation of concentrations of the primary and secondary amines. The measurements are carried out by IR spectroscopy (FTIR) in the nearIR. Two epoxy formulations are prepared. Bisphenol A epoxy resin (DGEBA)/m-xylenediamine and DGEBA/ mXDA/12.8% benzyl alcohol (BA), being R determined at different temperatures. The BA formulation at 250 deg. C has the highest value of R which should be related to the maximum chemical resistance. A coating based on this formulation is prepared, cured at 250 deg.C and tested following UE regulations (foods and drinks). Global and specific migration is obtained. 20 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN; WESTERN EUROPE

Accession no.769455 Item 211 Journal of Coatings Technology 70, No.877, Feb.1998, p.69-74 POTENTIAL EXPOSURE TO BISPHENOL

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References and Abstracts

A FROM FOOD-CONTACT USE OF EPOXY COATED CANS Howe S R; Borodinsky L; Lyon R S SPI; Keller & Heckman LLP; US,National Food Processors Assn. The potential dietary exposure to bisphenol A from the use of food and beverage cans coated with bisphenol A-based epoxy resins was investigated. The calculation was based on migration data from extraction studies using foodsimulating solvents and time and temperature conditions recommended by the FDA. It was demonstrated that no detectable BPA was found in the extracts from beverage cans using a method sensitive to five parts per billion in the food stimulant. 6 refs. USA

Accession no.671437 Item 212 Surrey, PIRA International, 1997, pp.xi,334. 125.00. 28cms. 10/11/97. 938 FOOD PACKAGING MIGRATION AND LEGISLATION Ashby R; Cooper I; Harvey S; Tice P PIRA International Comprehensive information both on new directives published on food contact materials and draft directives related to the topic. Chapter headings include EU regulations on food contact materials and articles, standard methods of test for plastics and polymeric coatings intended to come in contact with food, practical aspects of migration testing, paper and board and regenerated cellulose films intended for contact with foodstuffs, and rationalising the testing of food contact plastics. Also covered are the future developments in directives for food contact materials and a review of recent migration research. Accession no.653405 Item 213 RadTech ‘96 North America. Volume 1. Conference proceedings. Nashville, Tn., 28th April-2nd May 1996, p.29-34. 895 CATIONIC UV COATING EXTRACTABLES Carter J W; Davis M S; Jupina M J Union Carbide Corp. (RadTech International) FDA-type migration experiments were conducted using a model cationic UV coating in an attempt to demonstrate that good container and packaging hygiene can be achieved if cationic UV inks and overprint varnishes are properly used to decorate and protect food containers and food packaging. After thermal processing, the coating samples were extracted two hours later using different food simulants (aq. ethanol solutions) and processing conditions to simulate different foods and applications. Extraction samples were analysed for epoxide and photoinitiator

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substances using GC and HPLC methods. Generally, ppb levels of UVR 6110, propylene carbonate (PC), diphenyl sulphide (DPS), and bis and thio salts were found. The concentrations of extractables depended on thermal treatment, processing temperature and solvent. 5 refs. USA

Accession no.628048 Item 214 Food Additives and Contaminants 12, No.2, March/April 1995, p.223-34 COMPOSITIONAL ANALYSIS OF SAMPLES OF THERMOSET POLYESTER AND MIGRATION OF ETHYLBENZENE AND STYRENE FROM THERMOSET POLYESTER INTO PORK DURING COOKING Gramshaw J W; Vandenburg H J Leeds,University The levels of ethylbenzene, styrene, benzene and benzaldehyde in samples of thermoset polyester were determined by dynamic headspace/gas chromatography. Styrene was present at levels from 50 to 1400 mg/kg, ethylbenzene up to 25 mg/kg and benzaldehyde up to 180 mg/kg. Benzene levels were usually less than 1 mg/kg, but one article contained 19 mg/kg. Levels of styrene dimers and trimers were estimated using SEC followed by gas chromatographic analysis and were present at about 100 and 700 mg/kg, respectively. The principal identified constituents of solvent extracts were stearic and palmitic acids, present at a combined level of nearly 1 wt % of the plastic. Styrene was shown to be produced by thermal depolymerisation at temps. of 175C and above. The migration of ethylbenzene and styrene into belly pork cooked in thermoset polyester dishes for 1.5 h at 175C was measured by Likens-Nickerson extraction of the cooked meat and GC/MS analysis of the extracts. Migration ranged from 6 to 2400 micro g/kg for styrene and from less than 6 to 34 micro g/kg for ethylbenzene. 13 refs. EUROPEAN COMMUNITY; EUROPEAN UNION; UK; WESTERN EUROPE

Accession no.548000 Item 215 Progress in Organic Coatings 22, No.1-4, May-Sept.1993, p.145-59 DIFFUSION CONTROLLED KINETICS OF CROSSLINKING Dusek K; Havlicek I Czechoslovak Academy of Sciences Reactions of polymer formation and crosslinking become diffusion-controlled when, during the reaction, the increasing Tg comes close to the reaction temp. The reaction still continues below the Tg, but the reaction rate decreases markedly. A theory is presented relating the apparent rate constant to the difference between the reaction temp. and Tg based on the free volume or the Adams-Gibbs theory of

© Copyright 2007 Smithers Rapra Technology

References and Abstracts

Tg. The theory is correlated with experiments on curing of diglycidyl ether of bisphenol A with 1,3-propanediamine. The implications for formation of chemically-crosslinked protective films are discussed. The presence of a solvent and its evaporation are shown to affect the reaction rate through a change in concentrations of reactants as well as in Tg. 34 refs. (18th International Conference in Organic Coatings Science & Technology, Athens, Greece, July 1992) CZECH REPUBLIC

Accession no.497034 Item 216 Radtech Europe - Creating Tomorrow’s Technology. Conference Proceedings. Edinburgh, 29th Sept-2nd Oct.1991, Paper 36, p.461-70. 89 PARAMETERS AFFECTING EXTRACTABLES OF CATIONIC UV CURED COATINGS IN CARDBOARD APPLICATION Gaube H; Ohlemacher J Degussa AG (Radtech Europe) The results are reported of a study of the critical parameters affecting extractable and potentially migratable residues from pigment-coated cardboard to which a cationic UV varnish based on a low odour epoxide monomer had been applied. Emphasis was placed upon substrate pretreatment and UV coating composition in order to minimise extractable residues along with increasing coating reactivity. 6 refs. EUROPEAN COMMUNITY; GERMANY; WESTERN EUROPE

Accession no.496359 Item 217 Analyst 113,No.2,Feb.1988,p.239-42 DETERMINATION OF OLIGOMER 340 AND POLYAMINES IN CURED EPOXY RESINS BY EXTRACTION AND HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY Henriks-Eckerman M.Laijoki T TURKU REGIONAL INSTITUTE OF OCCUPATIONAL HEALTH

Item 218 Structural Adhesives:Developments in Resins and Primers. Barking,Elsevier Applied Science Publishers Ltd.,1986,p.1-27. 6A1 CURE AND PROPERTIES OF THERMOSETTING POLYMERS Gillham J K PRINCETON,UNIVERSITY Edited by: Kinloch A J The time-temperature-transformation cure diagram (showing Tgs of fully cured system and of reactants, and temperature at which gelation and vitrification occurred together), properties of thermosetting systems, and the torsional braid analysis/torsion pendulum technique for characterising thermosetting systems were described with relevant equations. They were used to characterise rubber-modified (CTBN: prereacted carboxy-terminated NBR and ATBN: amino-terminated NBR) epoxy resin (cure, transitions, morphology, mechanical properties). Mechanical properties of the ATBN-modified system were more sensitive to cure history than those of the prereacted CTBN one. Fracture energy rose with temperature for all systems (due to rising matrix ductility) and usually in the order neat to CABN to ATBN systems. 22 refs. USA

Accession no.331091 Item 219 Step-Growth polymerizations New York, Dekker, 1972, p.95-113. 7221 POLYURETHANES: THE CHEMISTRY OF THE DIISOCYANATE-DIOL REACTION Lyman D J Solomon D H This chapter focuses primarily on the kinetics and mechanism of the diisocyanate-diol reaction. The effects of the structure of the reactants and the reaction medium are discussed. 87 refs. Accession no.731

The efficiency of acetone in extracting unreacted oligomer 340 and aliphatic polyamine hardeners (diethylenetriamine and triethylenetetramine) from cold-cured epoxy resins was investigated by HPLC. Several epoxy resins, including coatings and adhesives, were tested. Acetone-soluble amounts of oligomer 340 and polyamine were determined as a function of cure time and extraction was performed in an ultrasonic bath. The data obtained demonstrated the suitability of the method to evaluate health risks of cured epoxy resins and to obtain additional information on the curing kinetics of epoxy resins. 13 refs. FINLAND

Accession no.352838

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References and Abstracts

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© Copyright 2007 Smithers Rapra Technology

Subject Index

Subject Index A ABIETIC ACID, 94 ABRASION RESISTANCE, 36 175 183 ABSORPTION SPECTRA, 13 182 ACCELERATED AGEING, 205 ACCELERATOR, 32 55 84 195 ACETIC ACID, 4 ACETONE, 217 ACETYL TRIETHYL CITRATE, 117 ACID SCAVENGER, 76 ACRYLAMIDE COPOLYMER, 8 78 153 ACRYLATE, 12 207 ACRYLATE COPOLYMER, 27 ACRYLATE POLYMER, 202 ACRYLIC, 66 105 152 166 183 198 ACRYLIC ACID COPOLYMER, 160 ACRYLIC COPOLYMER, 15 16 164 ACRYLIC ELASTOMER, 32 84 142 ACRYLIC ESTER, 12 207 ACRYLIC ESTER COPOLYMER, 27 ACRYLIC ESTER POLYMER, 202 ACRYLIC POLYMER, 14 27 42 60 106 120 143 ACRYLIC RESIN, 14 143 ACRYLIC RUBBER, 32 84 142 ACRYLONITRILE POLYMER, 82 ACRYLONITRILE-BUTADIENE COPOLYMER, 142 ACRYLONITRILE-BUTADIENESTYRENE TERPOLYMER, 3 16 22 74 175 183 ACRYLOYLOXY GROUP, 27 ACTIVATED CARBON, 6 ACTIVATION ENERGY, 181 ACTIVE PACKAGING, 29 39 ACTIVE POLYMER MATERIAL, 161 167 179 ADDITIVE, 3 15 22 26 29 30 31 32 33 39 40 61 63 65 67 73 74 82 84 87 88 95 107 118 133 134 141 144 148 154 164 168 179 183 187 188 191 196 200 212 215 218 ADHESION, 27 35 100 101 110 114 121 122 147 168 204

ADHESION PROMOTION, 99 172 ADHESIVE, 27 28 34 35 39 40 42 45 46 49 50 51 52 53 57 59 66 96 99 100 103 104 105 120 121 122 124 147 151 152 159 162 163 166 172 174 186 196 197 202 217 ADHESIVE LABEL, 39 71 99 ADHESIVE TAPE, 27 AEROPLANE, 183 AEROSPACE APPLICATION, 183 AGEING, 37 AGGREGATE, 2 AGRICULTURAL APPLICATION, 22 70 76 81 84 98 103 148 AGROCHEMICAL, 40 71 AIR BARRIER, 44 AIR POLLUTION, 195 AIRCRAFT, 183 ALKENE POLYMER, 3 9 16 22 43 59 60 76 86 89 102 112 135 148 156 183 187 188 196 ALKYD RESIN, 63 ALKYL HYDROXIDE, 12 ALKYLPHENOL, 32 ALLOY, 183 ALPHA-OLEFIN POLYMER, 156 ALTERNATING COPOLYMER, 54 ALTERNATING COPOLYMERISATION, 54 ALTERNATING POLYMER, 54 ALTERNATING POLYMERIZATION, 54 ALUMINIUM, 73 100 157 ALUMINIUM FOIL, 35 ALUMINOSILICATE, 128 AMIDE POLYMER, 3 16 35 45 59 64 66 73 82 103 104 144 171 188 198 AMINE, 32 35 84 187 210 ANTI-BLOCKING AGENT, 26 133, 145 ANTI-FOAMING AGENT, 14 ANTI-SCORCH AGENT, 195 ANTIBLOCKING AGENT, 26 133 ANTIDEGRADANT, 32 84 ANTIFOULING AGENT, 41 ANTIFREEZE, 178 ANTIFUNGAL, 131 ANTIMICROBIAL ACTIVITY, 54 113 198 ANTIMICROBIAL AGENT, 124 131 133 154 155 161 192

© Copyright 2007 Smithers Rapra Technology

ANTIMONY, 3 23 ANTIOXIDANT, 22 30 31 37 39 61 76 133 168 187 ANTISTATIC AGENT, 39 133 168 AQUEOUS PHASE, 4 ARCHITECTURAL APPLICATION, 183 AROMA, 47 48 AROMATIC AMINE, 34 35 39 ARRHENIUS’S LAW, 198 ARYL ALKYL KETONE, 13 ARYL ARYL KETONE, 13 ASCORBIC ACID, 138 ATOM TRANSFER RADICAL POLYMERISATION, 160 ATOMIC ABSORPTION SPECTROSCOPY, 206 AUTOMOTIVE APPLICATION, 22 61 72 76 92 93 102 119 123 133 156 157 180 183 AZO COMPOUND, 8

B BACTERIA, 54 155 203 BACTERICIDE, 167 183 198 BAG, 12 26 31 71 98 135 148 188 189 BAG-IN-BOX, 35 BAKERY APPLICATION, 19 BAR CODE, 136 BARRIER COATING, 150 BARRIER FILM, 136 158 159 BARRIER LAYER, 129 136 BARRIER PROPERTIES, 12 25 34 38 39 40 44 47 49 50 51 52 53 70 73 81 91 100 122 149 150 158 170 171 181 183 184 190 197 202 BARRIER RESIN, 104 BATCH POLYMERISATION, 75 BEADS, 77 137 BEER, 167 211 BEER BOTTLE, 73 150 158 BELTING, 32 BELTS, 19 32 203 BENZALDEHYDE, 214 BENZENE, 214 BENZOPHENONE, 27 39 193 BENZOPHENONE POLYMER, 193 BENZOTRIAZOLE, 118 146 BENZOTRIAZOLYLBISMETHYL

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Subject Index

PHENYLETHYLPHENOL, 118 BENZOTRIAZOLYLPHENOL COMPOUND, 118 BENZYL ALCOHOL, 210 BEVERAGE, 38 99 108 189 BIAXIAL ORIENTATION, 12 22 38 60 66 99 103 104 187 BINDER, 12 33 85 192 198 204 BIOABSORPTION, 77 BIOCATALYST, 160 BIOCIDE, 30 41 131 133 161 168 BIOCOMPATIBILITY, 15 16 BIODEGRADABILITY, 12 16 48 56 71 78 81 96 105 116 124 133 166 BIODETERIORATION, 12 16 48 56 71 78 81 82 96 105 116 124 133 166 BIOLOGICAL ATTACK, 203 BIOLOGICAL DEGRADATION, 128 BIOMASS, 81 BIOMATERIAL, 2 BIOPOLYMER, 12 16 81 116 160 166 BIORIENTATION, 181 BIOSENSOR, 136 160 BIOTECHNOLOGY, 166 BIREFRINGENCE, 38 BISHYDROXYMETHACRYLOX YPROPOXYPHENYLPROPA NE COPOLYMER, 15 BISPHENOL A, 17 139 173 210 211 215 BISPHENOL A DIGLYCIDYL ETHER, 34 35 39 200 BISPHENOL DIGLYCIDYL ETHER, 34 35 39 200 BLEND, 22 23 43 73 76 116 117 123 145 164 175 184 187 BLISTER PACKAGING, 116 129 161 184 BLOCK COPOLYMER, 160 BLOW MOULDING, 12 16 73 116 137 164 168 BLOWING AGENT, 31 133 168 195 BLOWN FILM, 12 26 68 102 111 161 189 BOIL-IN-THE-BAG, 35 BOILING WATER RESISTANCE, 55 BOND STRENGTH, 100 BONDING, 101 107 121 175 183 186 BONDING AGENT, 27 168 BORON NITRIDE, 56 BOTTLES, 189 7 16 23 31 32 35

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49 50 51 52 53 59 73 82 96 135 136 137 139 150 158 181 164 181 190 BOVINE SERUM ALBUMIN, 2 BREAKING STRAIN, 92 93 BREAKING STRESS, 92 93 BREWING APPLICATION, 84 BRIGHTNESS, 182 BRITTLENESS, 12 BUILDING APPLICATION, 16 119 122 133 156 164 169 183 BUTADIENE-ACRYLONITRILE COPOLYMER, 32 84 142 218 BUTADIENE-STYRENE COPOLYMER, 16 164 BUTENE, 26 BUTYL RUBBER, 32 84 142 BUTYLENE, 26 BUTYLTIN, 164

C CABLE, 76 CAFFEINE, 83 CALCIUM CARBONATE, 26 216 CALCIUM PHOSPHATE, 15 CALCIUM SILICATE, 61 CALCIUM STEARATE, 126 CALCULATION, 29 218 CALENDERING, 32 164 168 CALIBRATION, 4 88 95 CALORIMETRY, 54 CAMPUS DATASHEET, 92 93 CAN COATING, 46 173 200 209 211 CANS, 26 32 73 86 167 200 211 CAP, 189 CAPACITY, 7 12 22 23 26 61 63 66 73 76 81 99 102 103 104 114 122 123 145 150 156 166 176 178 184 CAPACITY EXPANSION, 12 26 102 CAPACITY UTILISATION, 63 176 CAPROLACTAM, 130 CAPROLACTAM POLYMER, 25 36 130 136 CAPROLACTONE POLYMER, 2 48 CAPRYLLACTAM, 130 CARBON, 12 73 CARBON BLACK, 6 29 169 CARBON DIOXIDE, 12 73 CARBON FIBRE-REINFORCED PLASTIC, 122 CARBONATE POLYMER, 3 16 25 35 139 175 183 190 194 CARBONATED BEVERAGE, 108

CARBOXYL-TERMINATED, 218 CARCINOGEN, 30 CARCINOGENICITY, 75 CARDBOARD, 73 216 CARTON, 11 35 202 CAST FILM, 12 68 103 104 189 CASTING, 24 71 183 CATALYSIS, 69 111 145 189 CATALYST, 19 21 22 23 30 31 32 41 43 56 64 68 91 95 102 104 109 112 123 156 160 170 176 CATALYST SUPPORT, 129 CAULK, 88 CAVITATION, 69 CAVITY, 26 CELL MIGRATION, 31 CELLULAR MATERIAL, 16 82 116 122 133 201 CELLULOSE, 28 71 179 212 CELLULOSE NITRATE, 204 CERAMIC, 28 140 179 CERAMIC POWDER, 136 CERIC ION, 8 78 153 CHAIN CONFORMATION, 38 CHAIN EXTENDER, 16 35 CHAIN FLEXIBILITY, 15 CHALK, 26 CHAR, 6 CHARACTERISATION, 2 24 38 54 78 108 117 131 168 218 CHARPY, 92 93 CHARRING, 3 CHEMICAL COMPOSITION, 12 26 216 CHEMICAL IONISATION MASS SPECTROSCOPY, 138 CHEMICAL MODIFICATION, 4 32 40 110 160 CHEMICAL PROPERTIES, 19 22 25 42 55 72 120 149 183 210 CHEMICAL REACTION, 32 CHEMICAL RESISTANCE, 19 22 25 42 48 55 72 120 149 183 210 CHEMICAL SENSOR, 136 CHEMICAL STRUCTURE, 8 12 13 15 24 26 38 54 56 68 106 182 CHEMICAL TREATMENT, 114 CHEMICALS, 166 CHINA CLAY, 128 CHITOSAN, 160 192 CHLOROBENZENE, 9 CHLOROPRENE POLYMER, 32 84 CHROMATOGRAPHY, 4 10 11 17 29 35 37 59 62 82 84 88 90 94 108 118 130 138 142 146 173 174 193 195 197 200 206 207 209 212 213

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Subject Index

CHROME-FREE, 119 CHROMIUM COMPOUND, 141 CHROMOGEN, 1 CHROMOPHORE, 1 CIS-1,4-POLYISOPRENE, 84 CLARIFYING AGENT, 16 21 30 133 CLARITY, 12 21 25 61 73 97 102 111 164 171 184 CLAY, 48 61 73 136 158 CLEARCOAT, 131 CLING-TYPE FILM, 4 CLOSURE, 7 65 86 137 149 175 189 CLOTHING, 26 41 169 CO-COMBUSTION, 6 CO-INJECTION MOULDING, 73 COAT HANGER, 164 175 COATED FILM, 196 198 COATED METAL, 173 211 COATED PAPER, 35 46 192 COATHANGERS, 164 175 COATING WEIGHT, 152 159 197 198 COCONUT OIL, 118 146 COEFFICIENT OF FRICTION, 36 204 COEXTRUSION, 35 43 102 104 114 164 179 183 184 COEXTRUSION COAT, 47 COHESION, 35 COHESIVE ENERGY DENSITY, 40 COHESIVE STRENGTH, 147 COINJECTION MOULDING, 73 COLD-CURING, 217 COLD-SEAL, 34 104 152 COLORANT, 2 3 6 8 12 26 30 33 67 74 107 137 179 182 188 195 COLORATION, 58 157 COLORIMETRY, 34 35 74 COLOUR, 3 29 49 50 51 52 53 58 67 73 74 107 127 131 158 164 175 182 183 187 188 COLOUR BLEEDING, 182 COLOUR CHANGE, 158, 161 167 COLOUR COMPOUNDING, 85 COLOUR CONCENTRATE, 85 COLOUR CONTRAST, 3 COLOUR DENSITY, 107 COLOUR FASTNESS, 164 COLOUR MATCHING, 74 85 188 COLOUR MEASUREMENT, 107 COLOUR RETENTION, 85 182 COLOUR SHADING, 85 COLOUR STABILITY, 22 76 COLOUR STRENGTH, 86 COMMERCIAL INFORMATION,

12 22 26 66 74 92 93 103 158 162 163 165 166 178 187 COMMODITY POLYMER, 102 COMONOMER, 68 69 76 91 COMPACTION, 107 COMPATIBILISER, 32 76 117 133 COMPATIBILITY, 65 86 107 110 119 135 148 185 188 201 COMPOSITE, 15 16 36 67 92 93 96 117 122 125 183 195 COMPOSITION, 112 COMPOSTING, 12 81 99 124 COMPOUNDER, 144 COMPOUNDING, 12 26 85 168 COMPOUNDING INGREDIENT, 29 32 107 COMPRESSION, 188 COMPRESSION MOULDING, 19 COMPRESSION PROPERTIES, 107 COMPUTER CONTROL, 3 CONCRETE, 98 169 CONCURRENT ENGINEERING, 3 CONDENSATION POLYMERISATION, 150 CONFORMABILITY, 99 CONSTRUCTION, 183 CONTACT AREA, 32 84 CONTACT TIME, 8 32 84 CONTAINER, 4 11 12 32 35 40 56 69 73 82 102 148 164 165 188 193 194 CONTAMINANT, 9 59 62 128 181 CONTAMINATION, 29 31 33 CONTROLLED ATMOSPHERE, 38 82 167 CONVERTING, 26 28 31 35 68 110 125 163 164 CONVEYOR BELT, 19 203 COOKWARE, 17 39 214 COOLANT, 178 COPOLYESTER, 72 160 183 COPOLYETHER, 14 106 COPOLYMER, 26 COPOLYMER COMPOSITION, 47 79 COPOLYMERISATION, 54 CORN STARCH, 12 CORONA TREATMENT, 26 147 172 COSTS, 3 7 26 68 73 74 96 99 144 150 151 159 161 172 177 180 187 COUPLING AGENT, 32 133 CRACKING, 12 CRATERING, 14 CROSS-FRACTIONATION, 68

© Copyright 2007 Smithers Rapra Technology

CROSSLINK, 217 CROSSLINKING, 24 56 90 159 168 189 195 210 215 CROSSLINKING AGENT, 35 76 105 CRUDE OIL, 12 CRYSTALLINITY, 21 36 38 164 CRYSTALLISATION RATE, 21 CRYSTALLISATION TEMPERATURE, 21 68 CUP, 11 31 65 86 116 CURE TIME, 57 217 CURING, 11 13 19 27 32 33 35 42 45 46 55 56 57 60 105 110 115 147 152 159 172 174 180 186 189 197 201 202 205 207 213 215 218 CURING AGENT, 32 35 37 55 76 84 105 215 217 CURING LAMP, 110 CURING RATE, 172 CUSHIONING, 16 CUTLERY, 12 166 CYCLE TIME, 16 65 73 102 111 116 CYCLODEXTRINS, 56 CYCLOOLEFIN COPOLYMER, 184

D DAIRY APPLICATION, 70 84 DAMPING, 88 DART IMPACT, 26 DEBOTTLENECKING, 12 178 DECOMPOSITION, 195 DECOMPOSITION PRODUCT, 37 DECOMPOSITION RATE, 98 DECORATION, 58 DEFATTING, 130 DEFECT, 14 164 DEFLECTION TEMPERATURE UNDER LOAD, 92 93 DEFOAMING AGENT, 14 DEFORMATION, 12 DEFORMATION TEMPERATURE, 102 DEGASSING, 75 190 DEGRADATION, 12 16 31 33 37 48 56 71 81 96 105 107 108 116 124 127 133 148 160 166 171 195 205 209 DEGRADATION PRODUCT, 13 59 DEGREE OF CONVERSION, 15 DEGREE OF CRYSTALLINITY, 21 DEGREE OF GRAFTING, 78

111

Subject Index

DEGREE OF POLYMERISATION, 15 DEHYDROABIETIC ACID, 94 DELAMINATION, 73 DELIVERY SYSTEM, 85 DENTAL APPLICATION, 15 DEPOLYMERISATION, 214 DESIGN, 43 49 50 51 52 53 83 96 164 183 187 189 DESIGN FOR RECYCLING, 49 50 51 52 53 DESORPTION, 40 82 91 206 DETERGENT, 71 DIAGNOSTIC APPLICATION, 109 177 DIAMINE, 215 DIATOMACEOUS EARTH, 26 DICHLOROMETHANE, 138 DIESEL FUEL, 25 DIETHYLENETRIAMINE, 217 DIETHYLTHIOXANTHONE, 11 DIFFERENTIAL SCANNING CALORIMETRY, 38 54 78 112 117 153 181 DIFFERENTIAL THERMAL ANALYSIS, 38 54 78 112 117 153 DIFFRACTION, 24 36 112 153 DIFFRACTION PATTERN, 24 DIFFUSION, 4 9 18 40 79 82 91 112 146 181 215 DIFFUSION BARRIER AGENT, 158 DIFFUSION COEFFICIENT, 9 18 48 91 118 181 191 198 DIGLYCIDYL ETHER, 173 215 DIGLYCIDYL ETHER BISPHENOL A, 209 DIISOCYANATE 216 DIMENSIONAL STABILITY, 69 102 183 DIMETHACRYLATE COPOLYMER, 15 DIMETHYL SILOXANE POLYMER, 14 88 DIOL 216 DIPHENYLMETHANE DIISOCYANATE, 35 DIRECTIVE, 18 29 31 32 34 39 125 144 179 200 212 DISCOLORATION, 70 DISCRIMINANT ANALYSIS, 4 8 11 DISEASE, 203 DISINFECTANT, 203 DISPERSIBILITY, 188 DISPERSION, 26 42 65 85 131 137 DISSOLUTION, 40 138

112

DISTORTION RESISTANCE, 107 137 DOMESTIC APPLIANCE, 155 183 DOMESTIC EQUIPMENT, 16 155 183 188 214 DOMESTIC REFUSE, 49 50 DOSE RATE, 8 16 21 45 76 86 89 137 139 185 DOSIMETRY, 45 DRAINAGE PIPE, 182 DRINKING VESSEL, 11 31 65 86 116 DRINKING WATER, 19 23 109 210 DRUG CARRIER, 160 DRUG PACKAGING, 103 DRUM, 175 DRY BLENDING, 168 DRY BONDING, 35 152 DRY FILM, 137 DRYING, 12 33 80 92 93 DRYING TIME, 92 93 DUAL CURING, 110 DUAL INJECTION MOULDING, 73 DUAL REACTOR, 69 DURABILITY, 76 205 DUST, 26 148 188 195 DWELL TIME, 12 DYE, 2 8 77 107 171 177 182 DYNAMIC STABILITY, 164

E ECOLOGY, 141 EFFLUENT, 8 EFFLUENT TREATMENT, 6 EJECTION, 65 ELASTIC PROPERTIES, 88 ELASTICITY, 19 156 ELASTOMER, 3 6 16 19 28 32 34 37 42 57 67 72 76 84 85 108 121 123 137 138 142 145 148 156 164 175 179 194 195 200 201 203 212 213 ELECTRIC CABLE, 76 ELECTRIC KETTLE, 59 ELECTRICAL APPLICATION, 16 119 133 ELECTRICAL CABLE, 76 ELECTRICAL CONDUCTIVITY, 136 160 169 ELECTRON BEAM, 197 ELECTRON BEAM CURING, 35 42 45 46 57 147 159 172 174 180 202 ELECTRON MICROSCOPY, 36 78 112 117 153

ELECTRON SCANNING MICROSCOPY, 36 78 112 117 153 ELECTRONIC APPLICATION, 16 57 71 136 156 183 ELECTRONIC CIRCUITRY, 158 ELECTRONIC NOSE, 10 ELECTROSPRAY IONISATION, 90 173 ELEMENTAL ANALYSIS, 54 ELONGATION, 116 147 ELONGATION AT BREAK, 12 92 93 ELUTION, 5 EMBOSSING, 101 EMISSION CONTROL, 128 EMPLOYEE, 165 EMULSION, 105 162 163 187 EMULSION POLYMERISATION, 22 ENCAPSULATION, 77 ENDOCRINE DISRUPTER, 194 ENERGY CONSERVATION, 26 ENERGY CONSUMPTION, 150 169 ENERGY RECOVERY, 6 152 168 ENERGY SAVING, 111 ENGINEERING APPLICATION, 72 107 122 185 ENGINEERING PLASTIC, 22 72 107 122 185 188 ENGINEERING THERMOPLASTIC, 22 122 188 ENVIRONMENT, 49 50 51 52 53 75 82 96 141 194 ENVIRONMENTAL IMPACT, 12 57 128 152 ENVIRONMENTAL LEGISLATION, 73 84 107 128 ENVIRONMENTAL PROTECTION, 12 109 128 168 ENVIRONMENTALLY FRIENDLY, 12 187 ENZYMAIC SYNTHESIS, 160 EPICHLOROHYDRIN, 17 EPICHLOROHYDRIN POLYMER, 160 EPICHLOROHYDRIN RUBBER, 142 EPOXIDE POLYMER, 34 173 179 216 EPOXIDE RESIN, 34 173 179 194 200 209 210 211 215 EPOXIDISED OIL, 126 EPOXIDISED SUNFLOWER OIL, 126 EPOXY ACRYLATE, 197

© Copyright 2007 Smithers Rapra Technology

Subject Index

EPOXY ACRYLATE POLYMER, 110 EPOXY OLIGOMER, 197 EPOXY RESIN, 34 173 179 194 200 209 210 211 215 217 218 ESTER COPOLYMER, 72 160 183 ESTERIFICATION, 160 ETCHING, 5 58 183 ETHANOL, 10 90 94 108 118 130 146 166 181 ETHENE, 12 ETHENE COPOLYMER, 47 79 ETHER COPOLYMER, 14 106 ETHYL ACETATE, 10 ETHYL ALCOHOL, 10 90 94 108 118 130 146 166 181 ETHYL HEXANOIC ACID BISPHENOL A, 39 ETHYL LACTATE, 7 ETHYLBENZENE, 214 ETHYLENE, 12 ETHYLENE BUTENE COPOLYMER, 69 ETHYLENE COPOLYMER, 47 79 ETHYLENE GLYCOL DIMETHACRYLATE COPOLYMER, 15 ETHYLENE POLYMER, 7 9 10 12 16 26 31 35 40 43 49 50 51 52 53 61 64 65 68 69 74 91 95 96 99 103 104 111 113 114 129 133 143 144 161 172 176 179 184 185 187 188 189 190 192 ETHYLENE THIOUREA, 138 ETHYLENE-BUTENE COPOLYMER, 69 ETHYLENE-BUTYLENE COPOLYMER, 69 ETHYLENE-HEXENE COPOLYMER, 69 ETHYLENE-OCTENE COPOLYMER, 69 ETHYLENE-PROPYLENE COPOLYMER, 32 38 84 ETHYLENE-PROPYLENE RUBBER, 32 84 ETHYLENE-PROPYLENEDIENE TERPOLYMER, 16 156 ETHYLENE-VINYL ACETATE COPOLYMER, 35 43 192 198 ETHYLENE-VINYL ALCOHOL COPOLYMER, 35 64 66 104 112 150 ETHYLENIMINE POLYMER, 54 EXCLUSION CHROMATOGRAPHY, 214 EXPORTS, 7 63 103 178 EXPOSURE, 195

EXPOSURE LEVEL, 25 30 EXPOSURE LIMIT, 18 23 41 EXPOSURE TIME, 12 EXTRACTION, 1 4 5 17 29 34 35 37 39 62 82 83 90 130 138 142 144 174 191 211 216 EXTRUDER, 12 26 EXTRUSION, 12 16 19 25 32 35 68 71 137 150 161 164 168 175 185 189 EXTRUSION BLOW MOULDING, 164 168 EXTRUSION COATING, 47 102

F FABRIC, 169 170 FABRICATION, 68 FACTOR ANALYSIS, 10 FAN SHROUD, 93 FAST-CURING, 55 152 172 FATIGUE RESISTANCE, 72 FEEDSTOCK, 12 29 166 FENCING, 164 FERMENTATION, 12 FIBRE, 5 12 22 76 107 148 166 187 FIBRE-REINFORCED PLASTIC, 122 133 FICK’S SECOND LAW, 198 FILAMENT, 5 12 FILLER, 6 15 26 32 36 49 50 51 52 53 84 168 169 183 195 FILLER CONTENT, 16 FILMS, 1 4 10 11 12 20 22 25 26 38 43 42 43 44 45 46 47 48 49 50 51 52 53 60 61 64 66 67 68 70 71 73 76 79 86 91 98 99 101 102 103 104 106 110 113 114 116 121 123 129 135 136 137 148 149 151 156 157 158 159 161 164 166 171 172 176 181 183 187 188 190 196 198 202 204 212 215 FILTRATION, 138 169 FIRE RESISTANCE, 6 FISH-EYE, 14 FLAKE, 12 FLAME PROOFING, 16 67 95 122 133 168 FLAME RETARDANCE, 16 67 95 122 133 168 FLAME RETARDANT, 16 67 95 122 133 168 FLAMMABILITY, 6 16 61 76 FLAVOUR, 10 40 47 190 FLEXIBILITY, 12 35 42 47 156 164 188

© Copyright 2007 Smithers Rapra Technology

FLEXOGRAPHIC PRINTING, 14 FLEXURAL MODULUS, 21 102 FLEXURAL PROPERTIES, 21 38 68 69 72 102 111 122 129 184 FLOCCULANT, 8 FLOORING, 41 55 FLOW, 26 148 188 FLOW LINE, 157 185 FLOW PROPERTIES, 57 65 FLUORESCEIN ISOTHIOCYANATE, 2 FLUORESCENCE LIFETIME SPECTROSCOPY, 2 FLUORESCENCE OPTICAL MICROSCOPY, 29 FLUORESCENCE SPECTROSCOPY, 2 95 FLUOROCARBON RUBBER, 32 84 142 FLUOROELASTOMER, 32 84 142 FLUORORUBBER, 32 84 142 FLUX, 140 FOAM,3 16 82 116 122 133 201 FOAMING AGENT, 31 133 168 195 FOIL, 101 104 FOOD ADDITIVE, 29 30 63 82 87 88 196 FOOD APPLICATION, 54 67 75 83 108 140 FOOD INDUSTRY, 6 19 28 32 84 200 FOOD SIMULANT, 1 17 18 29 32 33 35 59 94 108 118 181 198 200 207 209 211 FOOD STORAGE, 32 FOODSTUFF, 146 148 149 181 FOOTWEAR, 163 175 FORM-FILL-SEAL, 71 FORMULATION, 14 32 74 84 107 110 131 144 147 164 168 188 201 205 210 FOURIER TRANSFORM INFRARED SPECTROSCOPY, 8 24 40 54 78 79 126 153 FRACTIONATION, 68 FRACTURE ENERGY, 218 FRACTURE MORPHOLOGY, 5 68 153 FRAGRANCE, 190 FRAGRANCE ADDITIVE, 40 FREE RADICAL COPOLYMERISATION, 8 FREE RADICAL POLYMERISATION, 8 54 FREE VOLUME, 9 215 FREE-RADICAL GENERATOR, 1 FREEZE-THAW STABILITY, 102

113

Subject Index

FRICTION, 65 FRICTION COEFFICIENT, 36 204 FRUIT JUICE, 70 FUEL, 6 FUEL TANK, 40 122 FUNCTIONAL BARRIER, 34 181 197 202 FUNCTIONAL GROUP, 121 FUNCTIONAL MONOMER, 83 FUNCTIONALITY, 110 FUNGICIDE, 183

G GAS ABSORPTION, 113 GAS BARRIER, 38 98 136 GAS CHROMATOGRAPHY, 4 10 17 29 35 37 59 62 82 84 90 108 142 193 206 207 214 GAS LIQUID CHROMATOGRAPHY, 39 GAS PERMEABILITY, 19 44 47 48 60 79 112 113 GAS PHASE POLYMERISATION, 68 129 GAS SENSOR, 167 GAS TRANSMISSION, 44 GAS TRANSPORT, 38 GASES, 12 149 195 GASKET, 39 175 GASOLINE, 25 GAUGE, 26 GEL COAT, 125 183 GEL CONTENT, 129 GEL FORMATION, 110 GEL PERMEATION CHROMATOGRAPHY, 88 GELATION, 164 168 218 GELLING, 164 168 218 GELLING AGENT, 160 GENETIC ENGINEERING, 81 GLASS, 73 GLASS FIBRE-REINFORCED, 93 122 125 GLASS FIBRE-REINFORCED PLASTICS, 16 93 122 125 178 183 GLASS TRANSITION TEMPERATURE, 184 199 215 218 GLOSS, 14 85 122 131 159 183 201 205 GLOVE, 32 GLYCEROL COPOLYMER, 160 GOGGLES, 25 GRAFT, 78 110 189 GRAFT COPOLYMER, 8 153 182 GRAFT COPOLYMERISATION,

114

78 GRAFT POLYMERISATION, 153 GRAFT YIELD, 78 GRAFTING, 78 110 189 GRANITE LIKE, 137 GRANULATION, 12 GRANULE, 148 188 GRAPHIC ART APPLICATION, 122 180 GRAVIMETRIC ANALYSIS, 3 24 54 78 91 GRAVURE COAT, 44 GREASE RESISTANCE, 72 GREEN STRENGTH, 152 GREENHOUSE, 76 148 GRIP, 72 GROUP IV A METAL COMPOUND, 4 41

H HARDNESS, 26 72 112 HARMONISATION, 19 84 HAZARDOUS MATERIAL, 144 HAZE, 21 26 97 131 164 HEADSPACE ANALYSIS, 37 HEADSPACE CHROMATOGRAPHY, 214 HEALTH HAZARD, 13 29 30 31 33 41 46 56 75 80 82 94 108 128 139 141 168 178 195 199 208 216 217 HEAT BUILD-UP, 119 HEAT CURING, 19 HEAT DEFLECTION TEMPERATURE, 92 93 HEAT DEGRADATION, 3 12 HEAT DISTORTION TEMPERATURE, 102 HEAT EXCHANGER, 32 HEAT INSULATION, 101 HEAT RESISTANCE, 12 47 48 65 76 102 120 129 137 156 164 182 187 188 HEAT SEAL, 34 HEAT SEALABILITY, 68 HEAT SEALABLE, 102 114 HEAT SEALING, 104 123 145 HEAT SENSITIVE, 20 HEAT STABILISER, 4 76 133 164 168 HEAT STABILITY, 85 92 93 107 119 HEAT TRANSFER, 26 88 HEAT TREATMENT, 100 HEAT WELDING, 175 HEATER BLANKET, 169 HEATING, 12 121 169

HEAVY METAL, 188 HELICAL CONFIGURATION, 160 HEPTANE, 94 HERMETIC SEAL, 149 HEXANE, 4 130 140 HEXENE, 26 HIGH DENSITY POLYETHYLENE, 7 9 26 31 35 40 49 50 61 65 74 91 96 99 104 129 179 187 188 189 HIGH MOLECULAR WEIGHT, 34 HIGH PERFORMANCE LIQUID CHROMATOGRAPHY, 11 108 118 138 173 217 HIGH TEMPERATURE, 22 HINDERED AMINE, 135 148 HINGE, 164 HISTORY, 13 168 HOMOPOLYMER, 38 102 168 HOPPER, 12 HORTICULTURAL APPLICATION, 183 HOSE, 32 HOT CURING, 19 HOT FILLING, 12 158 HOT MELT, 162 HOT MELT ADHESIVE, 34 163 HOUSEHOLD WASTE, 49 50 51 52 53 HOUSEWARES, 16 155 183 188 HOUSING, 25 HUE, 107 HUMIDITY, 79 HUMIDITY ABSORPTION, 92 HUMIDITY SENSOR, 177 HYALURONIC ACID, 166 HYDROGEN, 73 HYDROGEN ABSTRACTION, 27 HYDROGEN BOND, 79 HYDROGEN BONDING, 107 HYDROLYSIS, 200 HYDROLYSIS RESISTANCE, 22 HYDROPHILICITY, 140 198 HYDROPHOBICITY, 140 HYDROXYALKANOATE COPOLYMER, 48 HYDROXYBENZENE, 173 HYDROXYETHYL METHACRYLATE COPOLYMER, 15 HYDROXYVALERATE COPOLYMER, 48 HYGIENE, 26 121 203

I ICE CUBE MAKER, 19 IDENTIFICATION, 17 50 51 52 53

© Copyright 2007 Smithers Rapra Technology

Subject Index

96 173 183 IDENTIFICATION TAG, 136 IMAGING, 2 IMPACT MODIFIED, 92 IMPACT MODIFIER, 133 156 164 IMPACT PROPERTIES, 25 55 68 92 93 102 116 156 164 183 IMPACT RESISTANCE, 25 55 68 102 116 156 164 183 IMPACT STRENGTH, 92 93 IMPLANT, 2 88 IMPORTS, 26 63 104 176 IMPURITIES, 31 59 IN-MOULD COATING, 16 IN-MOULD DECORATING, 137 157 INDUSTRIAL APPLICATION, 189 INDUSTRIAL HAZARD, 75 INFRAED REFLECTION, 16 INFRARED SPECTRA, 40 54 78 79 126 153 INFRARED SPECTROSCOPY, 40 54 78 79 126 153 INITIATOR, 1 8 11 13 15 18 27 39 40 54 78 79 110 113 115 117 126 147 153 172 180 193 207 213 INJECTION MOULDABLE, 92 93 INJECTION MOULDING, 12 16 19 21 22 25 65 69 73 86 89 92 93 102 111 116 129 137 148 157 161 164 168 175 187 188 INJECTION MOULDING MACHINE, 73 INJECTION STRETCH BLOW MOULDING, 102 INK, 6 11 13 14 28 33 39 40 45 46 60 66 71 80 81 99 103 104 106 110 114 115 124 136 137 143 144 158 159 166 172 174 177 179 197 199 202 204 205 207 INK JET PRINTING, 177 INORGANIC PIGMENT, 85 INPUT-OUTPUT MODEL, 128 INSERT MOULD, 73 175 INSULATION, 101 INTELLIGENT MATERIAL, 28 29 113 136 161 179 INTENSIVE MIXING, 69 INTERFACIAL ADHESION, 44 INTERLAMINAR, 100 INTERMOLECULAR BONDING, 107 INTERNAL LUBRICANT, 65 133 INTERNAL MOULD RELEASE, 16 65 INTERNAL STANDARD, 130

INTRINSIC VISCOSITY, 54 INVERSE CHROMATOGRAPHY, 82 INVISIBLE MARKING, 143 ION EXCHANGE RESIN, 28 90 109 IRRADIATION, 146 148 IRRADIATION CURING, 201 205 216 ISOCYANATE, 34 35 42 ISOCYANATE CONTENT, 110 ISOCYANATE POLYMER, 55 ISOOCTANE, 118 146 ISOPROPYLTHIOXANTHONE, 11 39 ISOTHERM, 79

K KAOLIN, 128 KETONE, 13 KETTLE, 59 KINETICS, 9 79 198 209 210 215 217 KITCHENWARE, 19 KNIFE, 12

L LABEL, 39 71 99 161 167 LABELLING, 34 39 82 183 LABORATORY APPARATUS, 45 LACQUER, 143 159 209 LACTIC ACID, 12 LAMINATED, 35 59 149 LAMINATED FILM, 104 124 147 152 172 LAMINATING, 49 96 100 121 184 LAMINATION, 12 34 35 39 47 57 105 147 159 186 202 LANDFILL, 128 168 LANGEVIN EQUATION, 110 191 198 LANGMUIR SORPTION, 79 LASER, 58 183 LASER ETCHING, 58 LASER INDUCED BREAKDOWN SPECTROSCOPY, 2 8 LASER IRRADIATION, 77 LASER MARKING, 3 58 LAUNDRY, 71 98 LAUROLACTAM POLYMER, 3 LEAKAGE, 195 LEGISLATION, 29 31 32 34 39 49 73 81 82 84 95 105 107 125 128 133 134 171 196 208 212 LEISURE APPLICATION, 183

© Copyright 2007 Smithers Rapra Technology

LETDOWN RATIO, 137 LIDS, 39 69 149 LIFE CYCLE ANALYSIS, 96 128 LIGHT ABSORPTION, 3 161 LIGHT AGEING, 127 LIGHT DEGRADATION, 25 70 86 107 127 175 182 LIGHT EXPOSURE, 131 LIGHT FASTNESS, 86 107 127 LIGHT INTENSITY, 70 LIGHT RESISTANCE, 182 LIGHT SOURCE, 85 LIGHT STABILISER, 76 134 135 148 168 LIGHT STABILITY, 182 LIGHT TRANSMISSION, 12 70 LIMESTONE, 26 LIMONENE, 48 91 LINE SPEED, 44 116 152 159 180 LINEAR LOW-DENSITY POLYETHYLENE, 26 64 68 69 91 104 129 176 179 184 185 189 190 LINER, 26 73 189 LIQUID ADDITIVE, 22 LIQUID CHROMATOGRAPHY, 11 17 84 90 94 108 118 130 138 146 173 174 197 209 217 LIQUID CRYSTAL POLYMER, 185 LIQUID POLYMER, 123 LIQUID RUBBER, 19 LOW-DENSITY POLYETHYLENE, 10 12 31 35 49 61 91 104 161 176 179 184 192 LOW MOLECULAR WEIGHT, 32 34 108 LOW TEMPERATURE PROPERTIES, 102 155 LOW VISCOSITY, 122 LOW VOLTAGE, 202 LUBRICANT, 63 65 88 95 133 168 LUBRICATION, 164 LUMINESCENCE, 20 143 177

M MACHINERY, 12 26 32 73 121 152 202 MACROPOROUS, 90 MALEIC ANHYDRIDE, 63 MALEIC ANHYDRIDE COPOLYMER, 54 117 182 MANUAL SORTING, 7 MANUFACTURER, 26 31 73 144 165 187 MANUFACTURING, 128 148 164

115

Subject Index

MARBLE, 26 MARINE APPLICATION, 122 MARK-HOUWINK CONSTANT, 88 MARKET ANALYSIS, 6 73 102 MARKET GROWTH, 26 43 73 MARKET RESEARCH, 73 MARKET SHARE, 22 23 61 64 66 71 103 104 105 120 133 136 166 176 180 MARKET SIZE, 6 68 102 168 MARKET SURVEY, 73 MARKET TREND, 68 102 MASS SELECTIVE DETECTOR, 197 MASS SPECTRA, 37 90 94 108 142 173 174 207 MASS SPECTROSCOPY, 4 17 29 35 37 39 59 62 84 90 94 108 130 138 142 173 174 193 197 207 MASS TRANSFER, 31 MASS TRANSPORT, 18 MASTERBATCH, 16 61 67 73 85 144 161 169 MATERIAL REPLACEMENT, 12 61 68 90 102 116 183 194 199 MATERIALS SELECTION, 42 47 85 107 110 MATERIALS SUBSTITUTION, 12 61 68 90 102 116 183 194 199 MATHEMATICAL MODEL, 18 29 33 113 191 MATT FINISH, 85 137 MEAT, 84 MEAT PACKAGING, 32 70 MEDICAL APPLICATION, 6 16 21 25 27 41 44 54 75 109 122 133 168 169 183 199 MEDICAL EQUIPMENT, 25 MEDIUM-DENSITY POLYETHYLENE, 68 129 MELT BLOWN, 170 MELT FLOW, 65 MELT FLOW INDEX, 68 MELT FLOW RATE, 102 170 MELT INDEX, 68 MELT VISCOSITY INDEX, 68 MELTING, 26 48 56 72 164 MELTING POINT, 12 92 93 MELTING TEMPERATURE, 38 92 93 MELTS, 26 56 72 164 MEMBRANE, 24 112 140 168 MERCAPTIDE, 164 METAL, 100 164 183 206 METAL ADHESION, 110 122 METALLISED, 35 101 114

116

METALLISED FILM, 44 70 104 172 METALLOCENE, 21 43 68 91 104 112 123 145 156 170 176 METAMERISM, 74 85 METHACRYLATE COPOLYMER, 15 METHACRYLIC ACID POLYMER, 5 METHACRYLIC ESTER COPOLYMER, 15 METHANOL, 90 METHYL ALCOHOL, 90 METHYL CHLOROFORM, 9 METHYL METHACRYLATE POLYMER, 175 METHYLBENZENE, 9 10 39 MICA, 44 MICHAEL REACTION, 1 MICROBEAD, 137 MICROEXTRACTION, 5 MICROGRANULE, 188 MICROHARDNESS, 112 MICROMETER, 198 MICROORGANISM, 203 MICROPARTICLE, 56 MICROSCOPY, 29 36 117 MICROSPHERE, 188 MICROSTRUCTURE, 9 68 MICROWAVE, 82 206 MICROWAVEABLE, 161 MIGRATION RESISTANCE, 76 107 108 MILK, 139 148 MILK BOTTLE, 135 MINERAL, 26 183 MINERAL FILLED, 92 93 MINERAL WATER, 108 MINERALISATION, 206 MIXING, 12 32 69 73 MODIFIED ATMOSPHERE, 35 113 177 MODIFIER, 12 123 145 168 199 218 MODULATED DIFFERENTIAL SCANNING CALORIMETRY, 181 MODULUS, 38 184 MOISTURE ABSORPTION, 72 92 177 MOISTURE BARRIER, 184 MOISTURE RESISTANCE, 12 60 72 79 183 MOISTURE SENSITIVE, 71 171 MOLECULAR BONDING, 110 MOLECULAR CHAIN, 12 MOLECULAR CONFIGURATION, 38

MOLECULAR CONFORMATION, 38 MOLECULAR IMPRINTING, 5 83 MOLECULAR MASS, 13 18 26 32 34 88 106 107 108 110 129 140 142 168 181 MOLECULAR MOBILITY, 15 18 MOLECULAR MODELLING, 83 MOLECULAR SIZE, 110 MOLECULAR STRUCTURE, 8 12 13 15 24 26 38 54 56 68 106 182 MOLECULAR WEIGHT, 13 18 26 32 34 68 69 88 106 107 108 110 129 140 142 168 170 181 208 MOLECULAR WEIGHT DISTRIBUTION, 68 69 129 170 MONOLAYER, 73 144 181 MONOMER, 12 25 29 30 31 32 39 84 195 200 212 MONOMER RATIO, 147 MONTMORILLONITE, 36 MORPHOLOGICAL PROPERTIES, 5 68 153 218 MORPHOLOGY, 5 68 153 218 MOULD, 164 MOULD FILLING, 69 111 MOULD FLOW, 102 MOULD RELEASE, 164 MOULD RELEASE AGENT, 65 133 MOULD SHRINKAGE, 92 93 MOULD TEMPERATURE, 21 92 93 MOULDING, 12 16 19 21 22 25 56 65 67 69 73 86 89 92 93 102 111 116 122 129 137 148 168 185 MOULDING COMPOUND, 65 125 MULTILAYER, 33 34 35 39 73 144 150 183 184 MULTILAYER FILM, 64 99 113 129 MULTIMODAL, 102

N NANOCLAY, 136 NANOCOMPOSITE, 36 48 61 73 122 133 136 158 160 NANOCRYSTALLINE, 156 NANOFIBRE, 136 NANOFILLER, 48 61 102 133 136 158 171 NANOPARTICLE, 71 73 160

© Copyright 2007 Smithers Rapra Technology

Subject Index

NANOSTRUCTURE, 123 158 NANOTECHNOLOGY, 81 136 158 NANOTUBE, 136 158 NAPPY, 41 NATURAL FIBRE, 166 NATURAL FIBRE-REINFORCED PLASTIC, 16 133 NATURAL POLYMER, 12 NATURAL RUBBER, 16 32 84 NEAR-INFRARED SPECTROSCOPY, 15 NEOPRENE, 32 84 NETTING, 32 NEUTRALISING AGENT, 22 NICKEL COMPOUND, 141 NILE RED, 2 NIPPLE, 32 108 NITRIC ACID, 8 NITRILE RUBBER, 32 84 142 NITROCELLULOSE, 204 NITROSAMINE, 32 84 179 NITROSOAMINE, 32 84 179 NON-DESTRUCTIVE TESTING, 143 NON-HYGROSCOPIC, 122 NON-SLIP, 72 NON-STAINING, 87 NON-STICK, 19 164 NON-WOVEN, 12 170 NON-YELLOWING, 80 NORRISH-TYPE MECHANISM, 110 NOTCHED IMPACT STRENGTH, 92 93 NUCLEAR MAGNETIC RESONANCE SPECTRA, 54 83 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY, 54 83 193 206 NUCLEATING AGENT, 16 61 NUCLEATION, 102 NUMERICAL ANALYSIS, 29 NURSERY APPLICATION, 19 NYLON, 3 16 35 45 59 64 66 73 82 103 104 144 158 171 188 198 NYLON-11, 3 NYLON-12, 3 NYLON-12T, 3 NYLON-4,6, 3 NYLON-6, 25 36 130 136 NYLON-6,6, 25 92 93

O OCTANE, 9 OCTENE, 26 69 OCTYLTIN COMPOUND, 4

ODOUR, 10 67 76 115 124 129 183 190 197 202 216 ODOURLESS, 55 OFFICE EQUIPMENT, 164 OFFSET PRINTING, 110 OIL RESISTANCE, 72 120 OILS, 25 OLEFIN POLYMER, 3 9 16 22 43 59 60 76 86 89 102 112 135 148 156 183 187 188 196 OLIGOACRYLATE, 1 OLIGOMER, 30 31 32 108 191 OLIVE OIL, 108 OPACITY, 107 167 OPTICAL APPLICATION, 156 OPTICAL DENSITY, 45 OPTICAL MICROSCOPY, 29 36 OPTICAL PROPERTIES, 2 11 12 21 25 68 69 70 76 97 102 107 127 129 131 149 156 160 164 165 173 183 209 ORGANIC PIGMENT, 85 ORGANOLEPTIC PROPERTIES, 19 29 31 32 33 111 190 ORGANOPOLYSILOXANE, 14 29 88 ORGANOSILICON POLYMER, 14 28 29 88 202 ORGANOSILICONE POLYMER, 14 28 29 88 202 ORGANOSILOXANE POLYMER, 14 28 29 88 202 ORGANOTIN COMPOUND, 41 OVERMOULDING, 73 175 OXIDATION, 31 70 108 171 209 OXIDATIVE DEGRADATION, 31 108 171 209 OXIDISATION, 31 108 171 OXYGEN, 24 44 47 60 73 79 149 OXYGEN BARRIER, 44 OXYGEN PERMEABILITY, 24 38 48 161 OXYGEN SCAVENGER, 70 73 113 133 161 167 171 177 190 OXYGEN SENSOR, 158 177

P PACKAGING ADHESIVE, 42 186 PACKAGING APPLICATION, 12 25 26 46 47 56 73 101 144 145 148 149 157 164 165 183 189 PACKAGING CONTAINER, 11 35 40 69 82 102 194 202 PACKAGING FILM, 10 11 42 43 44 45 47 48 60 61 64 66 71 79 86 98 99 103 104 114 135 151 159 161 171 202

© Copyright 2007 Smithers Rapra Technology

PACKAGING WASTE, 49 50 51 52 53 PAD PRINTING, 3 PAINTING, 102 122 PAINTS, 40 131 162 163 PALLET, 43 PALMITIC ACID, 214 PAN, 82 PAPAIN, 160 PAPER, 35 46 94 104 124 183 192 PAPER COATING, 176 196 198 PAPER STRENGTH AGENT, 160 PAPERBOARD, 94 PARTICLE, 56 PARTICLE SIZE, 62 107 131 136 137 168 169 185 PARTICLE SIZE DISTRIBUTION, 107 PARTITION COEFFICIENT, 82 190 PARTITIONING, 18 181 PASSENGER TIRE, 74 PASSENGER TYRE, 74 PASTE, 168 PASTEURISATION, 73 PATENT, 205 PEARLESCENCE, 137 PECTIN, 160 PEEL STRENGTH, 27 147 PELLET, 12 22 73 92 93 PELLETISATION, 26 PERMEABILITY, 12 19 24 38 40 44 47 48 60 79 112 113 150 167 190 193 PERMEABILITY COEFFICIENT, 40 PERMEATION, 140 PEROXIDE, 32 PERSONAL CARE PRODUCT, 99 PESTICIDE, 41 63 PETROCHEMICAL, 12 PETROLEUM, 12 PHARMACEUTICAL APPLICATION, 75 103 109 164 PHASE CHANGE, 161 PHENOL, 173 PHENOLIC ANTIOXIDANT, 187 PHENOLIC COMPOUND, 187 PHOSPHITE, 187 PHOTOCHEMICAL DEGRADATION, 127 PHOTOCHEMICAL STABILITY, 127 PHOTODECOMPOSITION, 127 PHOTOINITIATOR, 1 11 13 15 18 27 39 110 113 115 147 172 180 193 207 213

117

Subject Index

PHOTOLABILE, 1 PHOTOLYSIS, 115 213 PHOTOOXIDATION, 70 PHOTOPOLYMERISATION, 15 PHOTOREACTIVE POLYMER, 180 PHOTOSENSITIVE, 171 PHTHALATE, 17 39 61 80 188 PHTHALATE ESTER, 199 PHTHALOCYANINE, 127 188 PHTHALOCYANINE GREEN, 132 PHYSICAL PROPERTIES, 12 14 31 60 69 92 93 106 PIGMENT, 2 3 6 8 12 16 26 49 50 51 52 53 61 65 67 70 71 74 85 86 87 89 95 96 97 98 107 119 122 127 128 132 133 134 135 137 141 148 150 157 168 182 185 188 216 PIGMENTED, 131 PIPE, 4 19 22 32 76 102 125 164 182 189 PLANT CONSTRUCTION, 22 26 61 63 76 122 156 176 178 PLASMA TREATMENT, 172 PLASTICISATION, 36 181 PLASTICISER, 32 39 61 80 84 117 133 168 178 195 199 204 PLASTICS WASTE, 181 PLASTISOL, 168 PLASTOMER, 184 PLUG ASSIST, 122 POLLUTANT, 181 POLLUTION, 7 195 POLY-EPSILONCAPROLACTAM, 25 36 130 136 POLYACETAL, 3 POLYACRYLATE, 202 POLYACRYLONITRILE, 82 POLYALKENE, 3 9 16 22 43 59 60 76 86 89 102 112 135 148 156 183 187 188 196 POLYALPHA-OLEFIN, 156 POLYAMIDE, 3 16 35 45 59 64 66 73 82 103 104 144 158 171 188 198 POLYAMIDE-11, 3 POLYAMIDE-12, 3 POLYAMIDE-12T, 3 POLYAMIDE-4,6, 3 POLYAMIDE-6, 25 36 130 136 POLYAMIDE-6,6, 92 93 POLYAMINE, 217 POLYAMINOPOLYAMIDE, 160 POLYANILINE, 160 POLYAROMATIC

118

HYDROCARBON, 84 POLYBENZOPHENONE, 193 POLYBUTYLENE TEREPHTHALATE, 3 122 175 POLYCAPROAMIDE, 25 36 130 136 POLYCAPROLACTAM, 25 36 130 136 POLYCAPROLACTONE, 2 48 POLYCARBONATE, 3 16 25 35 139 175 183 190 194 POLYCHLOROPRENE, 32 84 POLYCONDENSATION, 150 POLYDIMETHYL SILOXANE, 14 29 88 201 POLYDIMETHYLSILOXANE, 14 29 88 201 POLYEPICHLOROHYDRIN, 160 POLYEPOXIDE, 34 173 179 194 200 209 210 211 216 POLYEPOXY ACRYLATE, 110 POLYESTER POLYOL, 35 POLYESTER RESIN, 214 POLYETHER POLYOL, 35 POLYETHER SULFONE, 17 140 POLYETHYLENE, 7 9 10 12 16 26 31 35 40 43 49 50 51 52 53 61 64 65 68 69 74 91 95 96 99 103 104 111 113 114 129 133 143 144 161 172 176 179 184 185 187 188 189 190 192 198 POLYETHYLENE GLYCOL DIMETHACRYLATE, 5 POLYETHYLENE IMINE, 54 POLYETHYLENE NAPHTHALATE, 73 190 POLYETHYLENE TEREPHTHALATE, 7 12 16 22 23 31 35 44 48 49 50 62 64 66 70 73 76 82 96 100 101 103 104 114 118 137 144 146 149 150 161 172 181 190 POLYETHYLENEIMINE, 54 POLYETHYLENIMINE, 54 POLYFLUOROETHYLENE, 17 POLYGLYCOLIC ACID, 12 POLYHYDROXYALKANOATE, 81 116 166 POLYHYDROXYBUTYRATE, 12 POLYISOCYANATE, 55 POLYLACTIC ACID, 12 16 48 56 81 99 116 117 124 166 POLYLAUROLACTAM, 3 POLYLAURYLLACTAM, 3 POLYMER BEAD, 77 POLYMER CEMENT, 55 POLYMERIC CATALYST, 109 POLYMERIC MODIFIER, 199

POLYMERIC PHOTOINITIATOR, 13 POLYMERIC PLASTICISER, 204 POLYMERIC RELEASE AGENT, 65 133 POLYMERIC SURFACE ACTIVE AGENT, 106 POLYMERIC SURFACTANT, 106 POLYMERISATION, 5 15 22 54 68 75 102 110 129 150 160 179 POLYMERISATION CATALYSTS, 32 43 68 91 102 POLYMERISATION INITIATOR, 153 POLYMERISATION KINETICS 216 POLYMERISATION MECHANISM, 153 POLYMERISATION RATE, 21 POLYMERISATION TIME, 5 POLYMETHACRYLIC ACID, 5 POLYMETHYL METHACRYLATE, 175 POLYMETHYLMETHACRYLATE, 175 POLYOL, 34 35 42 55 POLYOLEFIN, 3 9 16 22 43 59 60 76 86 89 102 112 135 148 156 183 187 188 196 POLYOLEFIN ELASTOMER, 3 156 POLYORGANOSILOXANE, 14 28 29 88 201 202 POLYPHENYLENE SULFIDE, 3 POLYPROPENE, 16 21 22 31 35 38 39 40 53 60 61 64 65 66 70 74 76 96 97 99 102 103 104 110 114 123 129 133 144 145 156 159 170 172 175 179 182 184 187 190 POLYPROPYLENE, 16 21 22 31 35 38 39 40 53 60 61 64 65 66 70 74 76 96 97 99 102 103 104 110 114 123 129 133 144 145 156 159 170 172 175 179 182 184 187 190 POLYSACCHARIDE, 2 78 160 POLYSILICONE, 14 28 29 88 202 POLYSILOXANE, 14 28 29 88 201 202 POLYSTYRENE, 3 16 25 31 52 66 82 90 96 144 164 165 175 179 188 POLYSULFONE, 140 POLYTETRAFLUOROETHYLENE, 17 POLYTETRAMETHYLENE ADIPAMIDE, 3 POLYTRIMETHYLENE NAPHTHALATE, 73

© Copyright 2007 Smithers Rapra Technology

Subject Index

POLYTRIMETHYLENE TEREPHTHALATE, 12 POLYURETHANE, 3 16 34 35 42 66 76 105 110 131 133 143 151 169 172 175 186 202 POLYVINYL ACETATE, 66 149 POLYVINYL ALCOHOL, 12 24 71 98 POLYVINYL CHLORIDE, 3 4 31 41 51 61 66 74 75 76 82 96 102 104 116 126 133 144 164 168 179 182 184 187 188 199 POLYVINYL CYANIDE, 82 POLYVINYL HALIDE, 3 31 51 116 126 133 144 POLYVINYLBENZENE, 3 31 52 144 179 POLYVINYLCHLORIDE, 3 4 31 41 51 61 66 74 75 76 82 96 102 104 116 126 133 144 164 168 179 182 184 187 188 199 POLYVINYLIDENE CHLORIDE, 35 42 66 104 149 184 POST CURING, 15 POTABLE WATER, 19 23 109 210 POTATO, 12 POUCH, 31 64 103 114 120 184 POWDER, 85 157 POWDER COATING, 122 131 180 PRE-GELLING, 110 PRE-TREATMENT, 140 PREFORM, 73 PRESSURE, 24 26 121 PRESSURE SENSITIVE TAPE, 99 PRESSURE-SENSITIVE ADHESIVE, 27 34 57 147 196 202 PRETREATMENT, 140 216 PRIMER, 44 80 172 PRINCIPAL COMPONENTS ANALYSIS, 10 PRINTED CIRCUIT, 136 PRINTED WIRING BOARD, 136 PRINTING, 3 14 18 26 33 60 99 103 110 159 177 186 PRINTING INK, 14 28 33 39 46 80 106 110 115 136 172 205 207 PROBE, 91 PROBLEM PREVENTION, 201 PROCESS, 9 13 19 27 28 32 38 42 43 44 45 47 56 60 73 91 92 93 101 107 125 157 164 168 182 187 188 189 PROCESS CAPABILITY, 58 PROCESS CONTROL, 75 202 PROCESSIBILITY, 47 68 69 76 86 102 119 127 148 175 189 PROCESSING, 9 13 19 27 28 32

38 42 43 44 45 47 56 60 73 91 92 93 101 107 125 157 164 168 182 187 188 189 PROCESSING AID, 16 22 29 30 31 32 65 164 196 PROCESSING CONDITIONS, 92 93 182 PRODUCT DEVELOPMENT, 20 64 122 124 166 173 177 180 PRODUCTION, 12 144 164 168 PRODUCTION CAPACITY, 7 22 23 26 61 63 66 76 81 99 102 103 104 114 122 123 150 156 166 176 178 184 PRODUCTION COST, 85 99 150 PRODUCTIVITY, 26 152 180 197 PROFILE, 164 PROPANEDIAMINE, 215 PROPANEDIOL, 12 PROPAZINE, 5 PROPENE, 145 PROPENE COPOLYMER, 182 PROPENE POLYMER, 31 35 39 53 96 110 114 123 129 133 144 145 156 PROPERTY MODIFIER, 168 PROPYLENE, 145 PROPYLENE COPOLYMER, 182 PROPYLENE GLYCOL, 178 PROPYLENE POLYMER, 31 35 39 53 96 110 114 123 129 133 144 145 156 PROPYLENE THIOUREA, 138 PROPYLENE-ETHYLENE COPOLYMER, 38 PROTEASE, 160 PROTECTIVE FILM, 156 PROTECTIVE PACKAGING, 31 PROTEIN, 160 PROTEIN ADSORPTION, 2 PROTON MAGNETIC RESONANCE, 206 PROTOTYPE, 20 PUNCTURE RESISTANCE, 26 72 102 129 PURGING, 26 PURIFICATION, 6 109 PURITY, 7 23 29 46 157 PYROLYSIS, 6 PYROMELLITIC GLYCEROL DIMETHACRYLATE COPOLYMER, 15

Q QUALITY ASSURANCE, 6 28 144 151 QUALITY CONTROL, 6 26 28

© Copyright 2007 Smithers Rapra Technology

144 151 206 QUANTITATIVE ANALYSIS, 17 95 173 QUENCHING, 100

R RADIATION CURING, 105 197 RADICAL POLYMERISATION, 54 160 RADICAL SCAVENGER, 135 RANDOM COPOLYMER, 102 RATE CONSTANT, 210 215 RATE OF POLYMERISATION, 21 RAW MATERIAL, 28 29 63 128 178 197 REACTION CONDITIONS, 78 REACTION INJECTION MOULDING, 16 REACTION MECHANISM, 54 110 REACTION MOULDING, 16 REACTION PRODUCT, 37 191 REACTIVE ADHESIVE, 34 162 163 REACTIVE POLYMER, 180 REACTIVITY, 5 147 216 REACTOR, 68 RECORDING MEDIA, 114 RECOVERY, 6 7 9 96 RECYCLATE, 16 62 73 181 RECYCLED, 16 62 73 181 RECYCLED CONTENT, 150 RECYCLING, 6 7 9 16 39 49 50 51 52 53 62 73 82 94 96 119 133 150 168 179 181 212 RECYCLING RATE, 7 REDOX INITIATOR, 8 REFLECTIVITY, 137 REFRACTIVE INDEX, 38 88 107 REFRIGERATOR, 155 REFUSE BAG, 26 REGENERATED CELLULOSE, 28 179 REGIOSELECTIVITY, 160 REGRANULATION, 12 REGRIND, 12 REINFORCED PLASTICS, 16 36 67 93 122 125 133 183 195 RELATIVE HUMIDITY, 79 RELEASE AGENT, 65 133 RELEASE COATING, 202 RELEASE FILM, 71 RELEASE LINER, 169 RENEWABLE RESOURCE, 7 12 81 96 120 128 166 182 RESEARCH, 32 37 56 84 120 158 RESIDENCE TIME, 12

119

Subject Index

RESIDUAL ADDITIVE, 29 RESIDUAL MONOMER, 75 110 130 139 191 216 217 RESIDUAL SOLVENT, 10 66 151 152 RESIDUAL STYRENE, 125 RESIN, 1 12 25 26 72 73 74 144 145 183 189 RESPONSE CHARACTERISTICS, 161 RETORT POUCH, 100 129 RETORT RESISTANCE, 48 REVIEW, 6 28 29 31 32 35 39 58 84 109 115 168 179 186 212 216 RHEOLOGICAL PROPERTIES, 18 26 44 54 78 92 93 111 147 164 192 198 RHEOLOGY, 44 92 93 111 147 164 RIGIDITY, 12 69 102 164 188 RING-OPENING POLYMERISATION, 160 RISK ASSESSMENT, 13 29 30 41 141 179 RISK MANAGEMENT, 30 ROLL COATING, 44 ROSIN, 94 ROTATIONAL MOULDING, 111 122 129 ROTOMOLDING, 111 122 129 ROTOMOULDING, 111 122 129 RUBBER, 3 6 16 19 28 32 34 37 42 57 67 72 84 85 108 121 123 137 138 142 145 148 156 175 179 194 195 200 201 203 212 213 218 RUBBER-MODIFIED, 218 RUTILE, 141

S SACCHARIDE COPOLYMER, 8 153 SAFETY, 13 30 31 32 33 34 35 75 82 84 90 121 128 157 161 179 196 205 206 208 SAFETY GOGGLES, 25 SAGGING, 12 SANITARY APPLICATION, 71 SATURATED POLYESTER, 12 16 20 27 44 48 101 118 149 166 175 183 SCAFFOLD POLYMER, 160 SCANNING ELECTRON MICROGRAPH, 36 78 112 117 153 SCANNING ELECTRON MICROSCOPY, 15 36 68 78

120

112 117 153 SCRAP, 6 96 SCRAP POLYMER, 7 12 SCRAP REDUCTION, 137 SCRAP TYRES, 6 SCRATCH RESISTANCE, 65 102 156 159 201 SCREENING FACTOR, 29 SCUFF RESISTANCE, 65 159 SEAL, 32 39 81 96 149 SEALANT, 149 SEALING, 26 129 156 SECANT MODULUS, 93 SELF-ADHESIVE, 27 34 SELF-COOLING, 167 SELF-DRYING, 12 33 80 92 93 SELF-HEALING, 20 SEMI-SOLID, 88 SENSOR, 10 158 167 177 SERVICE LIFE, 85 SERVICE TEMPERATURE, 86 SHEAR MODULUS, 218 SHEAR PROPERTIES, 27 SHEAR STRENGTH, 27 SHEET, 12 124 164 165 169 183 SHEET MOULDING COMPOUND, 125 SHEETING, 125 SHELF LIFE, 35 70 73 81 82 98 113 149 150 158 161 171 177 190 SHIPMENT, 104 SHORE HARDNESS, 72 SHORT CHAIN BRANCHING, 68 SHRINK, 176 SHRINK FILM, 66 159 189 SHRINK HOOD, 43 SHRINKAGE, 12 68 92 93 102 107 110 111 SIDE CHAIN, 15 SIDING, 164 SILANE, 189 SILICA, 5 26 160 SILICON COPOLYMER, 14 106 SILICON DIOXIDE, 5 26 160 SILICON ELASTOMER, 19 32 84 108 SILICON POLYMER, 14 28 29 88 202 SILICON RUBBER, 19 32 84 108 SILICON-CONTAINING COPOLYMER, 14 106 SILICON-CONTAINING POLYMER, 14 28 29 88 202 SILICONE, 201 SILICONE COPOLYMER, 14 106 SILICONE ELASTOMER, 19 32 84 108

SILICONE POLYMER, 14 28 29 88 201 202 SILICONE RUBBER, 19 32 84 108 SILOXANE COPOLYMER, 14 106 SILOXANE ELASTOMER, 19 SILOXANE OLIGOMER, 108 SILOXANE POLYMER, 201 SILOXANE RUBBER, 19 SILVER, 101 155 157 SILVER ION, 131 SINGLE SITE CATALYSIS, 69 111 189 SIZE EXCLUSION CHROMATOGRAPHY, 214 SKID RESISTANCE, 72 SLIP AGENT, 133 SLIP PROPERTIES, 201 SMALL ANGLE X-RAY SCATTERING, 68 112 SMART MATERIAL, 160 SODIUM CARBONATE, 128 138 SODIUM SULFATE, 138 SODIUM TETRAETHYLBORATE, 4 SOFT DRINK BOTTLE, 73 189 SOFT-TOUCH, 72 137 SOFTENING POINT, 204 SOFTWARE, 74 95 144 SOIL REMEDIATION, 6 SOLID PHASE, 5 SOLID STATE, 38 68 150 SOLIDIFICATION, 56 SOLIDS CONTENT, 57 180 192 198 SOLUBILITY, 12 71 78 98 107 153 160 181 188 SOLUTION CASTING, 71 SOLVENT, 4 5 9 10 25 33 39 59 66 72 83 88 94 118 120 130 138 139 140 146 149 151 152 173 178 181 195 215 SOLVENT EMISSION, 152 SOLVENT EVAPORATION, 24 138 SOLVENT EXTRACTION, 17 37 62 82 90 130 191 214 217 SOLVENT PERMEABILITY, 40 SOLVENT RECOVERY, 7 152 SOLVENT RELEASE, 169 SOLVENT RESISTANCE, 48 SOLVENT RETENTION, 204 SOLVENT WASHING, 7 SOLVENT-BASED, 34 42 66 100 162 163 SOLVENT-BASED ADHESIVE, 186 SOLVENT-BORNE, 27 SOLVENT-FREE, 149 186 187

© Copyright 2007 Smithers Rapra Technology

Subject Index

SOLVENTLESS, 35 55 100 121 151 159 172 SOYABEAN OIL, 39 SOYBEAN OIL, 39 SPECIAL EFFECTS, 16 137 175 SPECIFIC GRAVITY, 26 SPECTACLES, 25 SPECTROPHOTOMETER, 74 85 131 SPECTROSCOPY, 2 8 24 37 40 54 78 79 90 94 95 108 126 142 153 173 174 182 206 207 SPORTS SHOE, 175 SPORTS STADIUM, 73 SPORTS SURFACE, 169 SPORTS UTILITY VEHICLE, 183 SPRAY DRYING, 12 33 80 92 93 STABILISER, 4 16 22 31 37 39 41 61 67 70 76 95 118 126 133 146 164 168 187 195 STABILITY, 26 47 48 65 76 102 120 129 137 156 164 182 187 188 STAMPING, 101 STANDARD, 19 31 33 92 93 95 130 164 212 STARCH, 2 56 116 117 160 166 STARCH POLYMER, 81 STATIC DISSIPATION, 183 STEARIC ACID, 214 STEEL FIBRE 22 STEERING WHEEL, 169 STERILISABILITY, 102 STERILISATION, 155 STIFFNESS, 21 38 68 69 102 111 122 129 184 STORAGE, 14 145 209 STORAGE CONTAINER, 32 STORAGE STABILITY, 209 STORAGE TIME, 190 STRAIN, 92 93 STRENGTH, 98 121 127 129 188 STRESS-STRAIN PROPERTIES, 38 93 STRETCH, 12 STRETCH BLOW MOULDING, 12 73 STRETCH FILM, 43 68 176 189 STRETCH HOOD, 43 STRUCTURE-ACTIVITY RELATIONSHIP, 30 STRUCTURE-PROPERTY RELATIONSHIP, 38 STYRENE, 125 214 STYRENE DIVINYLBENZENE COPOLYMER, 90 STYRENE POLYMER, 3 31 52 82 96 144 179

STYRENE-BUTADIENE COPOLYMER, 164 STYRENE-DIVINYL BENZENE COPOLYMER, 90 STYRENE-DIVINYLBENZENE COPOLYMER, 90 SUGAR, 166 SULFONE POLYMER, 140 SULFUR, 128 SUNFLOWER OIL, 126 SUNGLASSES, 25 SURFACE ACTIVE AGENT, 39 106 SURFACE AREA, 34 90 SURFACE COATING, 32 84 179 SURFACE FINISH, 16 85 116 137 201 SURFACE MODIFICATION, 32 168 SURFACE PROPERTIES, 65 SURFACE TENSION, 40 99 110 140 SURFACE TREATMENT, 26 32 40 44 60 99 110 168 172 SURFACTANT, 39 106 SURGICAL APPLICATION, 6 SURGICAL GOWN, 6 SUSPENSION POLYMERISATION, 75 SUSTAINABILITY, 81 128 166 SYNTHETIC FIBRE, 107 SYNTHETIC RUBBER, 121 123 137 138 142 145 148 156 SYRINGE, 184

T T-PEEL, 147 TABLEWARE, 116 166 185 TACK, 27 TAINT, 115 TAPE, 27 148 TARGET, 5 25 73 74 101 164 TASTE, 70 TATTOO, 77 TEAR RESISTANCE, 26 68 69 72 TEAR STRENGTH, 26 68 69 72 TEAT, 32 108 TEMPERATURE CONTROL, 169 TEMPERATURE DEPENDENCE, 9 60 92 93 TEMPERATURE RESISTANCE, 19 TEMPERATURE SENSITIVITY, 161 TENSILE MODULUS, 12 92 93 TENSILE PROPERTIES, 12 26 60 92 93 117 149

© Copyright 2007 Smithers Rapra Technology

TENSILE STRENGTH, 12 26 60 92 93 TENSILE YIELD, 26 TEREPHTHALIC ACID, 12 TERMONOMER, 25 29 30 31 32 TEST EQUIPMENT, 32 88 95 108 146 197 TEST METHOD, 18 29 30 31 32 33 34 35 38 39 40 65 69 73 82 83 84 88 92 93 95 108 125 131 143 144 146 168 179 181 191 195 197 200 202 211 212 TESTING, 18 29 30 31 32 33 34 35 38 39 40 65 69 73 82 83 84 88 92 93 95 108 125 131 143 144 146 168 179 181 191 195 197 200 202 211 212 217 TETRAETHOXYSILANE, 24 TETRAFLUOROETHYLENE POLYMER, 17 TEXTILE, 162 TEXTILE APPLICATION, 8 THERMAL ANALYSIS, 78 112 117 153 THERMAL DEGRADATION, 3 12 214 THERMAL GRAVIMETRIC ANALYSIS, 3 24 54 78 91 THERMAL HISTORY, 97 THERMAL INSULATION, 101 THERMAL MECHANICAL ANALYSIS, 181 THERMAL PROPERTIES, 72 92 93 THERMAL RESISTANCE, 12 74 127 149 188 THERMAL STABILITY, 47 48 65 76 102 120 129 137 156 164 182 187 188 THERMODYNAMIC PROPERTIES, 60 THERMOFORMING, 12 16 116 122 137 149 164 168 184 THERMOGRAVIMETRIC ANALYSIS, 3 24 54 78 91 THERMOMECHANICAL ANALYSIS, 181 THERMOPLASTIC ELASTOMER, 32 72 76 84 123 164 175 THERMOPLASTIC RUBBER, 32 72 76 84 123 164 175 THIN FILM, 45 158 190 THIOESTER, 187 THIOUREA, 138 THIOXANTHONE, 13 THRESHOLD LIMIT VALUE, 30 THRESHOLD VALUE, 30 196

121

Subject Index

TIE LAYER, 34 35 TIE MOLECULE, 38 TIME-TEMPERATURE INDICATOR, 167 177 TIN, 164 TIN COMPOUND, 4 41 TIN OXIDE, 3 TIN PLATE, 173 TISSUE ENGINEERING, 2 TITANATE FIBRE, 22 TITANIA, 141 TITANIUM DIOXIDE, 141 TITANIUM OXIDE, 26 TITRATION, 83 TOILET SEAT, 61 TOLUENE, 9 10 39 TOOLING, 73 TOPCOAT, 164 TORQUE, 65 TORSION PENDULUM, 218 TORSIONAL BRAID ANALYSIS, 218 TOXICITY, 13 30 46 56 82 94 128 139 141 195 199 208 217 TOXICOLOGY, 29 30 134 179 200 TOYS, 16 61 164 175 199 TRACEABILITY, 28 39 TRANSFER MOULDING, 19 TRANSISTOR, 136 TRANSLUCENCY, 12 74 137 TRANSMISSION ELECTRON MICROSCOPY, 36 68 78 112 117 153 TRANSPARENCY, 12 21 25 70 76 97 102 107 149 156 164 165 175 183 TRANSPORT PROPERTIES, 79 TRANSPORTATION, 128 145 183 TRIAZINE, 5 TRIBOLOGICAL PROPERTIES, 36 TRICHLOROETHANE, 9 TRIETHYLENE GLYCOL DIMETHACRYLATE COPOLYMER, 15 TRIETHYLENETETRAMINE, 217 TRIMMING, 12 TROPOLONE, 4 TROUBLESHOOTING, 201 TRUCK, 175 TUBING, 199 TURBINE, 122 TYRE, 6 74 TYRE DERIVED FUEL, 6

U ULTRA LOW-DENSITY POLYETHYLENE, 190

122

ULTRAMARINE BLUE, 128 ULTRASONIC, 217 ULTRAVIOLET CURING, 11 13 27 42 46 57 60 110 147 172 174 180 201 202 205 207 ULTRAVIOLET IRRADIATION, 1 101 146 148 173 203 ULTRAVIOLET LIGHT, 146 148 ULTRAVIOLET SPECTROSCOPY, 2 UNDERGROUND PIPE, 182 UNIVERSAL CALIBRATION, 88 UNSATURATED POLYESTER, 12 63 125 178 183 214 URETHANE DIMETHACRYLATE COPOLYMER, 15 URETHANE POLYMER, 3 34 35 110 131 133 143 151 186 UV COATING, 1 UV CURING, 11 13 27 34 35 3942 46 57 60 110 147 172 174 180 201 202 205 207 213 216 UV DEGRADATION, 60 UV LIGHT, 146 148 173 203 UV POLYMERISATION, 110 UV RADIATION, 101 146 148 UV RESISTANCE, 70 85 148 183 UV SCREENING, 76 UV SPECTROSCOPY, 2 182 UV SPECTRUM, 2 UV STABILISER, 16 22 70 76 118 133 146 158 187 UV STABILITY, 25 127 175 182 UV VIS SPECTROSCOPY, 182

V VACUUM PACKAGING, 35 64 VAPOUR, 12 195 VAPOUR DEPOSITION, 73 VARNISH, 14 28 33 101 106 216 VEGETABLE OIL, 209 VEHICLE EXTERIOR, 157 VEHICLE WIRING, 76 VIBRATION DAMPING, 88 VIBRATIONAL SPECTROSCOPY, 40 54 78 79 126 153 VIDEO TAPE, 114 VINYL ACETATE POLYMER, 149 VINYL ACETATE-ETHYLENE COPOLYMER, 35 VINYL ALCOHOL COPOLYMER, 47 79 VINYL ALCOHOL POLYMER, 12 24 VINYL CHLORIDE, 75 168 179

VINYL CHLORIDE COPOLYMER, 168 VINYL CHLORIDE POLYMER, 3 31 51 82 116 126 133 144 VINYL CHLORIDE TERPOLYMER, 168 VINYL HALIDE, 75 168 179 VINYL HALIDE POLYMER, 3 31 51 116 126 133 144 VINYL PYRROLIDINONE COPOLYMER, 54 VINYL PYRROLIDONE COPOLYMER, 54 VINYLIDENE CHLORIDE POLYMER, 42 149 VINYLPYRROLIDONE COPOLYMER, 54 VIRGIN POLYMER, 26 181 VISCOELASTIC PROPERTIES, 88 VISCOMETRY, 88 VISCOSITY, 18 26 54 78 111 147 192 198 VISCOSITY MODIFIER, 168 VISIBLE SPECTRA, 182 VISIBLE SPECTROSCOPY, 182 VOC-FREE, 80 202 VOLATILE CONTENT, 39 VOLATILE ORGANIC COMPOUND, 10 57 76 120 180 201 VOLATILE REMOVAL, 29 VOLATILITY, 90 199 206 VULCANISATE, 32 VULCANISATION, 195 VULCANISATION TIME, 57

W WALL COVERING, 41 WALL THICKNESS, 102 122 WARPAGE, 61 86 107 111 188 WASHING, 7 WASTE, 49 50 51 52 53 96 161 181 WASTE DISPOSAL, 12 107 128 179 WASTE MANAGEMENT, 6 81 128 152 168 WASTE SORTING, 7 WASTE WATER, 8 WATER, 4 12 36 73 79 90 94 118 130 138 140 146 148 149 181 189 WATER ABSORPTION, 36 76 79 92 117 WATER CONSUMPTION, 7 WATER PERMEABILITY, 48 79

© Copyright 2007 Smithers Rapra Technology

Subject Index

WATER PIPE, 4 19 22 125 182 WATER REMOVAL, 76 WATER RESISTANCE, 55 WATER SOLUBLE, 71 78 98 160 WATER TREATMENT, 6 75 109 WATER VAPOUR TRANSMISSION, 98 184 WAX, 28 29 WEAR, 26 WEAR RESISTANCE, 36 175 183 WEATHER RESISTANCE, 16 74 107 127 WEATHERABILITY, 76 119 164 183 WEATHERING, 16 74 107 127 WEATHERING RESISTANCE, 16 74 107 127 WEATHEROMETER, 131 WEBSITE, 74 144 WEIGHT LOSS, 29 WEIGHT REDUCTION, 16 66 102 WELDABILITY, 25 WELDING, 175 183 WET BONDING, 35

WET-OUT, 26 WETTABILITY, 110 WETTING, 40 67 WHEEL COVER, 92 WIDE ANGLE, 6 WIDE TYRE, 6 WIND TURBINE, 122 WINDOW, 164 WINE, 108 WIRE, 158 WOLLASTONITE, 61 WOOD FIBRE-REINFORCED PLASTIC, 16 133 WOOD FIBRE 22 WOOD FINISH, 180 WOODWORKING, 162 163 WORK FORCE, 165 WORLD WIDE WEB, 74 144

X X-RAY DIFFRACTION, 24 36 48 68 112 153 X-RAY FLUORESCENCE SPECTROSCOPY, 95

© Copyright 2007 Smithers Rapra Technology

X-RAY SCATTERING, 24 36 48 68 112 153 X-RAY SPECTRA, 95 X-RAY SPECTROSCOPY, 95

Y YELLOW DYE, 107 YELLOWING, 73 175 YTTRIUUM ALUMINUM GARNET, 3

Z ZIEGLER CATALYST, 38 68 69 129 145 ZIEGLER-NATTA CATALYST, 38 68 69 129 145 ZINC STEARATE, 126 ZIRCONIA, 15 140 ZIRCONIUM OXIDE, 15 140 ZIRCONYL DIMETHACRYLATE COPOLYMER, 15

123

Subject Index

124

© Copyright 2007 Smithers Rapra Technology

Company Index

Company Index A

C

E

ACCO BRANDS CORP., 101 ADEKA CORP., 21 55 ADVANCED PLASTICS TECHNOLOGIES, 73 AGROTECHNOLOGY & FOOD INNOVATIONS BV, 182 ALGIERS,ECOLE NATIONALE POLYTECHNIQUE, 126 AMCOR PET PACKAGING, 73 150 AMERICAN PLASTICS COUNCIL, 91 AMPACET CORP., 26 ANHEUSER-BUSCH, 73 ANSON PACKAGING, 12 APME, 125 ARCHER DANIELS MIDLAND CO., 12 ASAHI KASEI CORP., 165 ASAHI KASEI LIFE & LIVING CORP., 165 ASHLAND, 1 ATHENS,GENERAL CHEMISTRY STATE LABORATORY, 4 ATHENS,NATIONAL TECHNICAL UNIVERSITY, 9 ATHENS,UNIVERSITY, 4 ATOFINA CHEMICALS INC., 164

CARGILL, 12 CASE WESTERN RESERVE UNIVERSITY, 38 CASTELLON,UNIVERSITY, 48 CEFIC, 125 CEREPLAST INC., 12 CHEMICAL MARKET ASSOCIATES INC., 26 CIBA SPECIALTY CHEMICALS, 74 107 118 131 187 188 COCA-COLA CO., 73 COLORMATRIX CORP., 73 CONAIR, 12 COOP BOX, 12 COORS BREWING CO., 73 COUNCIL OF EUROPE, 106 CRODA POLYMER ADDITIVES, 65 CROMPTON CORP., 187 CSIC, 48 79 CYCLICS CORP., 122 CYTEC, 57 CZECHOSLOVAK ACADEMY OF SCIENCES, 215

EASTMAN CHEMICAL CO., 12 ECO2, 7 EDLON MACHINERY LTD., 159 ENERGY SCIENCES INC., 45 159 EUROPEAN COMMISSION, 209 EUROPEAN PLASTICS CONVERTERS ASSN., 28 EVAL AMERICAS (USA), 47 EX-TECH PLASTICS INC., 12 EXCEL POLYMERS LLC, 85 EXXONMOBIL CHEMICAL CO., 43 149 170

B BASELL, 129 BASF, 12 86 89 127 132 135 141 148 157 188 BATTENFELD GLOUCESTER ENGINEERING CO., 26 BAYER AG, 188 BAYSHORE INDUSTRIAL INC., 26 BCC RESEARCH, 12 BIOBAG, 12 BLACK CLAWSON CONVERTING MACHINERY INC., 44 BLOOM PACKAGING PVT.LTD., 40 BOOTS CO.PLC, 194 BOREALIS 102 189 BUSINESS DEVELOPMENT ASSOCIATES, 73

D DAINICHISEIKA COLOR & CHEMICALS MFG.CO., 124 DAINIPPON INK & CHEMICALS INC., 165 DEGUSSA AG, 216 DENMARK-VETERINARY & FOOD ADMINISTRATION, 206 DEUTSCHER VERBAND DER INERALFARBENINDUSTRIE, 141 DEVTECH LABS, 73 DOW CHEMICAL, 12 38 91 DOW CORNING LTD., 14 106 DRESDEN,TECHNISCHE UNIVERSITAT, 173 DUBLIN,CITY UNIVERSITY, 83 DUNDEE,UNIVERSITY, 143 DUPONT, 12 DUPONT ENGINEERING POLYMERS, 92 93 DUPONT TITANIUM TECHNOLOGIES, 74

© Copyright 2007 Smithers Rapra Technology

F FABES GMBH, 118 144 FABRI-KAL CORP., 12 FAR WEST TECHNOLOGIES, 45 FORMOSA PLASTICS GROUP, 26 FOROYA BJOR, 73 FREEDOM-2, 77 FREISING,FRAUNHOFER INSTITUT VERFAHRENSTECHNIK & VERPACKUNG IVV, 18 FRIENDS OF THE EARTH, 194 FROST & SULLIVAN, 64 FULLER H.B., 162 163 FUTURA POLYESTERS, 73

G GAIRESA, 210 GALACTIC SA, 12 GBC FILMS GROUP EUROPE, 101 GE SPECIALTY CHEMICALS, 187 GERMANY,INSTITUTE OF PLASTICS PROCESSING, 73 GEROSA, 152 GRAHAM PACKAGING, 73 GREAT LAKES CHEMICAL CORP., 187

H HACETTEPE,UNIVERSITY, 54 HAMBURG,UNIVERSITY, 173 HENKEL KGAA, 186

125

Company Index

HERITAGE BAG, 26 HERITAGE PLASTICS INC., 26 HILEX POLY CO., 26 HITE BREWERY CO., 73 HOLLIDAY PIGMENTS LTD., 128 HONEYWELL PERFORMANCE PRODUCTS, 73 HONEYWELL SPECIALTY POLYMERS, 73 HOSOKAWA ALPINE AMERICA, 26 HUHTAMAKI, 12 HUSKY INJECTION MOLDING SYSTEMS LTD., 73 HYOSONG CORP., 73

I IATA, 48 IMERYS PERFORMANCE MINERALS, 26 INDIAN INSTITUTE OF TECHNOLOGY, 36 INDIAN PETROCHEMICAL CORP.LTD., 113 INDITHERM, 169 INGENIA POLYMERS GROUP, 26 INRA, 87 INSTITUT NATIONAL DE LA RECHERCHE AGRONOMIQUE, 191 206 INSTITUTO DE CIENCIA Y TECNOLOGIA DE POLIMEROS, 112 INTEPLAST GROUP, 26 INTERTECH-PIRA, 12 INVISTA, 73

J JAUME I,UNIVERSITAT, 79 JUNIPER, 6

K KANEKA, 12 KANPUR,CHHATRAPATI SHAHU JI MAHARAJ UNIVERSITY, 8 78 153 KANSAS STATE UNIVERSITY, 117 KARNATAK UNIVERSITY, 24 KCL FINLAND, 33 KELLER & HECKMAN LLP, 46 154 196 211

126

KEURINGDIENTS VAN WAREN, 206 KIEFEL INC., 26 KING’S COLLEGE, 2 KOREA,UNIVERSITY, 192 KORTEC INC., 73 KOSA, 73 KYUNGNAM,UNIVERSITY, 192 198

O

L

P

LANXESS CORP., 188 LASER INSTALLATIONS LTD., 143 LEEDS,UNIVERSITY, 214 LIMERICK,UNIVERSITY, 83

PANALYTICAL BV, 95 PARIS II,UNIVERSITE, 206 PARKINSON TECHNOLOGIES INC., 12 PIRA INTERNATIONAL, 31 70 125 105 144 212 PISA,UNIVERSITY, 20 PLANTIC TECHNOLOGIES LTD., 12 PLASTIC ENGINEERING ASSOCIATES INC., 12 PLASTIC SUPPLIERS INC., 12 PLASTICS TOUCHPOINT GROUP INC., 26 POLYMER LABORATORIES LTD., 88 POLYMER PROCESS COMMUNICATIONS, 12 POLYONE, 97 POLYVAL PLC, 98 PORTUGAL,INSTITUTE FOR BIOTECHNOLOGY AND BIOENGINEERING, 2 PRINCETON,UNIVERSITY, 218 PROBOS SA, 162 163 PURAC AMERICA, 12

M M AND G POLYMERS, 73 MARSHALL & WILLIAMS, 12 MARTENS, 73 MATCHMYCOLOR.COM, 74 METABOLIX, 12 MICA CORP., 44 MICHIGAN,STATE UNIVERSITY, 10 MINHO,UNIVERSIDADE, 2 MITSUBISHI CHEMICAL, 165 MITSUBISHI GAS CHEMICAL AMERICA INC., 73 MITSUI CHEMICALS, 12, 123 145 156 MOMENTIVE PERFORMANCE MATERIALS INC., 19

N NAKAMOTO PACKS CO.LTD., 121 NANOBIOMATTERS LTD., 48 NANOCOR INC., 73 NATUREWORKS LLC, 12 NELLI RODI TRENDLAB, 74 NESTLE WATERS, 96 NEXANT CHEM SYSTEMS, 176 NISSEI CHEMICAL CO.LTD., 121 NORWEGIAN FOOD SAFETY AUTHORITY, 59 NORWEGIAN INSTITUTE OF PUBLIC HEALTH, 59 NOVA CHEMICALS, 111 NOVAMONT NORTH AMERICA INC., 12 NYLON CORP.OF AMERICA INC., 25

OMYA INC., 26 ORIENTAL BREWING, 73 OSAKA,CITY INSTITUTE OF PUBLIC HEALTH AND ENVIRONMENTAL SCIENCES, 94 OVIEDO,UNIVERSITY, 140

R RADTECH FOOD PACKAGING ALLIANCE, 46 RADTECH INTERNATIONAL NORTH AMERICA, 46 57 RAHN USA CORP., 147 RAPRA TECHNOLOGY LTD., 32 35 37 39 84 90 108 133 142 RECKITT BENCKISER, 49 50 51 52 53 96 REIFENHAUSER INC., 26 REIMS,INSTITUT NATIONAL DE LA RECHERCHES AGRONOMIQUES, 181 REIMS,UNIVERSITY, 206 REXAM, 73 ROCHESTER,INSTITUTE OF TECHNOLOGY, 60

© Copyright 2007 Smithers Rapra Technology

Company Index

ROHM & HAAS CO., 42 100 120 152 ROHM & HAAS FRANCE SAS, 109

S SABERT CORP., 12 SABREEN GROUP INC., 3 58 SAFEPHARM LABORATORIES LTD., 179 SAINSBURY, 12 SANITIZED AG, 155 SBA-CCI WORLDPET, 73 SCHOENWALD CONSULTING, 73 SCHOTT HICOTEC, 73 SEALED AIR CORP., 28 SHELL CHEMICAL, 73 SHEPHERD COLOR CO., 119 185 SHIMADZU CHEMICAL, 12 SICPA, 110 SICPA PRINTING INKS, 207 SIDEL INC., 73 SIG CORPOPLAST, 73 SINGAPORE,AGRI-FOOD AND VETERINARY AUTHORITY, 139 SIPA INC., 73 SOVEREIGN SPECIALTY CHEMICALS INC., 174 197 202 SPAIN,INSTITUTO NACIONAL DE INVESTIGACION Y TECNOLOGIA AGRARIA Y, 5 SPARTECH CORP., 12 183 SPECIALCHEM, 74 144 SPI, 96 211 SPLIT,UNIVERSITY, 75 SRI CONSULTING, 12 STANELCO PLC, 12 STARNA INDUSTRIES, 80 STUTTGART,CHEMISCHES UND VETERINARUNTERSU CHUNGSAMT, 11

SUN CHEMICAL LTD., 115 SURFACE SPECIALTIES, 46 SWINBURNE,UNIVERSITY OF TECHNOLOGY, 62 SZCZECIN,UNIVERSITY OF TECHNOLOGY, 27

T TATE AND LYLE BIOPOLYMERS, 12 TICONA, 72 TNO NUTRITION & FOOD RESEARCH, 37 200 203 TNO QUALITY OF LIFE, 29 TOKYO,INSTITUTE OF TECHNOLOGY, 56 TORAY PLASTICS (AMERICA) INC., 114 TREOFAN GROUP, 12 TURKU REGIONAL INSTITUTE OF OCCUPATIONAL HEALTH, 217

U UK,CENTRAL SCIENCE LABORATORY, 34 138 UK,DEPT.FOR THE ENVIRONMENT,FOOD & RURAL AFFAIRS, 17 34 130 143 193 UK,FOOD STANDARDS AGENCY, 37 UNION CARBIDE CORP., 213 UNIVATION TECHNOLOGIES, 68 US,ENVIRONMENTAL PROTECTION AGENCY, 139 US,FOOD & DRUG ADMINISTRATION, 30 46 72 73 91 106 118 127 139 146 148 174 US,NATIONAL FOOD PROCESSORS ASSN., 211

© Copyright 2007 Smithers Rapra Technology

US,NATIONAL INSTITUTE OF STANDARDS & TECHNOLOGY, 15

V VALENCIA,POLYTECHNICAL UNIVERSITY, 140 VALSPAR CORP., 73 VISY TECHNICAL CENTRE, 62

W WACKER SILICONES CORP., 201 WACKER-CHEMIE GMBH, 201 WAL-MART, 12 WASHINGTON,EARTH POLICY INSTITUTE, 12 WASTE & RESOURCES ACTION PROGRAMME, 6 WELLMAN INC., 73 WENTUS, 12 WILD OATS MARKETS, 12 WILKINSON INDUSTRIES INC., 12 WROCLAW,ACADEMY OF ECONOMICS, 109

X X-RITE, 74 XALOY INC., 12

Z ZURICH CANTON,OFFICIAL FOOD CONTROL AUTHORITY, 208

127

Company Index

128

© Copyright 2007 Smithers Rapra Technology

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