European Coatings Journal 2010,10

Primer 10 | 10

Growing and evolving There is a number of voices in the coatings industry declaring that looking at their business units' strong performances they cannot perceive the effects of the crisis any more. They seek to grow their market footprints further and at the meantime evolve the underlying technologies. Polyurethanes are a good example of a raw material that has played an increasingly important role in coatings formulations during the past years, due to their excellent performance and versatility. Philippe Barbeau and his co-authors explain in their review on page 18 that urethanes consumption is currently showing fastest growth in China. If you want to learn more about the European market players in this segment do not miss Damir Gagro's PUR market overview on page 9.

Miriam von Bardeleben

Intumescent coatings are widely and successfully used to protect wood and metal surfaces, but there is little evidence of their use on plastics. Find out on page 26 why Maude Jimenez et al think that an intumescent coating for plastics would be the best option, offering further growth potential for this impressive technology.

Source: HSH Aerospace Finishes (left); Perstorp (middle); Bayer MaterielScience

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Market Watch Industry news

 Metal coatings

Interview Raw materials

“Focusing on efficiency and a strong culture of innovation” Maurizio Garlaschelli, Air Products The financial downturn has affected the entire industry. Maurizio Garlaschelli, General Manager Performance Materials EMEA at Air Products, expects the market recovery to be a long process. The chemicals producer's goal is to compete in the market with the latest technology instead of competing with commodities. _How has Air Products performed during the crisis? To what extent have market opportunities risen for the Performance Material business unit? Maurizio Garlaschelli: We were not excluded from the negative effects of the recession. Our last fiscal year began in October 2008, which was a very challenging time for us. In the second half our of fiscal year, there was a positive development in our business, so we were able to recover. Focusing even more on efficiency and a strong culture of innovation were key to us during the crisis. Equally it was crucial for us to continue to review and validate our strategy, as well as concentrate on developing new products. We generate approx. 20 - 25 % of our total sales with new products that have been introduced to the market within the last five years. _What end market areas are driving growth in the coatings market? Garlaschelli: We have seen growth in all areas. With regards to additives and surfactants, the business is well above where it was last year and almost as high as in our record year in 2008. However, we expect the market recovery to be a long process with new peaks but also with dips in demand and sales. In Western Europe, the major markets in Germany, Italy, France and the U.K. contributed very well to our overall

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growth where sales of our latest technology have continued steadily. As a result, we expect further growth in these markets. In the emerging markets of Eastern and Southeast Europe, we have witnessed a more rapid growth during the last two to three years. The same applies to the Middle East and Russia. _How is the current economy affecting the demand and production of coatings raw materials in mature and emerging markets? How do you act in this situation?

Teknos and Oliva merger in Poland Finland-based company Teknos and Polish paint producer Oliva have signed an agreement to serve the Polish metal paint market with a joint venture. According to the agreement the new company will operate as Teknos-Oliva. This merger needs legal approvals of governmental bodies. The paint producer expects that the deal can be closed by the end of October 2010. The Polish company offers metal industry paints and yacht paints, has personnel of 90 employees and operates an office as well as a paint factory in Gdynia. The net sales of the Polish business are approx. EUR 8 million. www.teknos.com

 Automotive coatings

Garlaschelli: Many companies are cutting down production capacities and are therefore tight on raw materials. In contrast, we have not reduced capacities and are looking to invest in capacity expansion in the EMEA region. Both the decrease in production and the lack of vessels available to transport goods brought about the raw materials shortage. Distribution companies have also reduced their activities. As a result, there is still uncertainty as to what the future brings.

AkzoNobel makes strategic move in China

_To what extent have customers’ demands and needs changed?

AkzoNobel is to significantly boost its presence in the Chinese automotive market after agreeing to acquire Changzhou Prime Automotive Paint Co., Ltd. Prime is one of China’s largest vehicle refinish suppliers and a leader in the fast-growing mid-market segment. This sector is estimated to double in size within the next five years. Based in Jiangsu Province, the company develops, manufactures, markets and distributes automotive coatings, primarily for the refinish market. Through its Car Refinishes business, AkzoNobel has so far mainly been active in China’s premium and commercial vehicle refinish sector. AkzoNobel currently employs around 6,500 people in China, with the country hosting 11 % of the company’s Research, Development and Innovation resources. Revenue for 2009 totaled USD 1.5 billion. www.akzonobel.com

Garlaschelli: The demand for eco-friendly products is rising. In response to this need, our R&D teams are focusing on continuing to reduce emissions and VOCs within our product portfolio. Instead of competing with commodities, our goal is to compete in the market with the latest technology. Apart from this, flexibility and customised products are demanded. Through the acquisition of S.I.Q., we now offer more tailor-made solutions for our customers and improved service capabilities. This will secure and strengthen our position, as well as establishing the basis for further growth. (gag)

Source: AkzoNobel

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Market Watch Industry news Interview Metal decorating coatings and inks

“A stable business”

Conrad Keijzer, AkzoNobel AkzoNobel has recently acquired the worldwide assets of Lindgens Metal Decorating Coatings & Inks AB, a Sweden-based manufacturer of coatings and inks for the metal packaging industry. Conrad Keijzer, Managing Director of AkzoNobel’s Industrial Coatings business, explains how this acquisition strengthens the company's position in niche segments. _What synergies do you expect from the acquisition of Lindgens? Conrad Keijzer: In metal packaging coatings we distinguish between two and three piece cans. Two piece coatings are used for beverage cans and three piece coatings for food cans and industrial packaging like paint cans. Through the acquisition of ICI, AkzoNobel entered the coatings market for two and three piece cans. However, we were lacking a range of inks which are applied on the outside of two piece cans. Lindgens focuses on inks for both applications and, consequently we can now offer our customers an entire range of coatings and inks. Additionally, we acquired interesting products for niche markets in the food industry. _What are these niche segments? How do you rate the growth potential?

now supply. In Australia, for instance, the wine producing industry has switched to metal closures; an interesting growth market that we can now supply. In Russia Vodka caps and closures represent an interesting market as well. The inks for three piece coatings applications also strengthen our positions in North Africa, Turkey and the Middle East. _How will the market for packaging coatings develop? What are future projects for AkzoNobel in the packaging coatings business? Keijzer: We expect a positive development. The market for packaging coatings, compared to other segments in the coatings industry, is a stable business - following GDP. During the financial downturn our business has been less affected. In our biggest markets people will eat and drink, no matter what the economic situation is. I see decoration of packages of all kinds becoming more and more important, and hence, demand for quality coatings and inks applied on packages are growing. We will focus on key target markets with large populations. We expect high growth potential in areas as Asia, Latin America and North Africa. (gag)

Unviar espands in Greece Univar has announced that the legal entity it established in Greece at the end of July is now fully operational and has signed a distribution agreement with Dow Corning’s Life Sciences and Aim divisions. The company has invested in this new territory in order to service an expanded agreement with Dow Corning’s Life Sciences and Aim divisions, with an initial emphasis on selling products for Personal Care, Household and Industrial Cleaning,

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IMCD and Columbian Chemicals extend partnership The raw materials supplier Columbian Chemicals has announced an extension of its partnership with IMCD Group as their Specialty Carbon Black distribution partner into the Coatings, Inks, Plastics and other non Rubber applications. The new agreement will include Russia, Latvia, Lithuania, Estonia, Belarus, Kazakhstan, Ukraine, Morocco, Tunisia and Algeria, in addition to the existing territories of Belgium, France, Luxembourg, Netherlands, Turkey, the UK and Ireland. With immediate effect, IMCD will handle the “Raven”, “Conductex”, “Statex” and “Neotex” product ranges and support the ongoing direct sales activity of Columbian Chemicals in all of the above regions. www.imcdgroup.com

 Emulsions Celanese appoints Boysan as distributor in Turkey Celanese Emulsion Polymers, a global leader in the production of water-based vinyl emulsions, announced that it has signed an agreement with Boysan to be its distributor in Turkey. “Celanese Emulsion Polymers is confident that Boysan is the right distributor for our sales efforts in Turkey which is an important growth area to our business,” said Dr. Rolf Kuropka, sales director for European region. Boysan has already begun distributing Celanese’s broad range of emulsion technologies into the paints & coatings, construction and adhesives industries. www.celanese.com

 Expansion

Keijzer: Caps and closures for bottles, like wine and Vodka, are segments we can

 Distribution

 Co-operation

Thor has inaugurated a new research centre in Germany Coatings and general industrial applications throughout Greece. The agreement will come into effect on 1 October 2010. The new entity is headed by Markos Roussos who, as General Manager Greece, will focus on developing business with customers with manufacturing capabilities in the region. Univar already has experience selling into Greece through exports from France and the UK. Roussos, who joined Univar from Tesa Tapes on 19 July, will also be responsible for recruiting additional team members in Greece. www.univareurope.com

Thor, a global manufacturer of specialty chemicals, has recently completed a new research centre at its site in Speyer, Germany. The 3.500m² building was constructed at a cost of EUR 6.5 million and Thor’s research and development team have been moving into the premises over the past few months. The modern, three story building is characterized by clear lines and structures and is furnished and equipped according to the highest industry standards. The research centre is a clear signal of the Thor Group’s on-going commitment to its major site in Speyer. www.thor.com

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Market Watch Polyurethanes

Source: Bayer MaterialScience

Overview of the PUR market Polyurethanes: Versatility combined with enormous development potential Damir Gagro Polyurethane raw materials were first used to make paints and coatings more than 50 years ago. Thanks to their versatility and scope for combination, they can be used to produce targeted and customized solutions that meet all kinds of requirements. Since its introduction, this class of raw materials has been experiencing a turbulent market development, which shows no signs of abating.

A

ll around the world, PUR chemistry has established itself in all kinds of applications involving painting, coating, bonding and sealing. Nevertheless, there is still potential for development. Just a few years ago, experts were predicting that PUR raw materials would enjoy aboveaverage growth commensurate with the steady rise in importance of solventless, waterborne and UV-curing systems. Polyurethane chemistry is thus almost a textbook example of how ecological improvements, higher quality and economic success need not be contradictory, but rather can harmonise with each other. Over the last decade, polyurethanes

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have increased their share of global consumption of coatings raw materials from 9 to 13 %. A value-based comparison of classes of coatings raw materials reveals that traditional systems now account for only about 30 % of world consumption. PUR coatings raw materials make up 18 % of sales, clear evidence that this class of raw materials is primarily found in high-end market segments. The main components of PUR coatings raw materials are polyisocyanates and polyols, such as polyacrylates, polyesters and polyethers.

PUR coatings primarily used for wood and automobiles Before the global economic crisis, experts were forecasting that global consumption of PUR coatings raw materials would grow by around 5 % a year. More specifically, they said that Asia-Pacific region would enjoy average growth of up to 10 % annually, while the European and American markets would average 3 to 4 %. In Europe, the Middle East, Africa and America, especially, most of this growth is in waterborne PUR coatings raw materials, whereas solventborne PUR coatings raw materials are also still growing strongly in the Asia-Pacific region.

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European Coatings Conference "Polyurethanes for high performance coatings VI" 7. & 8. December 2010, Berlin www.european-coatings.com/events

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Market Watch Polyurethanes The most important sectors within the paint and coatings industry in EMEA are wood/furniture and automotive, with 30 % and 25 % of consumption, followed by the paint industry with 15 %. This clearly shows that highend PUR coatings raw materials mainly find use wherever high quality and long-term stability are needed and, accordingly, are positioned in the higher price segments.

PUR market is recovering Currently there are no concrete figures to paint a satisfactory picture of actual rates of consumption and growth. However, Dr. Ulrich Meier-Westhues, Bayer MaterialScience AG, notes that the paints and adhesives market has made a substantial recovery from the financial crisis in 2010. “Monthly demand for polyurethane raw materials in many application areas has returned to the level it was at before the downturn in 2008, and is even higher in some cases. Growth rates are well above market average. This is a trend seen all around the world and is most pronounced in the Asia-Pacific region.” Stephane Champ Long, Perstorp A, is of a similar opinion. The recovery, which set in at the start of the year, is attributable to the automotive industry, to growth in Asia, and to a lesser extent to the North American market. “We expect the PUR market to be relatively stable, despite the fact that costs are rising steadily and that there is a shortage of raw materials at present.”

PUR adhesives and sealants for long-term durability The polyurethanes contained in adhesives and sealants are mainly composed of isocyanates/polyisocyanates or prepolymers, and polyols, such as polyesters and polyethers. Adhesives and sealants can be formulated from natural substances and a large number of polymeric materials, in addition to PUR-based raw materials. Polyurethane accounts for about 9 % of the total market for adhesives raw materials. Applications within the overall market can be broken down into 30 % transport, 18 % sealants, 17 % packaging, 16 % furniture and 12 % construction. The remaining 7 % is spread across assembly, shoes, pressure sensitive adhesives, household/DIY, disposable items and bookbinding. The high-quality polyurethane adhesives and sealants raw

materials are mostly employed in high-end applications where quality and long-term stability count, i.e. in the higher price segment, just as in the case of coatings.

Ecological and economic benefits The above-average growth rates are due to the ongoing trend for modern PUR systems to replace conventional technologies, says Meier-Westhues. This process is characterized on one hand by regional expansion with established products and on the other by ongoing innovation. Current development work on PUR systems is focused on sustainability, with equal status being accorded to environment, quality and economy. A key factor, according to the expert from Bayer MaterialScience, is the fact that the coatings are substantially more durable than conventional systems, and thus offer extended maintenance cycles. According to MeierWesthues, the growth also stems from the vast number of different ways to formulate ecologically sound paints and adhesives, which in turn bolster the trend even further. To comply with regulations and environmental stipulations, the industry offers ecologically sound polyurethane systems in various technologies: low-solvent, solventless, water-thinnable, radiation-curing, and waterborne. New to the market are totally solventless PUR dispersions for making totally solventless paints and adhesives. These represent a major step on the road to eradicating VOCs. Progress has also been made recently in the area of quality. Thus, PUR dispersions are now available which yield adhesives possessing even greater levels of initial and final strength.

New technologies coming to the fore As for ease of processing, highly reactive, waterborne 2-pack PUR formulations boasting a long potlife were launched not so long ago. The end properties of these coatings are on a par with their solventborne counterparts. Polyaspartic technology is rapidly gaining in importance for high-solids and super-high-solids coatings. It is being driven by a combination of highly efficient processing, low VOC levels, and high-quality coating results. Typical applications are to be found in corrosion protection, general industrial coatings, concrete coatings and gel coats for composite parts. New radiation-curing, waterborne dispersions now allow PURs to be used in pigmented coatings for wood/furniture and plastic substrates for the first time. And novel low-viscosity urethane acrylates which are completely VOC-free are also available for weather-resistant outdoor use.

Tapping renewable raw materials

World consumption of coating raw materials by product type (volume), total: 8.2 million tons Source: From the book Polyurethanes. Coatings, Adhesives and Sealants by Dr. Ulrich Meier-Westhues

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The prospect of a shortage of fossil-based raw materials in the future is spurring demand for renewable feedstocks with which to formulate paints and adhesives. Yet, classic, plant-oil systems, such as those based on alkyd resins, are still being replaced for the most part by petroleum-based systems for reasons of quality. The only way to reverse this trend and make greater use of renewable raw materials is to find a way to maintain or even enhance the high quality of modern coatings and adhesive systems under economically attractive conditions. The feedstocks used to make the polyol components for polyurethanes could be supplemented, for example, with renew-

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Market Watch Polyurethanes able raw materials. Dicarboxylic acids and diols can now be obtained by converting plant-based raw materials, as well as plant oils (e.g. castor oil), into polyester building blocks. Although it is early days yet, work is under way on sourcing renewable raw materials for polyisocyanate curing agents, too. Starch- and soy-based formulations are effective in PURbased adhesives and sealants where they confer properties similar to those of traditional systems. This is described in a study by a British market research company, Pira International, which reports that companies are focusing increasingly on developing new materials based on renewable raw materials for use in PUR-based adhesives and sealants. One caveat here is that that the land available for such sources is in competition for land for food crops and other uses. A decision needs to be taken as to whether this development makes ecological sense.

Challenges posed by legislation The industry is faced with increasing regulations regarding production and use of chemicals. The goal to improve consumer safety and protection of the environment is supported by all the parties concerned. REACH, the new European chemicals legislation, is weighing heavily on raw materials manufacturers in the coatings and adhesives industry. However, Meier-Westhues says that as things stand there is no need to expect significant restrictions with regard to

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PUR. In compliance with REACH, the range of PUR coatings and adhesives raw materials is now being systematically expanded to meet future requirements. However, the adhesives and sealants sector will be impacted by, for example, the reclassification of MDI. The industry is now actively looking for suitable alternatives.

New fields of application for PUR raw materials Direct coating is becoming an increasingly popular way to apply coatings. It consists in injection moulding a plastic part and applying the coating to it by the PUR-RIM process in two consecutive steps. This technology utilizes solventless raw materials and is highly efficient and economical. The resultant coating is of the same quality as PUR spray coatings. Lighting technology is a rapidly evolving area and one in which lightfast encapsulating compounds are gaining ground. For instance, LED strips for use in wet areas, such as bathrooms, saunas and indoor pools, as well as outdoors, are now being protected with clear, aliphatic PUR systems. Although this application area is still in its infancy, significant expansion is likely. To judge from previous and expected developments, sustained, above-average growth can be expected in the coming decades. The reason for this lies on one hand in the huge innovation potential afforded by PUR chemistry and, on the other, in increasing internationalization of the industry.

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"Polyurethanes” Ulrich MeierWesthues www. european- coatings. com/books

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Market Watch Titanium dioxide

Contracting TiO2 demand Decreasing figures in mature markets with mostly conservative outlook into the future

Contact: Machiel Keegel TZ Minerals International [email protected]

Machiel Keegel Karen Crosswell Global demand for titanium dioxide has decreased significantly between 2007 and 2009. Compared to Western markets, demand in emerging regions was much more robust. The markets are not expected to recover to pre-recession levels before the end of 2015, is one of the results of TZMI's latest TiO2 "Pigment Annual Review".

Pigment demand Global TiO2 demand was 4.7 million tonnes in 2009, down 3 % over 2008 and 8 % over the historical peak in 2007. In the more mature Western markets, TiO2 pigment demand collapsed by more than 16 % over the last two years and it is not expected to recover before the end of the forecast period to 2015 (Table 1). However, demand in the emerging regions contracted only marginally. The strength of the emerging markets, particularly those in Asia-Pacific and the Middle East, are expected to lift the global pigment consumption rate to 2015 while mature economies are expected to remain static at best. Since 2000, China has emerged as the dominant growth market for TiO2 pigment, supported largely by the rise of a domestic sulfate-process TiO2 industry. In recent years the ultrafine, or nano-TiO2, markets have undergone significant growth, both in terms of volume and scope of application. However, while these markets are currently highly profitable, the total volumes are no more than 1 % of the global marketplace.

Pigment production The global TiO2 pigment industry reached a record production level of 5.1 million tonnes in 2007. The following

(‘000 tonnes)

Table 1: Global demand growth rate between 2007 and 2015

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2007-2015

Asia-Pacific

4.1%

Central & South America

3.2%

Central and Eastern Europe

2.4%

Middle East & Africa

5.6%

North America

-0.1%

Western Europe

-0.4%

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two years have seen declining output; falling by more than 15 % to 4.4 million tonnes in 2009. The fourth quarter of 2008 was a turning point following the onset of the Global Financial Crisis: global output for the full year declined by 3.3 % to 4.95 million tonnes. The first quarter of 2009 was one of the worst the industry has ever encountered, with production down 34 % compared to the first quarter in 2008. Consumers of TiO2 saw product sales drop off sharply in the fourth quarter of 2008 and as a result orders for pigment collapsed. Some pigment producers predicted the oncoming rise in inventories early and moved to trim production levels, while others were less reactive. The latter group had to cut production even more drastically in the first, and in some cases the second quarter of 2009. While most plants were operating at full rates again in the second half of the year, others did not survive the recession; the Grimsby (Huntsman) plant was the first to be shut, closely followed by Savannah (Tronox).The Baltimore (Cristal) plant was cold idled, and Cristal recently (August 2010) announced permanent closure of base pigment production at this plant.

Pigment trade In international trade there are five main inter-regional routes, where more than 100,000 tpa of TiO2 is traded. When the US housing market started to deflate in 2006, domestic demand for TiO2 began to decline and North America significantly increased TiO2 exports into Western Europe, Asia-Pacific and South and Central America. The export rate, (exports divided by production) increased from a level of approximately 20 % to more than 35 % (Figure 1). TZMI expects the position of North America as a major exporter to remain unchanged, based on excess production capacity and the relatively low regional manufacturing cost. Western and Central Europe export similar quantities of pigment to each other; high quality, high cost products flow into Central Europe from Western Europe, while the relatively low cost product from Central Europe flows back into Western Europe. Asia-Pacific is a net importer of TiO2 pigment, although it has the largest manufacturing base of all regions. The imports tend to be of a higher quality than is widely available within the region.

Pricing The long term real TiO2 global pigment price has declined over the last 20 years in US dollar terms (Figure 2); however, there are significant differences in the pricing

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Market Watch Titanium dioxide behaviour within different regions and different end-use markets. The declining price levels have resulted in margin erosion below re-investment economics, especially in the last three years. As a result of re-stocking, unplanned capacity outages, and plant closures, the current supply for TiO2 has become very tight, despite the fact that demand has not recovered full to pre-crisis levels. This has resulted in a waterfall of price increase announcements by the major producers and climbing prices throughout the global markets.

Capacity expansion Over the last 5 years, industry transactions have been executed at real 2009 USD capacity tonne values of USD 1,500-2,000. This is in stark contrast with the cost of Greenfields expansions which have averaged almost USD 5,500 per tonne of annual capacity (real 2009 USD total investment basis including land and support services). Brownfield expansions tend to vary anywhere from USD 500-4,000 per tonne of annual capacity depending on the scope of the expansion. Access to the newer chloride process has been tightly held by a handful of global manufacturing companies and those organisations that successfully licensed technology from these companies during the 1970s and 1980s. No Greenfields chloride route pigment plants have been commissioned since 1994. New processes for the manufacture of TiO2 pigment have been, and still are, constantly under development, but no alternative manufacturing routes have been successfully commercialised to date. In most growth markets for TiO2 products the Global Financial Crisis of 2008/09 is a past memory, while in other more mature markets the demand outlook is still somewhat conservative. The full extent of the changing forces in the industry will be felt as 2010 unfolds, so this new publication is most timely in seeking to put all these items into perspective. TZMI Group (TZMI) has published its inaugural edition of the TiO2 Pigment Annual Review (PAR). TZMI has published information on the USD 11 billion global titanium dioxide TiO2 pigment industry since 1997, but the inception of the latest publication now adds an annually recurring update on the dynamics of the TiO2 industry to TZMI’s regular publications offering. More info: www.tzmi.com

Figure 1: North American exports versus demand between 2001 and 2009

Figure 2: Real 2009 USD weighted average global TiO2 pigment pricing

Wettability • Spreadability • Interfacial Tension • Pigment Wetting • Film Elasticity • Surface Defects

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The experts in Surface Science.

Please visit us at the k´2010 show in Düsseldorf, hall 1, stand 10D04 coatings_176x28.indd 1

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Association BCF

A sustained interest in coatings The BCF teams up with associations and academia to develop sustainability strategies As the very purpose of coatings is to protect and preserve, the contribution they make to a sustainable future is significant. However, this must sit alongside responsible manufacturing. With this in mind, Tony Mash, CEO of the British Coatings Federation, explains the importance the association places on continual improvement. The British Coatings Federation (BCF) is the sole trade association representing the interests of over 110 companies in the decorative, industrial and powder coatings, printing inks and wallcovering industries in the UK. At its core is a broad knowledge of regulatory and technical matters, which it employs to educate, communicate and influence widely. Added to these activities, the BCF has formulated a broad range of training programmes, seminars, support services and statistics, which keep members up-to-date on trends and best practice. A common thread that runs through these different elements and one that is crucial to the association's role is the issue of sustainability.

Sustainability policy improves manufacturing processes Members of the BCF are committed to a longterm journey towards a sustainable industry and as such the BCF published its Sustainable Development Policy. This details members’ commitment to the principles of Sustainability in terms of economic and social responsibility and economic viability - setting standards against which members will measure themselves. This policy builds on the established principles of Coatings Care, the BCF's international care and sustainability programme, aimed at continually improving the performance of the coatings industry. Since its inception in 1996, the Coating Care Indicators of Performance have demonstrated significant improvements by the industry in its manufacturing processes. Energy used per tonne of product by kWh has almost halved and the percentage of waste sent to landfill has reduced by 55%. The Indicators of Performance also monitor solvent usage and show a steady fall over the last ten years in solvents purchased per tonne of production. Tony Mash, CEO, British Coatings Federation

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Awarding sustainabilty efforts An annual award is presented to the member site that can best demonstrate improvements in overall perform-

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ance indicators, which include: health and safety, energy consumption, waste and recycling, VOC emissions, management and communications. The Coatings Care Award gives recognition to those manufacturers working towards continuous improvement to contribute actively to a sustainable environment. In addition this year, the BCF has created a new Sustainable Innovation Award. This will be presented to the company whose manufacturing processes and products have most effectively reduced their impact on the wider supply chain. This award is structured to encourage product designers to consider not only how their new products will be made and applied in a safe and economic manner, but also how they will behave when they are sent into the waste stream for recycling or disposal.

Co-operations to exchange knowledge The BCF's Sustainable Development Policy, Coatings Care programme and awards have been so well regarded that CEPE, the European trade body for coatings and inks, has invited the BCF to lead a team of European coatings trade associations to develop a sustainability strategy for the whole of Europe. The BCF has risen to the challenge and is working with the Chemical Industry Knowledge Transfer Network, the Chemical Industries Association and the University of Manchester to encourage the development and use of a consistent way of measuring the carbon footprint of coatings products, aiming for a clear approach that will enable the industry to compare like for like. One area of particular interest to the BCF is the University of Manchester's new CCaLC (Carbon Calculations over the Life Cycle of Industrial Activities). The programming tool together with an extensive database of information about chemicals, manufacturing processes and services, allows for the consistent calculation of carbon footprints and represents a significant landmark on the Sustainability path. Sustainability is an evolutionary process, facilitated by research and development, effective management procedures and above all, a shared vision and a commitment by all those involved. The BCF believes that the Coatings Industry already makes an invaluable contribution to society. However, adopting clear and consistent practices towards issues of Sustainability will ensure the industry’s contribution remains a positive one.

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AB Pro 70 Ph e-m

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Expert Primer Voices Polyurethanes

Stupendous spectrum of strength The quality is based on the broad range of performances Polyurethanes offer a broad application range with lots of technical advantages. Possible weaknesses can be eliminated in different ways. Dr. Olga Kameneva, Zellik, Belgium, describes a solution for waterborne topcoats: good technical know-how during the production process. Dr. Neil Carter, Incorez Limited, UK, presents a method of blending polyurethanes with other resins, which could also lower the price.

“PUR is extremely versatile in its chemistry.”

1 2the relatively Is it possible to compensate higher costs compared

What are the advances of PUR and how do you solve the weaknesses?

to other coatings systems?

Dr. Neil Carter Head of Technical Incorez Limited Preston, UK

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PUR can be used in all kinds of applications. It allows the resin formulator to design a broader range of performance properties compared to other polymer types such as acrylics and epoxies. It also boasts outstanding performance, including great resistance to scratching and chemicals. This renders PUR coatings tough and also flexible, compared to epoxies and acrylics. Indeed PU is often used to enhance the performance of acrylics, particularly in the waterborne area where PUDs are blended or copolymersised with acrylic emulsions to enhance coating properties. PUR is extremely versatile in its chemistry. You can vary its hardness from very hard to very soft – making PURs easier to tailor to performance requirements. Aliphatic PURs have good UV stability, good chemical resistance and gloss retention. What’s more, another advantage of PUR is that a higher content of renewable raw materials are becoming readily available to PUR formulators compared to other resin technologies. It is leading the way for resins in with sustainable building blocks. In terms of weaknesses, the need to reduce VOC levels

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by using less solvent is an issue for harder PURs as much as for other polymer types. Aromatic PURs do not have good UV stability. If that is a requirement, then you must either use aliphatic types or add photostabilizers. Another area of weakness is the problem of gassing, carbon dioxide generation from moisture reaction with isocyanate which can lead to deficiencies (pin holes) in solvent-based and solvent-free products. This can be eliminated by using scavenging additives such as oxazolidines

2

Getting top performance at a low price is always a balancing act. A roof coating, for example, must be durable. An acrylic coating will last a guaranteed 10 years. A PUR coating will last up to 25 years. To get the same performance from the acrylic coating, you would therefore have to re-coat. But that means you would double the cost as well false economy. One way to lower the cost while exploiting the benefits of PUR would be to use in a blend with an acrylic.

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Primer Voices Expert Polyurethanes

“The possibility of combination of resins with isocyanates is so wide that every requirement can be met.”

“Polyurethanes” Ulrich MeierWesthues www.europeancoatings.com/ books

Dr. Olga Kameneva Technical Director HSH Aerospace Finishes Zellik, Belgium

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The technology of polyurethane is not new but there are still advances in environmental behavior and solving of challenges relating to performance issues. One of the major changes of the last decade is the introduction of a full range of waterborne products. Waterborne two component polyurethane topcoats find use in many industrial applications. Often mechanical stirring is needed to achieve homogeneous mixtures of components. Application time (pot life) is limited and varies between 3 and 5 hours and is not so easy detectable as for the solvent version. Polyisocyanates used as hardener are sensible to air humidity. Flash off time should be respected in order to avoid blistering and other film defects. These disadvantages require special mixing equipment installation for continuous application process. These weaknesses relate to the chemical principals of polyurethanes and there is no general solution to solve it. However continuous progress of developments in this area helps us to reduce these problems. In spite of these weaknesses two component polyurethane topcoats are still in the lead of the market because of their benefits, such as excellent chemical and mechanical resistance, better weathering resistance and durability (in case if aliphatic isocyanates are used). The possibility of combination of resins with isocyanates is so wide that practically every customer requirement can be met.

contain application costs and maintenance. Thanks to advanced adhesion of polyurethane coatings on most of substrates, they could be applied directly without using of primer on the most non-ferrous surfaces. Excellent chemical resistance and durability allow to prolong a life cycle of coating and to reduce repainting maintenance frequency. It does mean that in the long run the polyurethane topcoats costs are legitimate.

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The higher price of waterborne two component polyurethane topcoats is evidence. However the total price of coating application and maintenance process is a composite value. In addition to coating costs, it does

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Technical Paper

Source: Perstorp

Polyurethanes

The isocyanate link High-performance PU coating resins continue to evolve

* Corresponding author: Philippe Barbeau Perstorp, France philippe.barbeau@ perstorp.com

Philippe Barbeau Kent Sörensen Use of polyurethanes has grown relatively rapidly due to their excellent performance and versatility. Markets, technologies, current and future developments are reviewed. The main emphasis in recent development has been on high solids and waterborne systems, elimination of toxic NMP and the introduction of some higher quality raw materials. For the future, the industry faces many different environmental challenges.

S

ince the pioneering work by O. Bayer and his coworkers in the 1930s [1], polyurethane polymers have expanded their role in many manufacturing sectors. These include flexible and rigid foams, durable elastomers (for rollers wheels etc.) adhesives and sealants, high performance plastic parts and, of course, paints and coatings. Chemically, polyurethanes (PU) are based on the reaction between a multifunctional alcohol and a polyisocyanate.

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This provides the basis for designing polymers for a vast range of different applications. More recently their appeal has grown because of the ability to formulate low VOC eco-friendly systems. Polyurethanes are thus ideal for many coatings applications, providing high chemical and mechanical resistance, very good adhesion on various substrates, fast film formation, excellent weathering resistance and low temperature curing when required. After a brief overview of the market situation, this article discusses some of the most recent trends observed in polyurethane coating systems, and sets out the main challenges for the future.

Global market situation and main technologies From 1994 through to 2006, global consumption of urethane coatings in industrial use grew by an estimated 3.5 % per year on average [2], to some 711 000 metric tons of polyols and isocyanates in 2006 (on a 100 % solids content basis). In the same period, consumption of all coating resins grew by about 2.3 % annually.

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ECJ_BY

Technical Paper Polyurethanes They are also being used in OEM vehicle clearcoats, although conventional 1K acrylic-melamine systems still dominate this segment. The many advantages of urethanes in this application justify their higher cost: »»Better overall chemical and environmental resistance (towards acid rain, bird droppings etc); »»Improved mechanical properties such as scratch/mar resistance and flexibility; »»Better durability; »»Lower energy consumption due to lower curing temperatures.

Designing high-solids systems: problems and solutions Figure 1: World consumption of polyols and isocyanates for urethane surface coatings in 2006 in kilotons (from [2])

From 2002 until 2007–early 2008, volume growth rose to nearly 6 % per year. Although the economic downturn in late 2008–2009 seriously affected the coatings industry and polyurethanes in general, the market now seems well on the way to recovery. Predicted annual growth in isocyanate consumption over the next five years is 6 %. Today, most polyurethane coatings are still consumed in North America and Western Europe (see Figure 1), although Asia, and in particular China, shows much faster growth than the other regions [2]. Urethanes are mostly used for industrial coatings applications (>80 % by volume), and only a small part for decorative (architectural) coatings through modification of conventional alkyds. Urethane systems can be classified into two main types: two-component (2K) systems and single pack. In 2K systems, the OH functional polyol component and the polyisocyanate are packaged separately and mixed prior to application. One-component (1K) systems comprise: »»Those with the isocyanates blocked externally or internally (the latter mostly used in powder coatings); »»Moisture-cured PU; »»Polyurethane dispersions; »»UV-curable modified PU; »»Urethane modified alkyds (mostly for architectural coatings).

Two-component systems drive automotive coatings forward European Coatings CONFERENCE "Polyurethanes for high performance coatings" 7.& 8.12.2010, Berlin www.europeancoatings.com/ events/ecc-pur.cfm

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2K systems are clearly one of the largest categories of polyurethane coatings for various applications: transportation (including automotive, aircraft, buses, trucks, motorbikes and railroad cars), agricultural and construction equipment, industrial wood, plastics, marine and protective, coil and can. Both aromatic and aliphatic types are used, with aliphatic systems strongly preferred for outdoor and non-yellowing applications. Since the mid-1980s, aliphatic 2K PUs have become very popular in car refinishing, and now account for 80 % of topcoats/clearcoats.

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Due to environmental pressure to reduce VOC emissions, recent developments in 2K PU systems have been largely focused on designing high solids (or super high solids) and waterborne systems. High solids imply designing low viscosity polyols and polyisocyanates while retaining the same performance. However, reducing viscosity usually implies reducing the molecular weight, which adversely affects the properties of the final coating. For that reason, polyester-type polyols are often used since their stepgrowth esterification can ensure that all molecules are OH-functionalised, unlike free radical polymerisation (acrylic polyols). But these low Mw polyesters have

Results at a glance Use of polyurethanes continues to grow more rapidly than the average for coating resins, due to their high performance. Technologies and future prospects are reviewed. Two-component systems are used widely as industrial coatings, particularly in demanding exterior applications, including automotive finishes. Demands for ever-lower VOC levels have placed the main emphasis in PU development on high solids and waterborne systems. Each creates specific problems for the resin manufacturer, which are briefly described. Recent developments in polyurethane dispersions (PUDs) have largely focused on eliminating the versatile but toxic solvent NMP. Higher quality macrodiols such as polycarbonates have now been introduced to enhance resistance properties. For the future, the industry faces many environmental challenges, including the quest for bio-based raw materials, and stricter controls on both the catalyst DBTL and isocyanate raw material MDI.

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H f

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Technical Paper Polyurethanes

Figure 2: Self-emulsification of hydrophilic polyisocyanate (“Easaqua”) into water (right) vs. standard hydrophobic polyisocyanate (left)

some drawbacks: problems of surface wetting due to resin polarity, a longer drying time and lower hydrolytic resistance. An alternative way to design high solids coatings is to use reactive diluents: these low viscosity components act as solvents but also participate in the final polymer network by (co)polymerising with either the polyols or the polyisocyanates (for instance aldimines or oxazolidines [3]). Low Mw polycaprolactones can also be used: their low acid value helps to reduce viscosity of conventional polyols without affecting the hydrolytic stability of the coating [4].

Good progress on the waterborne route to low VOCs Waterborne 2K systems are another key technical development, in which an unblocked polyisocyanate hardener is dispersed in an aqueous medium containing an emulsion of the polyhydroxylated binder. The most efficient way to emulsify the isocyanate is to modify it (by grafting on hydrophilic chains or incorporating surfactant systems) to achieve “spontaneous emulsification” when poured into an aqueous medium (Figure 2) [5]. The blend is applied by conventional means and the polymer network develops after removal of water and (co)solvents (Figure 3). In theory, these systems are out-

"Polyurethanes" Ulrich MeyerWesthuis www.europeancoatings.com/books

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standing as they combine the properties of PU without the need to use large amounts of solvents. But in practice, their development has not been easy: recurrent problems such as the sensitivity of isocyanate towards water and the “incompatibility” of emulsification systems caused film defects that initially limited the use of this technology. Significant improvements in understanding the physicochemical mechanisms underlying those systems have been achieved [6]. The newest generations of 2K WB PUs can match the performance of most solvent-based systems, and are used successfully to an increasing extent, for instance for plastic and wood coatings, concrete flooring, anti-graffiti coatings and leather finishing.

The quest for faster drying Another development driver for 2K PU systems is the request for greater ease of application (longer potlife) and higher productivity (for car refinishing, for instance). Fast-drying systems traditionally contained IPDI (isophorone diisocyanate) trimers in the hardener, well known for enhancing “surface cure” thanks to their hindered and high Tg structure, together with catalysts/activators for the urethane reaction. But IPDI trimers adversely affect film flexibility. Consequently, suppliers have developed new polyisocyanate structures (mostly based on HDI (hexamethylene diisocyanate) structures) offering a better compromise, while minimising the need for higher solvent levels [7]. Further advances in drying speed while retaining acceptable pot-life require other curing mechanisms and equipment, such as UV systems. Although UV-curable coatings have been greatly developed over the past 20 years, there remain drawbacks related in particular to oxygen inhibition and inadequate curing of shadow areas. Several developments have been studied (for instance the use of photoactivatable 2K systems [8]) in order to overcome these problems.

Polyurethane dispersions: a major one-component system Polyurethane dispersions (PUDs) have developed considerably since the 1990s because of environmental, health and safety benefits and their excellent performance. To-

Figure 3: Schematic representation of the application and film formation of a 2K WB polyurethane system: (a) and (b) dispersion of the polyisocyanate hardener in the aqueous phase with polyol emulsion; (c) water and solvent evaporation with particle coalescence; (d) polymer network and film formation

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Technical Paper Polyurethanes tal global consumption in 2009 was almost 228 000 wet tonnes and is expected to grow at a 5.2 % yearly average to 2014 [9]. Their major uses are in coatings and the leather & textile markets. PUDs will continue to replace solventborne technologies, though as they are more expensive, ways are constantly sought to make them cheaper. But the main issue in recent years has been to find NMP-free processes, as PUDs with more than 5 % NMP (N-methyl-2-pyrrolidone) must be labelled as toxic. The preferred production process today is the acetone process where the solvent is distilled off at the end of manufacture. Other processes used are the prepolymer mixing process, ketimine/ketazine process and melt process [10, 11]. PUDs normally have a solids content of 35-45 % and development is ongoing to reduce the water content to lower transportation and energy costs during drying, both by modifying the process [12] and by optimising the formulation [13]. Polyester diols are the macrodiol workhorse for PUDs. There has recently been increased interest in higher quality macrodiols such as polycaprolactones and polycarbonates, and several new grades of these have been introduced. They enhance outdoor durability (Figure 4), hydrolytic stability (Figure 5), abrasion resistance and chemical resistance. Polycaprolactones are generally found to offer very good toughness (see Figure 6) and abrasion restistance. Recently a new polycarbonate diol with extreme hydrophobicity has been launched giving a contact angle of 74 ° compared with 54 ° for hexanediol polycarbonate [14]. Polycarbonate diol based PUDs have also found use in soft-feel coatings for automotive interiors as they offer improved resistance against suntan lotion and cleaning agents [15]. Most PUDs are anionically stabilised with the aid of dimethylolpropionic acid and only a few are non-ionically stabilised. Normally an MPEG (methoxypoly(ethylene glycol)) chain is used, but lately a non-ionic diol has been launched giving the opportunity to more easily build in the stabilising non-ionic segment along the polymer backbone (Figure 7). Non-ionic stabilisation improves the shear and low temperature stability, tolerance to electrolytes and low pH [16]. It can be combined with anionic stabilisation to reduce the amount of stabilising amine. A lower amine content can reduce yellowing on wood substrates.

Figure 4: Improvement of weathering performance of PUDs using polycaprolactone diol structures (“CAPA 2101 A”) compared to other macrodiols

Figure 5: Hydrolysis resistance of different PUDs based on polycarbonate diols (“Oxymer M112” and “C112”, 1.6 HDO polycarbonate) compared to standard polyester and polyether diols

Several crosslinking techniques exist for PUDs In many applications, in order to improve the final coating performance, the PUD is crosslinked with materials such as polyaziridine, carbodiimide or a waterborne polyisocynate. The isocyanate reacts with active hydrogen groups such as residual hydroxyls or with primary and secondary amines located on the polymer backbone. Isocyanates can also self-condense through reaction with water followed by decomposition of the carbamic acid formed in the reaction, releasing carbon dioxide and generating an amine that quickly reacts with an isocyanate to give a urea bond.

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Figure 6: Tensile properties of different PUDs based on polycaprolactone diol (“CAPA 2201 A”) compared to other macrodiols

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Technical Paper Polyurethanes

Figure 7: Chemical structure of a nonionic diol

There is also a trend to develop self-crosslinkable PUDs. The driver is to have a stable one-component system without using hazardous components, for example by using a ketone/hydrazine reaction or acetoacetoxy reaction [17, 18]. A more recent trend is to use acrylate-modified PUDs (by end-capping with a hydroxy functional acrylate such as pentaerythritol triacrylate and by having pendant acrylate groups along the polymer backbone as shown in Figure 8) and to crosslink these materials through photopolymerisation of the double bonds. The advantages of UV-PUDs over classical UV systems are that: »»They can be spray applied without the use of any hazardous diluting acrylate monomer or solvent; »»Reduced shrinkage during cure gives better adhesion on tricky substrates; »»Less UV initiator is required, reducing costs; »»Matting is easier due to volumetric shrinkage. Even mirror-like finishes can now be made [19]. Well designed, they are even tack-free before UV cure and can have good coating properties in shadowed areas [20]. These radiation-curable PUDs are a relatively new technology with more than 20 % growth annually; they are of greatest interest in the Nordic countries and Germany for PVC floorings and wood coatings. There is also a great interest in UV PUDs for plastic coatings e.g., automotive, electronics (mobile phones, MP3 players, laptops) and for outdoor applications.

The future is cleaner and greener...

Video interviews on polyurethanes: www.european-coatings.com/videos/

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The world of coatings has always been evolving over the years, driven by different demand factors such as environmental requirements, improved performance and just fashion. Among the main future challenges, growing awareness of the global fossil oil and energy situation is crucial. This has initiated huge programmes to develop a more sustainable approach in all parts of our life and to reduce carbon footprints. Since the concept of an eco-footprint is based on life cycle thinking and environmental Life Cycle Assessment (LCA), this will impact not only on raw materials, but also

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industrial processes, the supply chain, recyclability of end products etc. A direct consequence for coating design is the quest for high performance raw materials from “green” chemistry. In polyurethanes, bio-based raw materials are not new and some are already commercial: most are carboxylic acids and glycols/polyols for making polyesters, such as succinic anhydride, dimer fatty acids, propane diol, isosorbide and pentaerythritol. Modified PUDs have been on the market for some years, using macrodiols containing oxidatively drying fatty acids [21]. Ongoing researches on acrylic acid from 3-hydroxypropionic acid from biomass may provide green acrylic polyols and greener UV-curable polyurethanes. The hardest urethane component to make from renewable resources is the (poly)isocyanate, but research is also ongoing in this field. Also, VOC emission regulations will undoubtedly be more and more stringent: the need for zero VOC already exists, with limited solutions so far. Recently, polyaspartic coating technology (using an aliphatic polyisocyanate reacted with an amine terminated polyaspartic ester) has been intensively promoted to meet this need, particularly for concrete flooring, but it still suffers from drawbacks such as poor flexibility and short potlife.

...safer... In parallel to the shift to bio-based materials and VOC reductions, the continuous need for safer raw materials will push the chemical industry and paint formulators towards new developments. In the case of polyurethanes, the change of labelling of dibutyl tin dilaurate (DBTL) [22], the long-established workhorse catalyst for urethane reactions, is an example. A similar situation is likely to occur soon with crosslinkers based on methylene diphenyl diisocyanate (MDI): the 30th Adaptation to Technical Progress (EC 2008/58/EC) aiming to re-classify MDI as a carcinogenic substance will come into force from December 1st 2010 [23]. As MDI and its derivatives are widely used in many coatings systems, this change will certainly have an impact on end-use applications and will require the development of alternative systems.

...and smarter Last but not least, new challenges will arise as the role of coatings develops further beyond protection and decoration. More and more “smart” coatings are emerging. Some paint systems already offer “selfhealing” or “self-cleaning” functionalities: self-cleaning coatings are now used at a commercial level in applications such as window glasses, cement and textiles [24], with advantageous savings in labour time, energy and water wastes. No doubt this is not a passing trend: one can imagine that coatings will play a key role in energy savings or energy transmission, monitoring information etc. Polyurethanes will obviously be the materials of choice for a number of those developments, opening new horizons for innovation.

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Technical Paper Polyurethanes

Figure 8: UV-PUD with pendant acrylate groups along the polymer chain

REFERENCES [1] Ardaud P. et al, Waterborne & solvent based surface coating resins and their application, Vol. III Polyurethanes, John Wiley & Sons, 1998. [2] Linak E., Kishi A., Urethane Surface Coatings, SRI consulting, October 2007. [3] Carter N., Urethanes Technology International, 2009,Vol. 26, No. 2, pp 25ff. [4] Klucker R., Jomier A., CAPA-polycaprolactone polyols: reactive diluents for 2K PU, St Louis Paint & Coatings Society meeting, January 19, 2010. [5] Barbeau Ph., Loubet J. L., Pavan S., Europ. Coat. Jnl., No. 12, 2005, pp 42ff. [6] Olier Ph. et al, Europ. Coat. Jnl., No. 3, 2008, pp 22ff.

The World’s Most Widely Used Weathering Tester

[7] Granier V., Forum de la Connaissance, Paris, December 2003. [8] Dogan N. et al, Europ. Coat. Jnl., No. 11, 2005, pp 36ff. [9] The Global Overview of the PUD Market, IAL Consultants, Oct 2009. [10] Gidwani A. T., PaintIndia, Aug. 2009, pp 69-84. [11] Athawale D. V., Kulkarni M. A., PaintIndia, Oct. 2009, pp 67-96. [12] Erdem B., Bhattacharjee D., US Pat. App.

Accelerate the damaging effects of sunlight, moisture & high temperatures.

2010/0015341, assigned to Dow Chemical Company, Jan. 2010 [13] Lee S. K., Kim B. K., Jnl. Colloid & Interface Sci., 2009, Vol. 336, pp 208-214. [14] Ziegler G. et. al., Nürnberg Congress, 2007. [15] Irle C., Monfort J., Revista de Plásticos Modernos, 2008, Vol. 9, No. 623, pp 380-383. [16] Winberg P. et. al., Polyurethanes for High Performance Coatings V, Berlin, Feb. 2008. [17] Pajerski A. D., US Pat. 7476705, assigned to Lubrizol Advanced Materials, Jan. 2009. [18] Pajerski A., Ahrens G., Paint & Coat. Ind., Feb. 2009. [19] Deruyttere X., Radtech Europe 2009, Nice.

• Best simulation of short-wave UV sunlight • Meets world wide test methods • Trusted by customers world wide for 40 years

[21] Honcoop E., Geuking W., Ridderikhoff H., Europ. Coat.

40 th Anniversary

Jnl., No. 4, 2008, pp 22ff.

QUV Weathering Tester 1970-2010

[20] Bernquist H. et. al., Radtech Europe 2007, Vienna.

[22] Guhl D., Polyurethanes for High Performance Coatings V, Berlin, Feb. 2008. [23] Position paper from European Diisocyanate & Polyol Producers Association, (Isopa) November 2009 at http:// www.isopa.org/isopa/index.php?page=position-papers

Q-Lab, The Most Trusted Name in Weathering Q-Lab Europe Ltd. • [email protected] • www.q-lab.com Q-Lab Deutschland GmbH • [email protected] • www.q-labdeutschland.de

[24] Parkin I. P., Palgrave R. G., Jnl. of Materials Chemistry, 2005, Vol. 15, pp 1689-1695.

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Technical Paper Fire retardant paints

Keeping cool in the mass Waterborne intumescent coatings can prevent thermoplastics from burning

* Corresponding author: Dr. Maude Jimenez Université Nord de France T +33 3 20 33 71 96 [email protected]

Maude Jimenez* Sophie Duquesne Serge Bourbigot Although intumescent coatings are widely used to protect wood and metal against fire, plastics are normally protected by adding materials to the bulk polymer, which may impair its strength. Waterborne intumescent coatings were shown to achieve a high standard of fire retardancy on two types of thermoplastic in two distinct types of fire test.

T

he main way to fire retard plastics is currently by treatment in bulk, i.e. the use of flame retardants and stabilisers directly blended into the polymer. This effective approach tends, however, to have some limitations. Usually, substantial amount of additives are needed to act efficiently, which creates three major problems: » F irst, the migration of the additives from the bulk to the surface of the polymer may form a non-uniform compound after some time; » S econdly, because of the weak interaction between the additives and the polymer matrix, fragile points are formed in the matrix, decreasing the mechanical strength of the specimens; »A  nd finally, businesses seek to reduce the thickness of their products, leading to processing issues because of the high level of fire retardant additives. There is also nowadays a tendency to avoid the very efficient halogenated compounds because of their potential secondary effects, such as the corrosive fumes and highly toxic compounds which are emitted during burning. An emerging problem is also the recyclability of fireretarded polymers, which can be particularly problematic in electrical devices.

With phosphorus based compounds saving polypropylene.

"Flame Retardant Polymer Nanocomposites" Alexander B. Morgan, Charles A. Wilkie www.wiley.com

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A good example for the limits of actual bulk treatments is polypropylene (PP). PP is widely used in many fields, such as wire and cables, automobiles, electronic, and electric industry. It is highly combustible and needs to be flame retarded. Until last years, halogen-containing compounds, alone or in conjunction with antimony trioxide, were the main flame retardants for PP. Phosphorus and nitrogen based compounds, as well as metal hydroxides constitute are now a rapidly growing group of flame retardants which are in the focus of public interest concerning environmental friendly chemicals. Metal hydroxides, mainly magnesium hydroxide and aluminum hydroxide, are commonly used in the flame retardancy of polymers due to their low toxicity and cost. But sometimes more than 60 wt% loading of metal hydroxides is required in PP to obtain efficient flame retardant properties, and

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such high loading levels lead to a great decrease in the mechanical properties of the filled polymer materials.

How to avoid dripping of Polycarbonate Same kind of observations can be done for the polycarbonate (PC): PC is known for its transparency and it exhibits excellent mechanical strength, good electrical properties and is widely used in a variety of fields such as for example electric and electronic machinery, automobiles, architecture. The aim to meet safety criteria in these various applications is to develop a PC based component which is an efficient flame retardant system, which prevents dripping during fire and which allows maintaining the mechanical and optical properties of PC. Polycarbonate resin is usually fire retarded by incorporation of a retardant during processing. The most common flame retardants used are bromine-based e.g. decabromodiphenyl ether. Another way is to add a relatively large amount of phosphorous based flame retardants (10-30 %wt.). However, these phosphorous based additives can lower the impact strength of the PC or yellow it in high-temperature or high-humidity conditions. Sodium and potassium perfluoroalkanesulfonic acids were found effective in amounts well under 0.05-0.5 %, but these components are still halogenated compounds. Some recent works have developed fire retardant PC combined with polymethylphenylsilsesquioxane spheres, but mechanical resistance problems still exist.

How intumescence improves fire protection In recent years, intumescent flame retardant (IFR) additives have aroused great interest in relation to the flame-retardancy of polymers. The IFR system is usually composed of three components: an acid source, a char-forming agent and a blowing agent which liberates gases at high temperatures. This combination creates a foamed char when exposed to fire temperatures, insulating the material below and thus protecting it against heat damage. A typical and widely studied IFR system utilises mixtures of ammonium polyphosphate, pentaerythritol and melamine (APP/PER/MEL). The main problems associated with these IFR systems can be their moisture sensitivity and poor compatibility with the polymer matrix. Instead of incorporating these materials within the polymeric matrix by bulk treatment, the idea was developed of applying them as an intumescent coating on the surface of the substrate. This is an attractive alternative method as it allows the fire retardant properties to be concentrated at the polymer surface (where the flam-

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Technical Paper Fire retardant paints Test formulations and procedures summarised

Figure 1: Flame treatment apparatus

mability risk occurs) and thus allows the bulk properties of the material to be preserved. Very few studies have investigated the use of intumescent coatings on plastics. Intumescent coatings are used worldwide for steel [1] and wood [2], some studies have been carried out on textiles with a back coating of phosphorus-containing formulations [3, 4] but only one previous study in our laboratory has shown interest in applying an intumescent coating on polypropylene composites [5].

Resolving coating adhesion problems

This paper was presented at the European Coatings Conference "Fire retardant coatings IV" 3-4 June, 2010 Berlin Germany

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One problem, however, associated with the use of coatings can be the poor adhesion of the coating onto the polymeric substrate, particularly when waterborne coatings are used. Various ways, such as corona treatments, cold plasma and more recently atmospheric plasma, exist to improve the compatibility between a (polymeric) substrate and a coating. Flame treatment is also a well-established, low cost and rapid method to improve adhesion. Passing the flame over a surface leads to an increase in its surface energy and wettability, thus assisting in providing good contact with the fluids used for decoration of the surface. This concept, involving the combination of an intumescent coating and a treatment allowing adhesion to a plastic to be improved, offers a new way to fire retard plastics. Below, some results are presented on the use of a white waterborne intumescent coating based on PVA resin and of a waterborne transparent intumescent varnish based on an acrylic resin. Both fire barrier properties and adhesion of the coatings on flame-treated polypropylene (PP) and polycarbonate (PC) samples were studied.

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Pure polypropylene (PP) and polycarbonate (PC) were used as substrates. Polymer plates (100 x 10 x 3 mm, 130 x 10 x 1.6 mm and 100 x100 x 3 mm) were prepared using a Darragon moulding press. The waterbased intumescent varnish is an acrylic resin based formulation, transparent and halogen free, containing pentaerythritol (PER), silica and phosphoric acid. The white intumescent coating is based on a polyvinyl acetate resin (“Emultex 523” from Synthomer) containing ammonium polyphosphate (APP), pentaerythritol (PER) and melamine. Both formulations were applied by dip coating to reach a dry thickness of about 200 µm. Flame treatments were carried out using an IPROS flame apparatus (Figure 1). It is possible to modify the number of treatments, the speed of treatment and the distance between the substrate and the flame. The adhesion of the film on the substrate was evaluated according to the ASTM D3359-B standard using an “Elcometer 107” cross-hatch cutter. The cutter chosen was a 3 mm cutter, with 6 teeth, corresponding to thicknesses ranging from 121 to 250 µm. Using this procedure, the best adhesion to the substrate is classified as 5B and the lowest is classified as 0B. Water contact angle measurements of the flame-treated PP and PC were determined using a “GBX 100” contact angle goniometer. The thickness of the coating and varnish were analysed using an “Alphastep IQ” mechanical profilometer.

Results at a glance Although intumescent coatings are widely and successfully used to protect wood and metal surfaces from fire, there is little evidence of their use on plastics. Instead, suitable materials are added to the bulk polymer, which may reduce its strength and cause problems with additive migration over time. A clear and pigmented waterborne intumescent coating were therefore applied to two test substrates (PP and PC). Flame treatment of the plastic surface greatly improved the adhesion of the coatings. Two different fire retardancy tests were used. In the Limiting Oxygen Index (LOI) test, the rating was increased by 13 vol.% or more to comply with the normal commercial threshold of 32 %. In the vertical burning test to ASTM D3801-1996 UL94, both coatings achieved the highest rating of V0. It therefore appears that it may be practicable to protect plastics effectively with a relatively thin intumescent coating, regardless of substrate thickness.

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Technical Paper Fire retardant paints Table 1: Optical Microscopy images of the samples classified from 0B to 5B

Two separate fire resistance tests utilised

Flame treatment greatly enhances coating adhesion

Two types of fire resistance tests were carried out. The Limiting Oxygen Index (LOI) test was performed according to the ASTM D 2863/77 standard, using an instrument from Stanton Redcroft. This test allows the determination of the minimum oxygen concentration, in an oxygennitrogen mixture, which will ensure the combustion of a sample positioned vertically (standard size: 100 x 10 x 3 mm³). The vertical burning test was conducted using a vertical burning tester (sample size 130 x 10 x 1.6 mm³ bars) according to the ASTM D3801-1996 UL94 test. The best ranking is V-0 when the burning time is short and when there is no dripping of flaming particles, whereas the worst ranking corresponds to “not classified’’ when the sample burns for more than 30 seconds or up to the holding clamp at 130 mm from the point of ignition.

Table 2: Effect of flame treatment on the contact angle and adhesion of the coating and varnish Substrate

Number of flame passes

Treatment velocity (mm/s)

Contact angle (water), degrees

Crosscut rating varnish

Crosscut rating coating

Polypropylene

-

-

91 ± 5

0B

0B

Polypropylene

2

200

78 ± 3

5B

4B

Polycarbonate

-

-

85 ± 8

0B

1B

Polycarbonate

3

200

74 ± 1

5B

4B

Table 3: Fire retardant properties of uncoated and coated polymers (after flame treatment) Polymer

LOI test (vol%)

UL 94 test (1.6 mm thickness)

Uncoated PP

19

NR (Not Rated)

PP coated with PVA coating

32

V0

PP coated with varnish

33

V0

Uncoated PC

25

V2

PC coated with PVA coating

40

V0

PC coated with varnish

58

V0

30

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The flame treatment was applied to the substrates before coating, in order to clean the surface from organic residues, to oxidise the surface and thus facilitate the adhesion of the coatings. Different flame treatments were carried out on the PP and PC samples before coating. Flame treatment allows the surface to be oxidised: the contact angle with water decreases, showing that the wettability of the samples has increased. Some reactive functionalities such as hydroxyl groups are created on the sample surface, which allows better compatibility with the coating and thus better adhesion. The best adhesion was obtained for two successive flame passes at 200 mm/s in the case of polypropylene and three successive flame passes at 200 mm/s in the case of polycarbonate. As the polypropylene (thickness 1.6 mm) began to melt after three successive flame treatments, only two passes were utilised. The samples were then coated and the results obtained using the crosshatch test are presented in Table 1 for both the coating and the varnish. The flame treatment allows the adhesion of the coating to be increased from 0B crosshatch classification to 5B classification for PP and 0B to 4B for PC, and the adhesion of the clear varnish from 0B to 5B for PP and from 1B to 4B for PC. Optical microscopy carried out on an Olympus GX51 has been carried out on the different samples. Table 1 presents the different pictures obtained for the different classifications. When the sample is 0B, all the coating is detached during the tape test. When only a major part is detached, the sample is 1B classified. It is e.g. the case for the non flamed PC coated with the intumescent coating. When the coating flakes along the edges of the cuts partly or wholly in large ribbons, as it is the case for the PC flamed one time at 200 mm/s and coated with the intumescent coating (Table2), the sample is 2B classified. When the coating flakes along the edges and /or at the intersections of the cuts, the samples are 3B classified (example of PC flamed two times at 200 mm/s and coated with the intumescent coating or the intumescent varnish). When there is only small detachment of flakes of the coating at the intersection of the cuts, the sample is 4B classified.This ranking is the best obtained for both PP and PC coated with the intumescent coating. Finally, when the edges of the cuts are completely smooth and none of the squares of the lattice is detached, the sample is 5B

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Technical Paper Fire retardant paints classified. This ranking is the best one obtained for both PP and PC coated with the intumescent varnish.

A

B

Both fire tests show very good results The fire retardant performance of the coated samples was next evaluated. The LOI and UL94 tests were carried out on both PP and PC after first subjecting them to the appropriate flame treatment as described above, and then coating them by dip coating. The thickness of the coating was about 200 µm for both formulations after drying at ambient temperature. Table 3 presents the LOI and UL94 test results obtained for the uncoated and coated PP and PC. The LOI increased by 13 vol% for PP and 15 vol% for PC in the case of the PVA-based coating, and similarly by 14 vol% and 28 vol% in the case of the varnish. All the values obtained after treatment are above 32 %, which is usually considered to be commercially acceptable. As regards the UL 94 test, the pure PP was not rated because the whole sample burned. When the coating or the varnish were applied, it reached the V0 rating (short burning time, no dripping). This protection is attributed to the formation of an intumescent coating upon heating (see Figure 2a and 2b for the white coating, Figure 3a and 3b for the varnish). The pure PC is classified V2, but in both cases the coated PC reached a V0 rating, due to the formation of an intumescent coating when the flame was applied. In both cases the improvement of flame retardancy was outstanding, using only a relatively thin coating. These results show that the preliminary studies carried out on PP and PC with two different environmentallyfriendly coatings are extremely promising. This novel approach to imparting fire resistance to polymers might work satisfactorily regardless of the thickness of the polymeric substrate. In the tests reported here, The LOI was raised to meet the usual commercially acceptable level and the coated samples reached the highest V0 rating in the UL 94 burning test.

Figure 2: (a) PC and (b) PP protected by PVA-based coating after UL94 test

A

B

Figure 3: (a) PC and (b) PP protected by clear varnish after UL 94 test

REFERENCES [1] Duquesne S. et al, Intumescent paints: fire protective coatings for metallic substrates, Surface and Coatings Technology, 2004, Vol. 180/181, pp 302-307. [2] Gu J. W. et al, Study on preparation and fire-retardant mechanism analysis of intumescent flame-retardant coatings, Surface and Coatings Technology, 2007, Vol. 201 No. 18, pp 7835-7841. [3] Horrocks A. R. et al, The potential for volatile phosphorus-containing flame retardants in textile back-coatings, Jnl. of Fire Sciences, 2007, Vol. 25, No. 6, pp 523-540. [4] Magniez C. et al, Behavior of an intumescent system for flame retardant materials coated on polypropylene textiles, Jnl. of Industrial textiles, 2003, Vol. 32, No. 4, pp 255-266. [5] Duquesne S. et al, Fire retardancy of polypropylene composites using intumescent coatings, ACS Symposium series, 2009, Vol. 1013, Ch. 12, pp 192-204.

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Technical Paper Easy-to-clean coatings

Raising the barriers to dirt

B

Problems and solutions in formulating waterborne stain-resistant paints

* Corresponding author: Oliver Wagner BASF SE T +49 621 60-99854 [email protected]

Oliver Wagner* Chee Seng Yong Jonathan Allen In many interior applications, stain resistance and dry burnish resistance are desirable. Yet stains may penetrate the surface of even some “washable” paints and become almost impossible to remove. Some considerations in formulating paints to maximise stain resistance are discussed, with test results.

P

aint users today expect more and more of their paints. Properties typically only achieved by solventborne paints are now required of waterborne ones. Moreover, waterborne paints and coatings are expected to be eco-friendly and innocuous, as these are the driving forces for the replacement of solventborne paints. Additionally, paint manufacturers may desire either to upgrade their existing interior paint lines and/or offer a USP (unique selling proposition) to their clients. As a consequence, new product lines known as “stain resistant paints” are making their way onto both European and Asia-Pacific markets. These paints require the combination of a tailored polymer dispersion with a specialised paint formulation, in order to deliver stain resistance or cleanability along with other features such as dry burnish resistance, maximum service life and an elegant subdued sheen level (down to dead flat). Key issues in formulating such paints are considered below.

Washability does not equal cleanability In a recent market study for a leading European DIY chain, consumers rated “cleanability” (see Figure 1) as the most important feature for an interior paint. Yet most interior paints on offer are marketed instead on the feature of scrub resistance or washability. This is reflected by all sorts of national testing standards for scrub resistance.

However, there is no standardised testing procedure (nor even a common understanding) for the desired feature of cleanability. To make matters worse, a great variety of “standard household stains” have to be removable from the paint, which ultimately translates into protection from both hydrophobic and hydrophilic stains. The product should be so resistant that common marks and stains can be removed virtually without trace. With its high scuff-, dry burnish resistance and durability, it will be particularly suited to high-use living areas such as bedrooms, lounges and hallways.

Factors influencing cleanability Detergents dissolve or tend to dissolve in water (or other solvents). To enable them to do this, they require distinct chemical characteristics, namely both hydrophilic and hydrophobic groups in their molecular structure. What is known as the HLB value (Hydrophilic-Lipophilic Balance) basically describes the balance of the molecular weight or relative effectiveness of the hydrophobic to the hydrophilic portion. Similarly, it might be useful to devise a term or an approach which indicates the balance of resistance of a paint to hydrophilic and lipophilic stains. Stain resistance could be achieved by a controlled microstructure of the surface, which has to be based on a non-porous continuous polymer matrix. Resistance to hydrophobic stains is then mostly affected by the pigment/filler system, whereas lipophilic resistance is more a function of the choice of polymer dispersion. In practice, of course, a paint must provide resistance to both types of stain. Additives, thickeners, dispersing agents and in general everything water-soluble naturally also contribute to the success or failure of a stain-resistant surface. These, however, can be considered as fine-tuning of the formulation, once the two major points mentioned above are addressed. In general the issue can be summarised by saying that there are two critical factors for good stain performance:

V.O

Figure 1: All pictures left section, standard interior paint; right section, stain-resistant paint

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Technical Paper Easy-to-clean coatings walls of the bathroom with mum’s lipstick. On the other hand, lipsticks of different composition are fine representatives of lipophilic stains, with excellent reproducibility in their composition. Defined colour shades (mainly red, achieved by use of water-insoluble dye) assist colorimetric measurement. The two lipsticks used in Europe differ greatly in their oil content (beeswax and castor oil) and thus their hydrophobicity.

Scrub testing determines stain resistance

Figure 2: Stain removal properties of three commercial paints: top, superhydrophobic silicone effect paint; middle, semi-gloss paint; bottom, stain-resistant paint »»Firstly, stopping stains from penetrating into the film; »»Secondly, release of the stains from the film upon cleaning. This is an important point to make. The polymer must stop liquid stains from penetrating too deeply, or no amount of cleaning will remove them. This is more often than not a problem for standard polymer dispersions.

How stain resistance tests were carried out

European Coatings Conference "Easy-toclean/self-cleaning coatings" 8/9 February, 2011 Berlin, Germany www.european-coatings.com/events

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The drawdowns of the paints to be tested were made on black “Leneta” panels with two 120 µm wet paint layers and 24 hours’ room temperature curing between these individual drawdowns. Stain resistance was tested after final curing for seven days at a constant 23 °C. Roughly 1 ml of each selected stain was applied to the paint film at right angles to the length of the panel and left for five minutes. Similarly, solid stains were wiped perpendicularly across the drawn-down film about six times. In these tests, each individual stain needs to be spread until it is approximately 2 cm wide, and 2-3 cm distance must be allowed between stains to prevent cross-contamination. After the five minute exposure period, the excess staining substance was removed with a cloth. This must be done without any pressure, so as not to start the cleaning process prematurely. The stains to be included are not part of any international norm but should make sense either in terms of the type of soiling they represent or in the cultural context of the country where the respective paints are sold. Consequently eight different stains have been chosen over the years to be tested for the European market and seven for Asian markets. In Asia test stains include black tea, coffee, red ink, blue ink, black ink, lipstick and crayon. For Europe black tea, coffee, red wine, beetroot, mustard, ketchup and two different lipsticks are used. The use of lipstick should be explained in more detail since it may not be obvious at first sight. On the one hand, kids find it a great entertainment to decorate the

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The panels were then placed in a standard scrub machine with 4 ml of a 0.25 % solution of “Marlon A350” (alkylbenzene sulfonate, sodium salt) spread on the surface of the panel. The abrasive pad was saturated with the solution and the panel was subjected to 100 scrub cycles according to DIN EN ISO 11998. Subsequently the panels were removed from the wet abrasion tester, rinsed with water, and dried at room temperature for 24 hours. CIELAB measurements are performed on areas exposed to stains and subjected to the abrasive pad as well as on unstained, but washed sections of the panel. The difference between exposed and unexposed areas is then determined as ΔE values: the smaller the ΔE, the better the stain resistance. It has been established in project work that the level of reproducibility for liquid stains is ± 10% of ΔE. When comparing different paints/formulations, sometimes averaged ΔE values (overall staining) are considered; sometimes the averages of hydrophilic or hydrophobic ΔE values are considered separately. Figure 2 shows three test specimens after stain removal.

Results at a glance Waterborne paints are increasingly being required to offer properties which match those of solventborne ones. In many interior applications, stain resistance and dry scuff resistance are desirable but may not be easily achievable. Stain resistance is not the same as ‘washability’: a paint which is not damaged by washing may allow stains to penetrate the surface so that they become almost impossible to remove. Tests were carried out to evaluate and optimise formulations for stain-resistant paints in terms of binder type, extender type and major additives (as hydrophilic thickeners or dispersants may significantly reduce performance). An optimised starting point formulation is presented which uses a pure acrylic dispersion, HEUR thickeners, mica and clay as the ‘variable’ ingredients.

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Technical Paper Easy-to-clean coatings Burnish resistance test has practical significance Burnishing will occur with people walking in narrow hallways, standing against walls or when shopping bags rub on walls. This is a dry rub that polishes the film. For the test, a Leneta panel draw down is placed in a standard scrub machine and subjected to 500 scrub cycles. Instead of a brush, a PU block wrapped with a dry cotton cloth is used. Gloss measurements are then used to define a value for the so called “dry burnish resistance” by calculating the difference in 85 ° gloss before and after polishing, with a good value being below 1.0.

Initial comparison of some premium paint types Three different paint systems were compared for various properties, with the main emphasis being of course on stain resistance. What these systems have in common is that they are of premium quality and price. They are: »»Superhydrophobic silicone effect paint; »»Semi-gloss interior paint; »»Stain-resistant paint. Comparing the staining performance of the three different paints gives a picture of great contrast (see Figures 2 and 3). The semi-gloss paint performs very badly with hydrophilic stains, e.g. tea, coffee and red wine. The silicone effect paint in contrast is very bad on lipsticks and ketchup. On the hydrophilic stains it is still poor. Only the stain-resistant paint is able to perform well on all stains tested. The silicone paint is simply too porous to prevent initial stain penetration, making subsequent stain removal useless. The semi-gloss paint in contrast does exhibit a “closed” surface, but is apparently too sensitive towards hydrophilic stains. That stems either from water soluble/ sensitive materials in the paint film or a “non-optimised” microstructure of the surface.

Nine binders compared for stain resistance The comparison of binders and subsequent selection of the most useful polymeric vehicle was rather more difficult than is implied below. In fact it was the outcome of an iterative process. This is because only an optimum formulation lets one see all the advantages of the correct binder, but by the same token only the optimum binder lets one develop the correct formulation. In an optimised stain-resistant formula at a PVC of 45 %, nine different polymers were compared for their stain removal properties with the European stains (see Figure 4). The newly developed specialised stain-resistant straight acrylic binder (No.9) exhibits the lowest averaged ΔE value for all eight stains. However, there are binders with lower ΔE values in averages of hydrophilic stains alone (No.1), but they do not perform well on the hydrophobic stains. It comes as no surprise that the protective colloid based VAc/E copolymer (No.8) performs exceptionally poorly on the averaged hydrophilic stains. Overall, for the European stain testing the averaged ΔE value for all eight stains should be below 1.0 to provide a

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Figure 3: Comparison of premium paint systems where ΔE corresponds to stain removal rating (the lower the better)

Figure 4: Comparison of polymer dispersions with ΔE denoting stain removal performance (letters beneath numbering indicate monomer composition) well-balanced stain resistant formula with good performance. It appears at first sight that the underlying principle for good stain resistance stems from the choice of main monomers, where either styrene or methyl metha­crylate in combination with butyl acrylate would be suitable. The strongest influence with polymer dispersions lies, however, with their respective stabilising system, e.g. emulsifier and/or protective colloids, their nature and amount.

Optimising PVC for cost and performance The most basic formulation parameter is the PVC. To avoid any stain penetration, the surface must be nonporous, ie the PVC must be below the CPVC. Depending on the binder and fillers employed this allows a range of 0 % to 55 %. To restrict this, it must be considered that the paint should be of premium quality, e.g. class 1 according to

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“Coatings from A to Z” Paolo Nanetti www.europeancoatings.com/books

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Technical Paper Easy-to-clean coatings DIN EN ISO 11998 (abrasion loss less than 5 µm), as well as resistant to dry burnish and completely flat. Yet the raw material cost per unit volume should be as low as possible. These factors lead to a practical working PVC somewhere between 40 % and 50 %. For a modern interior formulation it goes without saying that the paint should not just be “VOC-free”, it should

Figure 5: Comparison of thickener systems with ΔE denoting stain removal performance (letters beneath numbering indicate chemical type)

rather be “emission free”, ie, free of solvents, coalescing agents, plasticisers, ammonia, formaldehyde, etc. This imposes some demands on the binder, and also on the choice of alkali, defoamer, in-can preservative, thickener and dispersing/wetting agent.

Effects of dispersants and thickeners Four different dispersing agent chemistries were compared for their stain removal properties with the Asian stains. As could be expected, hydrophobic types such as a maleic acid diisobutylene copolymer or a polycarboxylate significantly outperformed hydrophilic ones such as TKPP or polyacrylate. (In fact, the addition of 0.1 % TKPP negated all the good stain removal properties of the hydrophobic types.) Thickeners also significantly affect stain resistance. Cellulosic thickeners are very hydrophilic and so reduce stain resistance on hydrophilic stains (usually severely), and so are not useful here. Different thickener combinations were compared for their stain removal properties with the European stains (see Figure 5). For hydrophilic stains only, HASE (hydrophobically modified alkali-soluble emulsion) thickeners are the best choice. For overall balanced stain resistance modified bentonite clay/HASE (No.5) delivered the best values followed by No.1, an HEUR/HEUR combination. But a premium paint must offer other good properties, which further limits the choice of thickeners. Thickening with HASE alone leads to syneresis as well as an unacceptable increase in 85 ° gloss after the stain removal scrub. Formulations containing the clay thickener also showed a borderline dry burnish gloss increase, and the rheology profile was unsatisfactory. In terms of scrub resistance, all paints were class 1 according to DIN EN ISO 11998. Thus, ideally one should work with HEUR/HEUR or HASE/HEUR combinations for the best overall paint property profile.

Extender choice must be checked experimentally

Figure 6: Comparison of extenders, with ΔE denoting stain removal performance (letters indicate chemical nature of the extender)

Figure 7: Comparison of the same extenders as in Figure 6, 85 ° gloss and dry burnish

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Extenders have a significant influence not only on the overall properties of any interior paint but also on the key properties of stain- and dry burnish-resistance. The choice of extenders at first sight is limitless. However, the need to meet standard properties, such as hiding power, low gloss, freedom from cracking, availability, cost competitiveness etc narrows down the choice. Suitable individual extenders (along with a standard matting agent) were rated for their stain removal properties as shown in Figure 6. However, for a better rating of the individual extender performance, the 85 ° gloss and the dry burnish should also be considered, as in Figure 7. The specific clay tested gave the best performance against tea, inks and coffee stains, but had some deficiency in red wine and crayon resistance. The two talc products tested, however, come with very similar technical specifications but with huge differences in performance, which leads to the conclusion that one cannot just generalise from all the data presented on extender classes. Strictly speaking, the results therefore only hold true for the specific selected fillers, all from leading suppliers. Naturally, two or three of the above extenders should then be combined in such way that their “weak spots” are levelled

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Technical Paper Easy-to-clean coatings out. The most successful combinations turned out to be mica in a blend with clay or talc in a blend with clay. The addition of nepheline syenite also proved to be beneficial.

Starting point formulation and some practical issues From this work a starting point formulation emerges (Table 1) based on the findings above. At a PVC somewhere between 40 % and 46 % with a TiO2 loading of 20 % (plus 3 % of an organic hollow sphere), a filler content of 16  % to 18 %, the “emission free” paint has the specialised stain resistant straight acrylic binder as a backbone. The dispersing agent is hydrophobic in nature, the rheology package HEUR/HEUR and the filler combination is mica with clay. Finally it should be mentioned that the system is still a waterbased paint and not some kind of ceramic wall cladding, and marketing as well as consumers’ expectations should be adapted accordingly. Exposure times, e.g. how long the stain is allowed to sit on the surface of the coating, are of course crucial especially when attempting to clean hydrophilic stains after complete evaporation of the liquid. Of equal importance is the drying time of the paint (especially since it is coalescent-free) before soiling occurs. For example, if freshly brewed coffee was used to stain a 1 m² test panel after 1 day’s drying of the paint and the same testing was repeated after 7 days’ drying, then the first one yielded a ΔE of 1.96 and the latter 0.75.

Table 1: Starting point formulation for stain resistant paint Ingredient

Amount

Water

186

Pigment disperser “MD 20” (BASF)

12

In-can preservative

1

HEUR – pseudoplastic type

3

HEUR – newtonian type

12

Antifoam

3

Rutile TiO2

200

Matting agent (calcined diatomaceous earth)

30

Mica

75

Clay

75

"Acronal DS 6282 X" (BASF)

373

"Aqacell OS 6273" (opaque polymer)

30

Total

1000

Solids by weight (%)

58.1

Solids by volume (%)

42.6

PVC (%)

43.6

If all of the above mentioned points are taken into account, a new premium, high value paint emerges to address so far unmet needs of consumers.

European Coatings Tech Files

Polyurethanes Coatings, Adhesives and Sealants

Polyurethane chemistry is of great significance in many applications worldwide. Moreover, their development potential has yet to be exhausted by any means. New applications are being constantly identified and the product range will be further development. This is a completely updated version of the book “Polyurethanes for Coatings” published in 1999. It is extended by applications in adhesives as well as new operational areas. It begins with an exploration of the principles of polyurethane chemistry, enabling the reader to understand the current significance of the many applications and special developments and their future perspectives. >> Polyurethanes Coatings, Adhesives and Sealants Ulrich Meier-Westhues, Nov 2007, 342 pages, hardcover 109,– W� order no. 378

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Technical Paper Fillers

Micronised filler boosts anticorrosion performance Modern corrosion tests as development tool to test them

Corresponding author: Michael Klinar Kärntner Montanindustrie GmbH T + 43 4352 54535 - 37 [email protected]

Michael Klinar Micaceous iron oxides (MIOs) are functional fillers used in anti-corrosive and industrial coatings. They act both as a passive barrier and UV-absorbing pigment and have an important effect on a coating’s performance. Therefore, viable test methods for materials containing MIO play a crucial part in their monitoring. This article illustrates these test methods, the test results and the resulting conclusions for coatings formulators.

I

n the range of different accelerated laboratory tests that are used in work on MIOs, the deciding feature is best possible correlation to the natural corrosion behaviour of a coated structure. Thus, a combined cyclic weathering/corrosion test according to ISO 20340 is used for MIO product developments in the following areas: »»To evaluate the influence on the anti-corrosion performance of coatings of essential MIO quality criteria »»To develop novel micronised MIO grades for coatings with increased anti corrosion performance »»Together with coatings producing companies, to investigate new formulations and systems based on the use of micronized MIOs The salt spray test, according to ISO 9227 is a standardised test method to monitor the corrosion resistance of coated samples. Salt spray testing is popular, because it is cheap and fast. Furthermore, it is highly standardised and reasonably repeatable. This test is regularly used in material specifications. However, the correlation between the performance in a salt spray test and the expected life of a coating is poor. To overcome this, in the 1960s, cyclic corrosion tests were developed in order come closer to actual outdoor conditions. Many different types of test were developed such as a simple test involving cycles of salt mist and dry air and more sophisticated methods such as cycles of salt mist, with the condensation of moisture, dryness and other conditions.

In the 1980s, a cycle of corrosion and weathering was developed to include the influence of UV on coatings. This was thought to be necessary, because coatings degrade by UV exposure to a greater or lesser extent depending on the type of polymer and thereby lose their ability to protect against corrosion.

Variety of conditions Since then, much work has been done to establish the usefulness of these tests. Today, a broad range of cyclic tests is available for a variety of climate simulations, from an industrial environment in a desert to severe marine conditions (e.g. splash zones). They have been standardised as ISO 20340 (Annex A), ISO 19977-2, NF T 34-600-1997 and ASTM 8594. [1] All the testwork at KMI was carried out with two or three layer systems at different film thicknesses. Cold rolled steel, previously cleaned or sandblasted, was used as the substrate The following coatings were used: »»First coat: 2K epoxy with zinc phosphate, 78 % solids, 52 % PVC »»Second coat: 2K epoxy , containing MIO at different loading levels, qualities and MIO grades »»Optional third coat: 2K polyurethane high solids, 75 % solids, 57% PVC All the coatings were solvent based and spray applied. The panels were dried at room temperature for at least three days. The following table shows the different MIO products which were used for the tests (Table 1): As MIO is mainly used in heavy-duty, anticorrosion coatings, a test cycle according to ISO 20340 (Annex A) [2] was used. This standard is especially designed for coatings on offshore and related structures. It consists of the following seven-day cycle: »»3 days UV / condensation (according to ÖNORM EN ISO 11507) [3]; UV and condensation is alternated every four hours »»3 days salt spray (according to ÖNORM EN ISO 9227) [4]

Table 1: The different MIO products which were used for the tests "Anticorrosive Coatings” Jörg Sander et al. www.europeancoatings.com/books

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Sample identification

Brand name

Fineness

Fe2O3 content

Content of lamellar particles

MIO 1

MIOX SG

max 0,1 % > 105 µm

> 85 %

80 %

MIO 2

experimental product

max 0,1 % > 105 µm

> 85 %

10 %

MIO 3

MIOX Micro 30

d98 = 30 µm

> 85 %

80 %

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Technical Paper Fillers MIO´s basic properties

Figure 1: UV-VIS-IR Spectra of MIO compared with talc (PP film)

»»1 day low-temperature exposure (-20 ± 2° C) The specified test time is 25 cycles. The following equipment was used: »»A Q-Lab combined UV/humidity test chamber, type classic »»Erichsen salt-spray chamber, type 606/400 »»Climate chamber The nature of the cycle required the test panels to be moved between various test appliances three times a week. During the duration of the test, the panels were evaluated every week to see if one of the coatings systems fails earlier than expected. After the required number of test cycles, the following evaluations were carried out to quantify the coatings performance: »»Rusting according to DIN EN ISO 4628-3 [7] »»Blistering according to DIN EN ISO 4628-2 [7] »»Corrosion on scratch according to DIN EN ISO 4628-8 [7]

Table 2: Anticorrosion performance evaluation. Test method

MIO 2 (lamellarity 10 %)

MIO 1 (lamellarity 80 %)

Blistering DIN EN ISO 4628-2

sum 2(S2)

sum1(S1)

Rusting DIN EN ISO 4628-3

Ri 2

Ri 1

Delamination / Corrosion on scratch DIN EN ISO 4628-8

Grade 3/2

Grade 2/1

From the mineralogical point of view, MIO consists of hematite. This is one of the classic iron ore minerals used in the steel industry, but its particle shape is predominately lamellar. This is the biggest difference between common hematite iron ores and MIO products. It is a pure natural product that is extracted from the ground and mechanically processed. Due to the good polymer-filler properties, MIO can be used with almost every kind of resin. Surface coating or other kinds of chemical treatment are not necessary. MIO´s chemical formula is Fe2O3. Due to the predominantly lamellar structure of the particles and the regular orientation within the coating during application, MIO acts as a passive barrier pigment. Its highly efficient ability to absorb UV-radiation and to transfer the energy into heat, makes MIO perform like a “radiation shield” and thus preventing the degradation of the coating resin. Figure 1 shows a graph of the relative transmission rates of MIO and talc. MIO is close to 0 % right across the radiation spectrum.

Results at a glance Combined cyclic corrosion/weathering tests correlate well with the true behaviour of outdoor coatings. Therefore, they are excellent tools for coatings development work, especially for the comparative evaluation between different systems and/or formulations. The content of lamellar particles is a crucial quality criterion for MIO products. This was confirmed by cyclic tests according to ISO 20340. High-lamellar, micronised MIO improves the anticorrosive performance of coatings significantly. This offers the possibility of a number of new coating systems and formulation variations. The anticorrosive performance of coatings can be improved by replacing MIO standard grades with micronised grades in the formulations. A reduction of up to 50 % of MIO in formulations is feasible by using micronised grades, without compromising anticorrosive properties.

Table 3: The influence of fineness on the anticorrosive performance of the standard grade MIO 1 and the micronised grade MIO 3. Test method

MIO 1 (standard grade)

MIO 3 (micronised grade)

Blistering DIN EN ISO 4628-2

sum 1(S1)

0

Rusting DIN EN ISO 4628-3

Ri 1

Ri 0

Delamination / Corrosion on scratch DIN EN ISO 4628-8

Grade 2/1

Grade 1/0

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Coatings formulators have a wider scope in creating colours and gloss, the covering power is increasing due to lower coatings density. Formulators of waterbased coatings can generate high-performance anticorrosive coatings and are able to avoid the problem with high-loading levels of dense MIO products.

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International standards The standard grades have been well known for many years. They are defined by the international standards EN ISO 10601:2007 and ASTM D 5532. The main quality parameters defined are described in EN ISO 10601:2007: »»Iron oxide content at least 85 % »»Particle size distribution, not more than 0,1 % > 105 µm »»Content of lamellar particles, at least 65 % for grade A Market demands for the improvement of coating performances, has prompted the development of micronised MIO grades. The biggest challenge was the identification and adaption of the grinding and selective classifying technology in order to develop appropriate processing equipment. The main requirements were a smooth grinding process, to maintain the high lamellar content of MIO, and an efficient selective classifying process to remove the ultra fines, and thus to achieve a narrow particle-size distribution. The grades are defined by the top cut=d 98 and the medium particle size = d50 of the distribution.

Lamellar content One of the most important quality criteria of MIO products is the of lamellar-particle content. To evaluate the influence of lamellarity, the following coating systems were used: »»Substrate: pre-cleaned steel (1mm thick) »»Two-layer system »»First coat with zinc phosphate as filler (60 microns DFT) »»Second coat, with 40 % MIO 1 and MIO 2 as filler, , (60 microns DFT, 45 % PVC), formulated according to DB-TL 918 300 [8] Here, two coatings systems were tested, the only difference was the lamellar-particle content of the two MIO products. Table 2 shows the anticorrosion performance evaluation. Figure 2 shows test panels with the different MIO qualities after 25 cycles according to ISO 20340. The different grades of resin degradation are visible.

Product fineness As a next step, the influence of MIO´s product fineness on the anticorrosive performance was investigated. High lamellar MIO grades were used in these formulations. Therefore, the following test setup was made: »»Substrate: steel 1 mm thick, previous cleaned »»Two layer system »»Primer coat using zinc phosphate, (60 microns DFT) »»Second coat with MIO 1 and MIO 3 at a level of 40 %, (60 microns DFT, 45% PVC), formulated according to DB-TL 918 300 [8] The results show a further improvement of the coatings performance. It is assumed that micronised products, with finer particles and thus higher specific surfaces, show a more effective distribution within the polymer matrix and improve the adhesion to the substrate. (Table 3):

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Technical Paper Fillers

Figure 2: Test panels with different MIO qualities

Figure 3 shows test panels with the MIO grades 1 and 3 after 25 cycles according to ISO 20340 As coating performance can be seen to improve by using micronised instead of standard MIO grades, a new test series with modified systems and formulations was carried out. Its targets were: »»Reduction of the MIO content in coating systems by replacing standard grades by micronised grades without compromising the anticorrosive performance »»Reduction of film thickness by using micronised grades to reach the same anticorrosive performance The following test conditions were used: »»Substrate: sand-blasted steel (3mm thick), »»Two and three- layer systems »» Primer coat using zinc phosphate (60 microns DFT) »» Second coat: formulation a): MIO 1 at 40 % (100 microns DFT, 45 % PVC), formulated according to DB-TL 918 300 »» Second coat: formulation b): MIO 3 at 24% (100 microns DFT, 45 % PVC), MIO was partially substituted by a micronised talc grade , to keep the PVC constant) »» Second coat: formulation c): MIO 3 at 40 % (50 microns DFT, 45 % PVC) »» Optional: Third coat (60 microns DFT) The tests were therefore carried out with two and threelayer systems. The results show that there is no significant difference in anticorrosive performance between the three different systems. This is true for both the two-layer and the three-layer systems (Table 4).

Lamellar content crucial

Figure 3: Test panels, MIO standard grade and micronized grade

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The level of lamellar particles in MIO products is a crucial quality criterion. In addition, micronised MIO grades improve the anticorrosive performance of coatings. The cyclic corrosion/weathering tests are a highly appropriate test method for the evaluation of the effectiveness of the different MIO-products. The test results allow the following new approaches to anticorrosive coatings, systems and formulations: It is possible, to increase the anticorrosive performance by replacing the MIO standard grade by micronised MIO grades. Alternatively or additionally, the improved efficiency makes it possible to reduce the film thickness without compromising the anticorrosion performance compared with the standard systems. This is a particularly useful feature for thin film coatings. It is also possible, to reduce the required amount of MIO in formulations by almost 50 %, replacing the standard grades with micronised grades without any loss in anticorrosive performance compared to the standard systems. This gives coatings formulators more flexibility in colour choice, gloss and a higher covering power due to the lower density of coating. Lower loading levels of MIO are interesting in waterbased coatings. In these materials, high MIO loading levels with standard grades are difficult or impossible to achieve due to the faster sedimentation of coarser particles and some rheological problems. The result is reduced anti-corrosive performance. This can be avoided in waterbased, anticorrosive coatings by using micronised MIO grades at lower loading levels.

In

Im ful

• • • • w

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Technical Paper Fillers References [1] Regan J., Brennan P., Zeise D. and James Gauntner J., Q-Lab Corporation, USA, Q-labs, UK [2] ISO 20340 paints and varnishes performance requirements for protective paint systems for offshore and related structures [3] ÖNORM EN ISO 11507 UV/condensation test [4] ÖNORM EN ISO 9227 salt-spray test [5] EN ISO 10601:2007 micaceous iron oxide pigments for paint specifications and test methods [6] ASTM D 5532 standard specification for micaceous iron oxide pig-

Table 4: Anticorrosive properties after reducing MIO content and film thickness with two layer systems (results of the three layer systems in brackets) Test method

Formulation a

Formulation b

Formulation c

Blistering DIN EN ISO 4628-2

0 (0)

0 (0)

0 (0)

Rusting DIN EN ISO 4628-3

Ri 0 (Ri 0)

Ri 0 (Ri 0)

Ri 0 (Ri 0)

Delamination / Corrosion on scratch DIN EN ISO 4628-8

5.8mm/3.2mm (6.2mm/2.8mm)

1.6mm/1.4mm (5.3mm/2.8mm)

6.4mm/3.4mm (3.8mm/3.0mm)

ments for paint [7] DIN EN ISO 4628 -2/3 and 8 evaluation of coatings: blistering, corrosion grade and corrosion on scratch [8] DB-TL 918 300 guidelines for anticorrosive coatings from “Deutsche Bahn” (German Railways)

Figure 4 shows the three-layer test panels according to the test formulations a, b and c

Inxel™ B-series Improved handling and   full color range for waterborne coatings 

•  Solid Pigment Preparations, based on an acrylic polymer  •  Easy to incorporate  •  Complete color range available  •  Enables the formulation of low or zero VOC systems www.inxel.com

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07.09.2010 14:40:07 Uhr

Events

Let's stick together The European adhesives and sealants industry met in Helsinki

Sonja Schulte Strategies, markets and future trends were keynote topics at this year’s FEICA conference. The crisis in Europe is over, and the global market for adhesives and sealants is growing, but there are also cautionary voices that hold a second crisis to be possible. Technologically, the industry is particularly interested in 100% degradable systems made from renewable resources and is working on developing them. For more events: Datum www.european-coatings.com/events

U

nder the slogan “Let’s stick together”, the European adhesives industry met in Helsinki from 15 to 17 September for the FEICA European Adhesive and Sealants Conference. Over 230 international experts came together to appraise themselves of the current and future market situation for adhesives and sealants

European Coatings Conferences

Topics 2011 The European Coatings Conferences are highly specialized innovation platforms, focussing on carefully selected, strategically defined coatings topics. Each event drills down into the heart of the respective technology issue, emphasizing best-practice and anticipated perspectives. Each occasion is a unique forum for coatings technology professionals. In addition, highly interactive discussions on technical focus issues with experts from all over the world will round off the event!

All detailed information at 44 Network European Coatings J OURNAL Vincentz · Plathnerstraße 04 4cl ·2010 30175 Hannover | Germany T +49 511 99 10 274 · F +49 511 99 10 279 · [email protected]

and to discuss business and market strategies with colleagues. The plenary session on the first day of the conference opened with a presentation on REACH and CLP by Geert Dancet of the European Chemicals Agency (ECHA). He reported on, among other things, an exponential increase in registrations in recent months. Afterwards, the participants had to decide whether to stay in the plenary session or switch to the parallel session on legislation. Most opted for the plenary session and the presentation by Roger Martin Fagg from the Economist magazine. Fagg gave an outlook on the global and European economy and the challenges they face in the future. He predicted a second recession for most countries in the world in 2011. He believed that current growth was mainly attributable to inventory build-up. However, many participants were sceptical of this. The industry was witnessing a shortage of raw materials and sharp

Berlin | Germany Five reasons to attend  Select your must-attend topics  Benefit from scientific, yet tangible information  Profit from the best value  Capitalize on the proven interface  Tool up in the pre-conference tutorials

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Events

in the development of sustainable systems. Squinzi reported double-digit growth for the Mapai Group in August 2010 whose main business lays in construction. However, in his opinion, the second half of 2010 would not be as positive as the first. However, he did not take a rosy view of the near future, but rather agreed with Fagg that Europe still faced two to three years of recession. However, in the longer term, construction industry would experience steady growth. By 2018, China would have the biggest construction industry and have surpassed the United States. The market share of Western Europe would have fallen significantly by 2018 (24% as opposed to 31% in 2008). The strategy of the Mapei Group was to continue to make invest globally, to cut costs and increase efficiency in order to prosper even in times of small margins, he said.

upward price movements. “It’s very difficult to get anything on the market,” said Torsten Lanwost, H.B. Fuller. Nor did Klaus Becker Weimann, Managing Partner at Kleiberit believe that a second crisis would surface in 2011, as he stressed in his lecture on innovative business models in the Business Forum on the second day of the conference. This view coincided nicely with the market overview data presented by Monique Dunken from Chem Research and Dave Nick from DPNA International. Their data showed that demand for formulated adhesives and sealants was growing worldwide in 2010/2011. The strongest growth market in Europe were CIC and Turkey, with annualised growth of 8% in 2011. In Asia, the largest growth was expected in India (6%), followed closely by China at 5.4%. Flexible packaging was a huge market worldwide, but sustainable bio-based systems were deemed to offer huge market potential worldwide. “In many countries, investment is being increased in this area,” reported Dave Nick. Technological solutions were also being worked on. “Biodegradable systems based on renewable raw materials are an important area within the sector, where there is a great deal happening at the moment,” said Stephan Hinterwaldner from Hinterwaldner Consulting. Giorgio Squinzi, managing director of Mapai Group, confirmed this trend in his presentation about on the strategy pursued by his company. Two-thirds of the research and development budget of the Mapai Group were being invested

Note the dates Easy-to-clean III

Extra

Attendees discussed some conference topics intensively

torials

nce tu Pre-confere

08 & 09 February 2011

Biobased coatings II 10 & 11 February 2011

Novel biocide technology V 12 & 13 April 2011

High performance waterborne clearcoats II 10 & 11 May 2011

Improving durability of coatings 07 & 08 June 2011

Anti corrosive coatings V 06 & 07 September 2011

Construction chemicals 06 & 07 October 2011

Adhesives for wind and solar technology 22 & 23 November 2011

Automotive coatings 24 & 25 November 2011

Coil and can coatings 13 & 14 December 2011

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Market Place Novel products ERRATUM In the paper "With green credentials" in the July/August 2010 issue of the EUROPEAN COATINGS JOURNAL, pp. 20-23, Figure 1 was printed with a wrong order of colours. The correct figure is depicted below.

Gentle action with peristaltic pumps With their large output range of from 17 to 25 000 l/h and a wide variety of different hose materials, the “Dulcoflex” peristaltic pumps from ProMinent are just as capable of performing tasks in the laboratory as when used in industry. They are self-priming and operate without seals or valves. Peristaltic pumps have the advantage of a gentle conveying action and can run dry. They can convey pasty or high-solids media just as easily as viscous, abrasive, corrosive or gasreleasing ones. Because the load on them is low, even products that are sensitive to shear forces can be handled. The powerful peristaltic pumps in the “Dulcoflex DFCa” range and those for high throughput, the “DFDa”, run smoothly over a long service life because of their ball-bearing-mounted rotor. These ranges can be fitted with a vacuum attachment on request. ProMinent Dosiertechnik GmbH DE-Heidelberg [email protected] www.prominent.de

Figure 1: Phase behaviour of non-ionic surfactants with 30 moles of EO

UV-curing PU dispersion with good resistance values

Acrylic emulsion imparts corrosion protection

Additive gives improved scratch resistance in automotive coatings

“Bayhydrol UV XP 2775” is an aliphatic, UV-curing polyurethane dispersion which was originally developed specifically for use in white-pigmented waterborne UV wood finishes. Accordingly, it has good resistance to chemicals and discolouring liquids such as coffee. Unlike other waterborne UV dispersions, the product retains these properties even when used in highly pigmented white waterborne UV systems, and this gives greater flexibility when formulating coatings and consequently more options for their processing and application. What is more, systems based on the new dispersion are distinguished by high hardness and have no need of cosolvents for film forming. Apart from its good properties in white-pigmented systems, this dispersion has good mechanical and chemical resistance when used for clear coats too.

Alberdingk Boley GmbH introduces “Alberdingk AC 2403”, a new acrylic emulsion that was specifically developed for aqueous corrosion protection applications. Adhesion promoters added during the polymerisation phase provide the emulsion with good adhesion to all metal substrates, including critical galvanised surfaces. The corrosion protection properties of this product are made possible by a highly hydrophobic, steam impervious film. Thanks to the low water absorption, the corrosion tendency of the coating is significantly reduced and condensation resistance is greatly improved. The production process makes possible a low MFFT, which leads to a low-VOC content. A further advantage is the option of formulating the dispersion without the addition of active fillers. Thus by using the new acrylic emulsion it is possible to produce a “European Ecolabel” compliant corrosion protection coating.

Bayer MaterialScience AG DE-Leverkusen [email protected] www.bayercoatings.com

Alberdingk Boley GmbH DE-Krefeld [email protected] www.alberdingk-boley.de

With its brilliant new “Tivida” additives, Merck KGaA is opening up new perspectives for the automotive industry. The brand was developed for use in various coating systems and significantly increases scratch resistance, in automotive coatings in particular. Small everyday scratches such as those made by wiping over the surface can be avoided or reduced when these products are added. The first product in the brand family, “Tivida AS 1010”, was developed specifically for high-gloss solventbased two-component PU coating systems The effectiveness of the core-shell nanoparticle additive is attributed to its special structure: inorganic SiO2 nanoparticles are embedded in a covalent polymer shell with OH functionality. This means the additive can bind well to the functional groups of various binding agents in coating systems. The nanoparticles make the solventbased coating system harder and at the same time more elastic, due to the crosslinking of the polymer shell with the binding agent.

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Merck KGaA DE-Darmstadt www.merck-pigments.com

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Market Place Novel products

European Coatings Symposium

VOC-free defoamer “Byk-1719” is a glycol-free and VOC-free defoamer for waterborne printing inks and overprint varnishes. The new defoamer marries the apparently incompatible properties of being both environmentally friendly and highly effective at low dosages. The additive spontaneously defoams and at the same time has no negative impact on the surface properties. The manufacturer recommends it wherever the use of glycols or VOCs could be a concern.

Modern coatings for plastics 29 October 2010 | Düsseldorf/Germany

Plastic coating – Challenges and solutions

Byk-Chemie GmbH DE-Wesel [email protected] www.byk.com

They are still notoriously difficult – when it comes to coatings and coating processes, plastic parts, with their low surface energy and their often complicated shape, pose some of the hardest challenges.

In cases where a surface is to be covered with a uniform, reproducible film (film application), a large number of absolutely identical samples has to be produced or reliable information is needed on the relationship between the wet and the dry film thickness (drying time measurement), it is recommended to use an automatic film applicator. The inevitable irregularities and inaccuracies which are encountered when applying films manually are avoided by using the automatic drawing method. For this, the measuring and test equipment manufacturer Erichsen proposes its new combined film applicator and drying time recorder, the “Coatmaster 510”. The precision-engineered drive components, together with a correspondingly advanced control system, mean that the processing speeds are finely graduated. As a result the processing control provides the necessary basis for good reproducibility over the entire range of preselectable speeds, both in film application and in dryness testing.

This symposium provides an overview of the most recent developments in this field, ranging from new coating raw materials, to new coating systems and new surface modifications. The event is especially dedicated to innovative materials and technologies for the coating of plastic substrates - including coatability and pretreatment aspects of the substrate material itself, novel raw materials and formulations for coatings, as well as application aspects. Several presentations will be focused on waterborne technology, as this is one of the most important future technologies for the coating of plastics. Also functional coatings will be addressed as well as UV technology and renewable materials. For the first time this event takes place in Düsseldorf/Germany, contemporaneously with the K 2010, the world’s leading trade fair for the plastics and rubber industry. An excellent opportunity to get more mission critical information in less time. Pictures: Doc RaBe - Fotolia.com, Sulabaja - Fotolia.com, Maria Cristina Sterra - Fotolia.com

Film applicator and drying time recorder

Erichsen GmbH & Co. KG DE-Hemer [email protected] www.erichsen.de

All detailed information at Vincentz Network Plathnerstr. 4c 30175 Hannover Germany

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Contact: Nicole Steinbach · T +49 511 99 10-274 [email protected] http://www.european-coatings.com/events/ecc-symposium.cfm

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Market Place Novel products

Water jet pump for mobile cold cutting Water jet manufacturer Jet Edge, Inc., introduces the 80hp, 60,000 psi “iP6080DS” diesel-powered water jet intensifier pump. The water jet pump is capable of producing up to 5.1 l/m of ultra-high pressure water for mobile water jet cutting applications, and is especially suited for cold cutting in environments where heat and flames are restricted. Built with the contractor in mind, the pump is powered by a reliable four-cylinder Cummins turbocharged diesel engine and is designed for portability and ease of maintenance. Intensifier components can be accessed without having to get into the hydraulic center section and hydraulic rod seal. No special tools are required. Jet Edge, Inc. USA-St. Michael [email protected] www.jetedge.com

Looking for more novel products? Browse the EC Market Navigator, your supply network: www.european-coatings.com/ marketnavigator

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Accurate measurement of paint and powder thickness

Uninterrupted sample processing

The “Elcometer 415” paint and powder coating thickness gauge provides a simple, accurate and reliable way to measure coatings on all smooth, magnetic and non-magnetic metals. With its rugged housing of ABS plastic and a measurement range of 0 1000 μm, this gauge fits easily in the hand and is suitable for use in the paint shop, on powder coating lines and in the automotive sector. The unit has a fast, accurate reading rate of more than 60 measurements per minute. The large angled display makes it easy to read from any viewing angle, and on-screen instructions guide the user through the functions. Depending on the substrate the gauge switches automatically from the ferrous (F) to the non-ferrous setting, and the “Bigfoot” probe gives it a high level of measuring accuracy.

Entering sample tables and tasks into analytical instruments and automated pipetting systems takes time and is prone to error. And the larger the number of samples the more difficult it becomes to oversee the various samples that are being processed in parallel. The “Workflow Manager” from Manz is laboratory control software that takes over these tasks: processes can be flexibly configured and linked to the sample data. The software controls the generated tasks across all the connected instruments. Samples are identified by each instrument from their barcodes and are automatically processed using the appropriate method. Results are stored in the software’s database and are easily exported as a printed report or database records to an electronic laboratory notebook, LIMS or ERP.

Elcometer Instruments GmbH DE-Aalen [email protected] www.elcometer.de

Manz Automation AG DE-Reutlingen [email protected] www.manz-automation.com

Particle size analyser improves efficiency

Delo Industrie Klebstoffe has developed special adhesives for the photovoltaic sector. The new two-component epoxy resins “Delo-Duopox RM885”, “Delo-Duopox RM864” and “Delo-Duopox RM845” are used especially in the fabrication of wafers. In this, silicon ingots are applied to a carrier plate with adhesive and then sawn into paper-thin (170 to 200 µm) monocrystalline or polycrystalline silicon slices. Once cut, the wafers have to be separated and completely cleaned of adhesive. The new products display fast initial tack, very good removal behaviour and a high resistance to heat. Whereas “Delo-Duopox RM864” is very easy to remove after the cutting operation with a warmed weak acid, the other two adhesives – which can also be removed with acid – can alternatively be taken off simply with hot water.

The Rotex “Global Gradex 2000” particle size analyser is a patented PC-controlled device that improves efficiency and accuracy of quality control programs by providing reliable, fully automatic sieve analysis. The instrument performs analysis with immediate results, in the lab or on the plant floor, elevating test quality with improved test accuracy and repeatability. Designed to enhance quality control programs, the device reduces costs, ensures more accurate test results, and provides reliable performance. It lowers operational costs by providing greater testing capacity and operational flexibility without additional manpower. Tests can be initiated with a single keystroke while system automation frees technicians to perform other tasks as up to seven samples are being tested. Full automation also provides analysis on a more frequent and timely basis, allowing for closer control of raw material receipts, materials in process, and finished products. The ability to test more frequently decreases the quantity of off-spec product and reduces reprocessing costs.

Delo Industrie Klebstoffe DE- Windach [email protected] www.delo.de

Rotex Global, LLC USA-Cincinnati [email protected] www.rotex.com

Special adhesives for the solar industry

www.european-coatings.com

Market Place Novel products Measuring device for compact FT-IR spectroscopy Thermo Fisher Scientific Inc. announced the introduction of its newest FT-IR spectrometer, the Thermo Scientific “Nicolet iS5”, powered by “Omnic” software. The spectrometer is designed for users seeking no-compromise, affordable and compact FT-IR spectroscopy to assist in their product assurance testing, basic troubleshooting and chemistry teaching. The instrument establishes a new benchmark in small-footprint laboratory FT-IR spectroscopy. Delivering comparable performance to full-size spectrometers, the instrument has an open-architecture sample compartment that accepts a wide variety of sampling accessories. The spectrometer, its new iD sampling accessories and software solutions for raw materials, impurities and mixtures identification, creates a special user experience “from sample-in to answer-out.” Thermo Fisher Inc. USA-Madison [email protected] www.thermoscientific.com/ftir

Particle measuring instrument gives fast, accurate analysis The new “Camsizer XT” provides a marked improvement to quality control for fine powders of between 1 µm and 3 mm: faster, more accurate analysis of the particle size and shape gives higher-quality products, reduces reject rates and keeps costs down. The analyser is a new development on the “Camsizer” optical particle analyser but is designed for finer samples. Significant differences from the earlier unit include not only improved optical resolution but also new options for feeding the samples. Fine particles tend to agglomerate, which makes it difficult to record the properties of an individual particle. This means that there must be as wide a variety of ways to feed the sample to the measuring instrument as possible. So the new unit offers three different dispersion methods: pourable, non-agglomerating particles are measured in free fall; the “Dry Powder Feeder” disperses agglomerated particles through a nozzle at adjustable positive pressure; and wet dispersion is possible with optional ultrasound. Retsch Technology GmbH DE-Haan [email protected] www.retsch-technology.de

www.european-coatings.com

HEXA for THE EUROPEAN PRODUCER LEADER IN FLUOROCHEMICAL SPECIALTIES PRESENTS ITS NEW PRODUCT RANGE ®

HEXAfor™ high performance short chain

Fluoropolymers and Fluorosurfactants

Fe: ed pt z i n o icr 10 For m ov. 20 dorf .–3n üssel t c o 7 0 in d 2 1 0 2 s at K Visit u and c30 t S Hall7

MAIN APPLICATIONS

STONE, MARBLE, CONCRETE AND WOOD PROTECTION, ANTI-GRAFFITI PAINTS&COATINGS, FLOOR POLISH EASY TO CLEAN

JUST CONTACT MAFLON THE FLUOROCHEMICAL SPECIALIST

Guarniflon S.p.A. Maflon Division Via T.Tasso 12 Castelli Calepio (BG) IT Phone +39.035.4494311

Fluorochemical Specialties http://www.maflon.com email: [email protected] Technical Dept. Fax +39.035.4494331

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Calendar of Events 2010 Conferences 11 – 13 October 2010 2010 Tappi Advanced Coating Fundamentals Symposium Munich/Germany www.tappi.org 12 – 13 October 2010 Wood Coatings Congress Amsterdam/The Netherlands www.pra-world.com

2 – 4 November 2010 3rd Global Marine Coatings Forum Singapore [email protected]



3 – 4 November 2010 Car Body Painting 2010 Bad Nauheim/Germany www.automotive-circle.com 9 – 10 November 2010

12 – 13 October 2010 EC European Coatings CONFERENCES: Packaging coatings Berlin/Germany www.european-coatings.com/ events/ecc.cfm

 EC European Coatings

Conferences: Smart coatings VI Vincentz Network Berlin/Germany www.european-coatings.com/ events/ecc.cfm 9 – 11 November 2010

12 – 14 October 2010 5th World Congress on Emulsions Lyon/France www.cme-emulsion.com 13 – 14 October 2010 North African Coatings Congress 2010 Casablanca/Morocco www.coatingsgroup.com 29 October 2010 EC European Coatings SYMPOSIUM: Modern Coatings for plastics Vincentz Network Düsseldorf/Germany www.european-coatings.com/ events/ecc.cfm

Genoa/Italy www.fatipec2010.com/default. html

Exhibitions

23 – 25 November 2010

 Advances in Coatings Technology ACT’10 Katowice/Poland www.impib.pl

7 – 8 December 2010 EC European Coatings CONFERENCES: Polyurethanes for high performance coatings VI Vincentz Network Berlin/Germany www.european-coatings.com/ events/ecc.cfm



12 – 14 October 2010 COROSAVE Stuttgart/Germany www.corosave.de 9 – 11 November 2010 Eurocoat 2010 Genoa/Italy www.eurocoat-expo.com New   events in our list

or events with changes.

More coatings events at www.european-coatings.com events/coatings_calendar

Would you like to include your company event in our Events section? For more information please contact our advertising sales team: Sabine Wilkens Tel. +49 511 9910-255, [email protected]

Source: Pressmaster – Fotolia.com (left)



 XXX FATIPEC Congress

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