Paint & Coating Industry April 2011

April 2011 VOLUME 27, NUMBER 4

INSIDE Environmentally Friendly Wetting Agents

Paint

Silicone-Modified Polyurethane Dispersion

Coatings Industry

Adhesion-Promoting Oligomers

Globally Serving Liquid and Powder Formulators and Manufacturers

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CONTENTS PA I N T & C O AT I N G S I N D U S T RY , V O L U M E 2 7 , N U M B E R 4

April 2011

FEATURES 24 A New Environmentally Friendly Wetting Agent for Architectural Coatings, Air Products and Chemicals, Inc. 32 Environmentally Progressive Polyurethane Coating Technologies, Yantai Wanhua Polyurethanes Co. Ltd. 38 Low-VOC Colorants for Solventborne Industrial Coatings, Colortrend USA LLC 42 A New Substrate Wetting Additive for Low-VOC Aqueous Adhesive Products, Troy Corporation 46 Novel Silicone-Modified Polyurethane Dispersion Technology for Advanced Coating Systems, Evonik Industries Coating Additives 52 Acrylated Products Designed for Formability and Adhesion Enhancement in Direct-to-Metal Applications, Sartomer USA

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ONLINE FEATURES w w w. pcimag.com Why Manufacturing Is Leading the Economic Recovery, Fabricators & Manufacturers Association Bio-Based Solution for Self-Leveling Coatings, Bayer MaterialScience Sustainability Secrets of Material Safety Data Sheets, Actio Corporation New Urethane Gel Coat Targets Global Wind Energy Market, PPG Commercial Coatings Going Green – Automating Product Compliance Throughout the Product Life Cycle, IHS

DEPARTMENTS 6 8 12 14 18 60 63 64

Viewpoint Industry News Calendar of Events Company News Names in the News Products Classifieds Advertiser Index

BUSINESS TOOLS 20 Green Technology Profiles 22 Green Showcases 50 Supplier Showcases

PCI - PAINT & COATINGS INDUSTRY (ISSN 0884-3848) is published 12 times annually, monthly, by BNP Media, 2401 W. Big Beaver Rd., Suite 700, Troy, MI 48084-3333. Telephone: (248) 362-3700, Fax: (248) 362-0317. No charge for subscriptions to qualified individuals. Annual rate for subscriptions to nonqualified individuals in the U.S.A.: $115.00 USD. Annual rate for subscriptions to nonqualified individuals in Canada: $149.00 USD (includes GST & postage); all other countries: $165.00 (int’l mail) payable in U.S. funds. Printed in the U.S.A. Copyright 2011, by BNP Media. All rights reserved. The contents of this publication may not be reproduced in whole or in part without the consent of the publisher. The publisher is not responsible for product claims and representations. Periodicals Postage Paid at Troy, MI and at additional mailing offices. POSTMASTER: Send address changes to: PCI - PAINT & COATINGS INDUSTRY, P.O. Box 2145, Skokie, IL 60076. Canada Post: Publications Mail Agreement #40612608. GST account: 131263923. Send returns (Canada) to Pitney Bowes, P.O. Box 25542, London, ON, N6C 6B2. Change of address: Send old address label along with new address to PCI - PAINT & COATINGS INDUSTRY, P.O. Box 2145, Skokie, IL 60076. For single copies or back issues: contact Ann Kalb at (248) 244-6499 or [email protected].

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Associate Member

Printed in the U.S.A.

V I EWPOINT

Some Positive News About U.S. Manufacturing U.S manufacturing has been in the news a lot over the past several years – and not in a positive light. But two new reports issued in February tell a different story. According to an article in the Wall Street Journal on February 25, author Mark. J. Perry, a Professor of Economics at the University of Michigan, Flint, tells of a thriving and growing U.S. manufacturing sector. “In 2009, the most recent full year for which international data are available, our manufacturing output was $2.155 trillion (including mining and utilities). That’s more than 45% higher than China...” Perry also states that in 2009 the U.S. produced more than 20 percent of global manufacturing output, and points out that “excluding recession-related decreases in 2001 and 2008-09, America’s manufacturing output has continued to increase since 1970.” The article recognizes that although the United States is still making a lot of products, it is able to do it with far fewer workers than it needed in the past. Productivity-enhancing technology means fewer workers in the highly automated plants, and displaced workers are required to learn new skill

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sets. Shifting to a more efficient economy has been a bumpy road for many people. A second article, written by Dr. Chris Kuehl, Economic Analyst at the Fabricators & Manufacturers Association (FMA), claims that the manufacturing sector is leading our economic recovery. It states that in 2010 there were more jobs added in manufacturing than were lost – 130,000 of them. This is the first time this has happened since 1997. Kuehl says that the trend is heading in a positive direction, and some expect a net job gain of 500,000 by the end of this year. He offers three reasons as to why manufacturers have played such an important role in this stage of the economic recovery. 1) Better Management – Most companies’ executives today are actively engaged in strategic planning, market development and human resource management. Not many years ago, this was not the case – it was all about the fastest and cheapest way to get something out the door. 2) Emphasis on Strategy and Marketing – This either means that companies have launched new product lines to access new markets, or they have taken existing products into the global marketplace. Kuehl reports that as recently as 10 or 15 years ago the majority of small and medium manufacturers did no business at all overseas. But the average company now does about 30 percent of its business in global markets, and some have much higher rates. The weak dollar, making U.S. goods cheaper to foreign buyers, has accelerated this trend. 3) Adaptation – The manufacturing sector has aggressively adapted to new business environments. Manufacturers have become much more capital-intensive and are relying more on technology to stay competitive. The FMA article emphasizes that manufacturers must maintain their momentum. “In looking ahead, it is apparent that parts of the world will have an advantage when it comes to production costs in many situations. This means U.S. companies must out-manage and out-strategize their competitors,” Kuehl says. The full article is posted as an Online Article this month at www.pcimag.com. Obviously, not all manufacturers are going to find that these reports ring true to their own experiences. The coatings industry has had its own challenges with raw material shortages and price increases over the past several years, which have had, and continue to have, a very negative effect. But overall, I am glad to see some positive news about the manufacturing sector in general. I would be interested to hear your thoughts and comments on this topic. Feel free to e-mail me at [email protected].

By Kristin Johansson, Editor | PCI

Markets:

Architectural Coatings

Industrial Coatings

Container Automotive

Civil Aerospace Engineering

Coatings Technologies:

SolventBorne Coatings

WaterBorne Coatings

Powder Coatings

Surface/Substrate:

Wood

Brick

Concrete

Marine & Maintenance

UV Coatings

Metal

Stucco

High Solids Coatings

Vinyl

Plastic

Brenntag understands change is normal for the Coatings Industry. As the Coatings Industry has evolved through the years, Brenntag’s Paint and Coatings Team continues to provide our customers with the products and services to stay competitive in the marketplace. Whether you face different markets, technologies, or substrate applications, Brenntag’s Paint and Coatings Team can help you to adapt and make change work to your advantage.

Brenntag offers a complete specialty and industrial product portfolio, technical assistance with product development, formulations and applications know-how, superior logistics with versatile blending and re-packaging capabilities, and last, but not least, commitment to quality and safety. Change demands innovation and creativity. Brenntag Understands. Brenntag North America, Inc. (610) 926-6100 Ext: 3858 [email protected] brenntagnorthamerica.com

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I NDUSTRY NEWS

Good Economic Prospects Forecast for Euro Zone NÜRNBERG, Germany – In an analysis provided by NürnbergMesse, one of the 20 largest exhibition companies in the world, signs indicate growth again in Europe. In 2010, the majority of the members of the euro zone succeeded in leaving behind the consequences of the global financial and economic crisis. The leader is Germany with gross domestic product (GDP) growth of 3.8 percent. The euro region expects an increasing worldwide demand for products and services in 2011, and the industry is suitably prepared. The stability of the euro promotes exports, which are important for the euro zone. German companies in particular are profiting from the worldwide recovery. The machinery and plant manufacturers and the automotive industry are currently achieving large export growth. For example, Volkswagen, Daimler and BMW report huge rises in sales, and even shortened the holidays over Christmas. The orders in the component-supply industry are increasing accordingly. The development in the chemical, electrical engineering and building industries is similarly positive. The latter is

benefiting from energy-saving renovation work on buildings, and the large demand for solar and photovoltaic products. The economic power of Germany’s neighbors, Belgium, Denmark, France, Luxembourg, the Netherlands, Austria and the Czech Republic, increased by approximately two percent in each country in 2010. Growth in Slovenia and Slovakia also picked up speed in 2010. Finland proved its capacity once again with some three-percent growth. This Scandinavian country is one of the most

EPA Awards $5.5 Million to Support Nanotechnology Research

competitive economies in the euro zone. A strict cost-cutting plan, along with privatization and investment in the hightech sector and the educational system, rescued the country from bankruptcy after trade with Eastern Europe came to an end, triggered by the collapse of the Soviet Union. Today, Finland is distinguished by its extremely low national debt and small budget deficit. The difficulties experienced by individual countries in the euro zone in 2010 were offset by loans from the Eurogroup. At the same time, the body of the European Union, in which the euro zone states coordinate their fiscal and economic policy, imposed strict rules on the countries in deficit. The number of customers from emerging economies who are interested in European products is growing. This is because the economies in China, Brazil and the emerging countries of Southeast Asia recovered more quickly than in the industrial countries. In addition, Europe should be able to expand its position as a leading supplier of eco-technologies in the future.

Turkcoat Eurasia Returns to Istanbul ISTANBUL, Turkey – Turkcoat Eurasia 2011, the 4th International Coatings, Inks, Adhesives, Sealants, Construction Chemicals, Raw Materials and Production Technologies Exhibition will take place Oct. 6-8, 2011, at the Istanbul Expo Center, Istanbul, Turkey. Visit www.turkcoat.com for additional information.

WASHINGTON, DC – The EPA has awarded $5.5 million to three consortia to support research on nanotechnology. The EPA is collaborating with the United Kingdom’s Natural Environment Research Council on the project. The grants will help researchers determine whether certain nanomaterials can leach out of products such as paints, plastics and fabrics when they are used or disposed of, and whether they could become toxic to people and the environment. In addition to EPA’s $5.5 million, the Consumer Product Safety Commission has contributed $500,000 through a new research partnership between the two agencies. Grant awards were made to three consortia consisting of researchers from the United States and the UK.

LAS VEGAS – The 30th Biennial Western Coatings Symposium (WCS) will take place October 23-26, 2011. Sponsored by the Arizona, Golden Gate, Pacific Northwest and Los Angeles Societies for Coatings Technology, the WCS will be held at The Mirage Hotel, Las Vegas, NV. Additional information about the event can be found at www.wcsshow.com.

Sink or Swim Symposium Set for May

Register Now for the Windy City Coatings Course

CLEVELAND – The 54th Annual Sink or Swim Technical Symposium will be held at the University of Akron, in conjunction with the Department of Polymer Engineering, on May 24-25, 2011. The event will feature a one-day exhibit on May 24 and a reception in the exhibiting hall. Organizers promise a strong technical program again this year, as well as a short course. Visit www.clevelandcoatingssociety.org for additional information.

CHICAGO – The Windy City Coatings Course will take place April 27-28, 2011, in Rolling Meadows, IL. It is a two-day educational course that offers introductory and advanced sessions led by industry experts. It also provides an opportunity to network and discuss best practices with both veteran and novice coatings professionals. Visit www.windycitycoatingscourse.com for additional information.

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Western Coatings Symposium Seeks Technical Presentations

I N DUSTRY NEWS OBITUARIES Industry Loses Stuart Aronson

Bring on all your bright ideas. Our global UV/EB resources help make them winners. Wherever you need UV/EB support, Sartomer is there for you – in the Americas, Europe, and Asia. We deliver leading-edge UV/EB technology and responsive local manufacturing. We can also help with the complexities of product/country registration issues. Our in-depth expertise and high-performance specialty chemicals will help you

NORTH OLMSTED, OH – Stuart Aronson, age 69, passed away on January 23. A veteran of the industry for over 40 years, Aronson held positions at Neville Chemical, Polyvinyl Resins (now DSM), SP Morell, Focus Chemical and, most recently, Palmer Holland. Aronson was a member of SACI, the FSCT and the Baltimore Society for Coatings Technology. He served on the Board of Directors of the New York Society for Coatings Technology as the Employment Chairman. Aronson is survived by his wife Eileen, two daughters, a stepdaughter, a stepson and four grandchildren.

President of Cianflone Scientific Instruments Corp. Passes Away PITTSBURGH – Bob Cianflone, President and CEO of Cianflone Scientific Instruments Corp., passed away unexpectedly on February 19. He was preceded in death by his wife, Rose, and is survived by three sons and seven grandchildren. Cianflone Scientific Instruments Corp. will continue to remain in business, as this was Cianflone’s wish.

bring all your ideas to life and get them to market – fast. Now you can take on any job – plastic and metal coatings, inks, display, automotive, adhesives – or even a totally new application. Rely on us from initial concept to final delivery. Formulators choose Sartomer for UV/EB innovation and consistent quality… batch after batch. Our broad line of more than 500 monomers and oligomers leads the world. If your formulation calls for something unique, we tailor a custom fit. Contact us now for the help you want to beat the competition. Call 800-SARTOMER, 610-363-4100 or visit www.sartomer.com.

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SSCT Annual Meeting to be Held in May HATTIESBURG, MS – The Southern Society for Coatings Technology’s 2011 Annual Meeting will take place May 22-25 at the Mills House Hotel in Charleston, SC. The theme of the event will be “Beginnings of the Coatings Revolution,” and will include a Keynote Address on Macroeconomic and Sourcing Trends presented by Brad Walden of Buckman International. The 21/2-day meeting will include technical presentations, tabletop exhibits and the presentation of the A.L. Hendry Award. Visit www.ssct.org.

ICCE-19 Announces Call for Papers SHANGHAI – The 19th Annual International Conference on Composites/Nanoengineering (ICCE-19) will take place in Shanghai, China, July 24-30, 2011. The ICCE conference will provide a forum for the exchange of information and ideas in virtually all areas of composite materials research. Visit www.icce-nano.org for additional information. 䡲

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9-13 Introduction to Paint Formulation http://coatings.mst.edu 10-12 Radiation Curing Technology www.pra-world.com 11-13 Coat Expo China 2011 www.coatexpo.cn/en 11-13 Northwest Coatings Fest www.pnwsct.org 12 Fundamentals of Color and Appearance www.xrite.com 12-13 Hazardous/Toxic Waste Management Workshop www.Lion.com 16-19 Paint Technology www.pra-world.com 18-19 Asia Coatings Congress www.coatings-group.com 22-25 SSCT Annual Meeting www.ssct.org 23 Fundamentals of Color and Appearance www.xrite.com 24-25 Powder Coating Technology www.pra-world.com 24-25 Sink or Swim Symposium www.clevelandcoatingssociety.org 30-June 1 EuroNanoForum www.euronanoforum2011.eu 31-June 2 Aluminium-21/Coatings www.eng.alusil.ru/2006

JUNE 7 Paint & Coatings Basics www.pra-world.com 7-8 Powder Coatings Forum www.powdercoatingsforum.com

WHAT ARE WE HIDING?

Breakthrough hiding technologies to make your TiO2 go further. Coming in 2011. www.dow.com/hiding

C O M PANY NEWS

Heucotech Completes Colorants Facility in Pennsylvania FAIRLESS HILLS, PA – Heucotech Ltd., a member of the Heubach Group, has completed construction of a facility in Fairless Hills, PA, for the production of universal colorants for decorative coatings for the NAFTA market. Heucotech will produce the Heucotint line of universal colorants in this facility to serve the needs of the architectural coatings market. An environmentally

friendly product line, Heucotint is VOC-, APE- and formaldehyde-free. It will work

in either aqueous or solvent-based products as well as in conventional technology or in low-VOC coatings. This new business in the NAFTA region will expand on the success of the Heucotint line in Heubach Europe, utilizing the existing base of global technology knowledge in colorants. The product line will address specific customer needs with innovative and custom solutions.

U.S. Zinc Facility Recognized for Recycling

Berkshire Hathaway to Acquire Lubrizol

HOUSTON – U.S. Zinc’s zinc oxide plant in Changshu, Jiangsu, China, has been certified as a model unit in the recycling economy by the Suzhou Municipal Government. The facility is located in the Changshu Economic Development Zone with many other corporations. These industries, all located within close proximity, work together to form a recycle chain where waste from one industry is then used by another industry as raw material for production. U.S. Zinc achieves zero waste in the operation of this facility. Additionally, U.S. Zinc’s plant uses natural gas and produces no wastewater in its processes.

OMAHA/CLEVELAND – Berkshire Hathaway Inc. and The Lubrizol Corp. announced a definitive agreement for Berkshire Hathaway to acquire 100 percent of outstanding Lubrizol shares for $135 per share in an all-cash transaction. The transaction is valued at approximately $9.7 billion, including approximately $0.7 billion in net debt, making it one of the largest acquisitions in Berkshire Hathaway history. It is expected to be completed during the third quarter of 2011. After the close of the transaction, Lubrizol will operate as a subsidiary of Berkshire Hathaway and will continue to be led by its current management team.

NEI Corp. and Sekisui Chemical Co. Sign Agreement

Sika Corp. Opens New Warehousing Operation in Ohio

SOMERSET, NJ – NEI Corp. and Sekisui Chemical Co. of Japan have signed an exclusive agreement to license NEI’s technology for surface protection of transparent polymers used in automotive applications. The NEI technology complements coatings developed by Sekisui Chemical Co. that enhance the weatherability of polymers.

MADISON HEIGHTS, MI – Sika Corp. announced the opening of a new 200,000-square-foot warehousing facility at its Marion, OH, location. Benefits of the new facility include a consolidated shipping point and expedited material flow for Sika business units. The new facility is located adjacent to the Marion plant and adds ample space for future growth. The new warehouse address is: Sika Corp., 1550 Cascade Drive, Marion, OH, 740/375.3021.

AkzoNobel Opens Industrial Coatings Plant in India AMSTERDAM, The Netherlands – AkzoNobel is one step closer to its goal of accelerating growth and increasing revenue in India to €1 billion within the next five years with the official opening of a new industrial coatings plant near Bangalore, Karnataka, India. The facility, which will produce coil and specialty plastic coatings, is located in Hoskote on an existing AkzoNobel site, which already manufactures marine and protective coatings, automotive coatings and powder coatings. The new facility will be capable of manufacturing up to 18 million liters per year, with scope for further expansion.

Valspar Names ChemPoint.com Exclusive Distributor MINNEAPOLIS – The Valspar Corp. has selected ChemPoint.com as the exclusive decorative powder coatings distributor for those customers who purchase in small quantities in the United States and Canada. ChemPoint will provide marketing, sales and order fulfillment for this key segment of customers. 14

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BASF Appoints New Polyurethane CASE Distributor WYANDOTTE, MI – BASF has appointed Ribelin Sales Inc. as a southeast and Gulf Coast U.S. distributor for polyurethane chemicals to the CASE (coatings, adhesives and binders, sealants and elastomers) market.

Oxea Expands Specialty Ester Capacity OBERHAUSEN, Germany – Oxea has announced significant capacity expansion for specialty esters. The capacity of the existing Ester unit in Oberhausen, Germany, will be extended by 40 percent, effective the second half of 2011. Additionally, Oxea intends to build a new unit in Oberhausen, which is scheduled to come on line in the second half of 2012. These capacity increases will support the increasing market shift to phthalate-free plasticizers.

WHAT ARE WE HIDING?

WHAT ARE YOU HIDING?

EVOQUETM Pre-Composite Polymer Technology is something new- and very different-in hiding. A breakthrough in emulsion polymers, EVOQUETM Pre-Composite Polymer combines with TiO2 during the paint-making process to form a composite particle that enhances TiO2 hiding efficiency. It’s an advance that won’t put TiO2 out of a job-it just makes it work smarter. And that means less TiO2 to deliver equal or better levels of both wet and dry hiding. Contact Dow today about rethinking your approach to hiding using EVOQUETM Pre-Composite Polymer. When your experts talk to our experts,hiding good things happen. Breakthrough technologies to make your TiO2 go further.

Coming in Spring 2011. www.dow.com/hiding Coming in 2011. www.dow.com/hiding

C O M PANY NEWS Huntsman to Expand Capacity at Singapore Polyetheramines Plant THE WOODLANDS, TX – The Performance Products division of Huntsman Corp. is going ahead with the engineering design for a 40,000-ton capacity expansion program at its polyetheramine facility in Singapore.

Huntsman plans to invest more than $70 million at its Jurong Island plant in a move that will more than double the site’s manufacturing capabilities, help satisfy increasing global demand for polyetheramines and strengthen the company’s leadership position in this technology.

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Brenntag Opens New Distribution Facility in Indonesia JAKARTA, Indonesia – Brenntag, the global leader in full-line chemical distribution, unveiled its new distribution facility in Jakarta, Indonesia. The facility will provide a bigger storage capacity than the current warehouse in Jakarta and will allow Brenntag to improve and expand value-added customer support throughout the supply chain, from purchase and formulation through to packaging and logistics. With an in-house coatings application laboratory, the facility offers value-added services to its customers by meeting specific requirements for the formulation and customization of various blends of industrial chemicals. It provides further technical application support with a sample room, designated cool rooms and two rooms to safely store hazardous and flammable products. P.T. Brenntag, a subsidiary of the Brenntag Group, owns the new facility.

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FLORHAM PARK, NJ – BASF Future Business GmbH and Medi-Solve Coatings LLC will collaborate in the field of antimicrobial coatings for catheters and other minimally invasive medical devices. The collaboration combines Medi-Solve’s proprietary AquaCoat® coating technology with BASF Future Business’ proprietary HyGentic ® silver-based antimicrobial additive platform.

Clariant to Acquire Süd-Chemie AG MUTTENZ, Switzerland – Clariant AG is planning the acquisition of a controlling majority in Süd-Chemie AG, having signed a contract with the majority shareholders. Süd-Chemie operates two business units that hold a leading position in the areas of process catalysts and adsorbents. Furthermore, Süd-Chemie has a strong research and development pipeline for new business areas with substantial growth potential.

Momentive Specialty Chemicals Inc. Sells Ink and Adhesive Resins Business COLUMBUS, OH – Momentive Specialty Chemicals Inc. has completed the sale of its global Ink and Adhesive Resins (IAR) business to Harima Chemicals Inc., a leading producer of pine-based products headquartered in Tokyo, Japan. 䡲

Fan-tastic! COLORTREND® 808 No-VOC High Performance Colorants Introducing COLORTREND® 808HP No-VOC colorants and Vivid Expressions™, the newest color collection offering 460 of the brightest, cleanest colors in the coatings industry. Vivid Expressions™ provides the flexibility to expand an existing COLORTREND® system or be used as a stand alone point-of-sale color system. Now you will experience broader color space for brighter colors, plus high performance solutions for better durability, superior fade resistance and improved opacity. By utilizing this latest No-VOC colorant technology you will also meet growing market demands and exceed environmental regulations. As the largest independent colorant manufacturer and a global leader in specialty chemicals, Evonik continues to deliver eco-friendly, innovative, color system solutions. Just one more step to making our world safer, brighter, better – inside and out! colored by colortrend

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N AMES IN THE NEWS 䡲 HALOX®

䡲 National Coatings Corp. has named Brian Buck the Pacific Northwest Sales Manager. Buck’s territory will include Oregon, Washington, Idaho, Alaska and Hawaii. 䡲 Specialty Polymers Inc. has hired David Carnahan as the new Western Region Sales Manager. He will be responsible for overseeing the company’s sales in the western United States and Canada.

announced the appointment of Bodan Ma, President of P.T. Hutchins China Co., as HALOX Senior Technical Advisor. Ma will work closely with the company’s distributor partners in China and Taiwan.

Goff

Kim

䡲 Gary E. Hendrickson, currently Valspar Corp.’s President and Chief Operating Officer, will succeed William L. Mansfield as Chief Executive Officer. Mansfield will continue as Chairman of the Board.

䡲 Arkema Emulsion Systems

has announced Litynski the addition of John Hiel as the new North American Marketing Manager. Hiel will be responsible for program management, strategy and tactics across the region for all emulsion product lines.

䡲 Ray Hurst has joined Dowd and Guild Inc. Hurst will be responsible for sales in Texas, Oklahoma, Arkansas and Louisiana. 䡲 RBP Chemical Technology has named Ernest Litynski VicePresident of Operations for the company’s manufacturing facility in Milwaukee, WI.

Matisons

䡲 Gelest Inc. announced the appointment of Janis Matisons as Senior Technical Manager, reporting to Jerry Larson, Vice President R&D. Jonathan Goff has been promoted to Manager, Silicones R&D, and Yun Mi Kim to Technical Service Manager. The company also promoted company veteran Edward Kimble to Product Manager, Silicones, and has appointed Barbara Tsuie to the position of Product Manager, Silanes and Metal-Organics.

䡲 U.S. Zinc and Votorantim GmbH, both subsidiaries of Votorantim Metais, announced that Stephane Ryff has been hired as Regional Sales Manager, Europe, for both companies.

䡲 At his request, LANXESS AG has revoked the contract of Matthias Zachert, member of the Board of Management and Chief Financial Officer. Bernhard Düttmann, previous member of the Board of Management and Chief Financial Officer of Beiersdorf AG, Hamburg, Germany, has been appointed member of the Board of Management and Chief Financial Officer of LANXESS AG. 䡲

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APRIL 2011 | W W W . P C I M A G . C O M

Now, with a Ross Double Planetary Mixer you can mix materials up to 8 million centipoise.

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ADVERTORIAL

Green Technology ADDITIVES

ADDITIVES

Troy Corporation

Dow Coating Materials

Troy’s Multifunctional Wetting Additive for Low-VOC Systems Changes the Game: VOC-free, APE-free Troysol™ ZLAC

A Leader in Rheology Modifier Chemistry

In direct response to manufacturers’ efforts to comply with VOC regulations, Troy has introduced Troysol ZLAC, a substrate wetting and flow additive that contributes zero VOCs to aqueous systems. The product is the latest addition to Troy’s Z-line of “green” performance additives engineered to help manufacturers achieve regulatory compliance and still maintain optimum performance. Troysol ZLAC provides the same benefits and attributes long associated with Troysol LAC, but without the VOCs.

Silicone-free, APE-free Troysol ZLAC is part of Troy’s unique portfolio of multifunctional additives. Multifunctional additives are single additives that do the job of several. This is particularly valuable when overall system VOC level is a concern: the fewer the additives, the fewer the possible sources of VOCs. Troysol ZLAC promotes wetting of lowenergy substrates, and provides higher gloss, improved flow and leveling, and excellent color acceptance. Troysol ZLAC substantially reduces surface tension, providing coatings with strong surface wetting properties and enabling uniform coverage over low energy and contaminated substrates. For more information on Troysol ZLAC and to request samples, please visit www.troycorp.com and click on Performance Additives. There you can also find information on the full range of Troy specialty additives.

ACRYSOL™ RM-845 Rheology Modifier is a non-ionic, ultra-low solvent rheology modifier from Dow that exhibits outstanding thickening efficiency and spatter resistance in interior and exterior latex-based paints. Based on ACID SUPPRESION™ technology for use in low-odor and low-VOC formulations, this new rheology modifier offers a range of processing, manufacturing and application advantages. Using ACRYSOL RM-845 Rheology Modifier, paint and coating formulators can achieve low to high shear viscosity levels in a wide variety of coatings, including flat, gloss and semi-gloss paints, without adding solvents or significantly increasing VOC levels. Additionally, this product is designed for easy incorporation and use with traditional paint manufacturing processes. That same ease-of-use is seen at the end-user level as well, resulting in paints with excellent flow and leveling. Finally, as with all ACRYSOL™ products, this rheology modifier has an inherent resistance to microbial attacks, extending the product’s overall shelf life. Dow is an innovation leader in the development of rheology modifier chemistry and has a wide range of thickening products to meet the needs of paint and coating formulators.

www.troycorp.com [email protected] 973/443.4200 www.dowcoatingmaterials.com/additives 20

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APRIL 2011 | W W W . P C I M A G . C O M

ADVERTORIAL

Green Technology R E S I N S / P O LY M E R S

R E S I N S / P O LY M E R S

GEO Specialty Chemicals, Inc. Celanese Emulsion Solutions for Solvent-Free PUD Formulations Polymers In response to changing dynamics of the coatings resin market, Tri-Rez™ Polyols and DMPA® Polyols are two product groups specifically developed to assist the resin formulator in developing VOC-compliant and environmentally friendly coating formulations.

Introducing Avicor™ 601 and EcoVAE® 501 – Innovations in Emulsions

Tri-Rez™ Polyols: 1030 Series: 1230 Series: 1020 Series: 1220 Series:

Liquid polyesters for solvent-free textile coatings Liquid polyesters for VOC-compliant exterior/interior and textile coatings Highly crystalline polyesters for waterborne adhesives Semi-crystalline polyesters for waterborne adhesives and coatings

Tri-Rez Polyols are 100% solids polyester polyols developed with the intent to provide our polyurethane dispersion customers with additional tools for formulating solvent-free waterborne polyurethane dispersions for both the coating and adhesive markets. The product line includes a mix of products from low-viscosity liquids to highly crystalline resins. Tri-Rez Polyols are specifically designed for waterborne applications. They utilize raw materials designed to achieve maximum hydrolytic stability in finished formulations while providing low-viscosity pre-polymers for easy, solvent-free processing.

DMPA® Polyols: DMPA Polyol HA-0135 and HA-0135LV2 are linear, 100% solids saturated polyester polyols that contain primary hydroxyl and tertiary acid functionality. Both products are non-crystalline liquid resins, and when used in combination with Tri-Rez Polyol, the need for processing PUDs with n-methylpyrolidone is eliminated. DMPA Polyol HC-0123 is based on renewable resources and contains both hydroxyl functionality for urethane reactions and unsaturation for oxidative curing. PUDs formulated with DMPA polyol HC-0123 demonstrate excellent adhesion and moisture-resistant properties.

EcoVAE 501, the latest edition of our environmentally friendly line of EcoVAE emulsions, meets critical performance requirements across the spectrum of gloss levels for architectural interior paints. EcoVAE 501 is a vinyl acetate/ethylene emulsion designed to meet regulatory issues (VOC levels below 50 g/L, APE-free, ability to achieve green certifications) while maintaining the block, scrub and stain resistance, and gloss development demanded by the paint formulator. EcoVAE 501 is engineered to be compatible with acrylic-based emulsions, such as our new 100% acrylic Avicor 601.

Avicor 601 is a 100% acrylic emulsion designed for excellent performance at ultra-low VOC across the entire gloss spectrum. This APE-free emulsion has a low viscosity and fine particle size that offers very good adhesion and block resistance in flat through semi-gloss paints. Avicor 601 is unique as it is designed to be blended with vinyl-based resins (VAE and vinyl acrylic) to achieve the best attributes of both resins. Ask to see our blend studies. Blending Avicor 601 with any of our EcoVAE emulsions will help the paint manufacturer meet their performance, marketing and economic goals. Ask us how.

Adapting and developing technologies for a greener market

USA - (215) 773-9280, (888) 519-3883 UK - +44 1242 255 772 www.geosc.com

www.Celanese-Emulsions.com [email protected] 972/443.4669 PA I N T & C O AT I N G S I N D U S T RY

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21

GREEN SHOWCASES

Great Individually. Exceptional Together.

Arch Biocides 800.523.7391 [email protected] *This product is not meant for food applications *This product provides preservative properties to protect the product or coating *Arch Biocides is a business unit of Arch Chemicals, Inc. *Some Arch® biocides may not be registered or registered for only certain uses in your country

archbiocides.com/proxelbzplus

As with wine and cheese, when two excellent products with long track records come together, such as Proxel® preservatives and Omadine® antimicrobials, you get an exceptional result: Proxel® BZ Plus Preservative. This unique combination offers a dual mode of action for inhibiting microbial growth in latex emulsions, water-based paints, adhesives and pigment dispersions - preventing discoloration and providing the extra protection you need against mold, mildew and bacteria. Features include: • Color-stable formulations • Dual-action protection • Zero VOCs • CMIT / MIT and formaldehyde free • Long-term preservation • Broad-spectrum activity

Pour in the profitability.

THINGK AC 2403 THINGK Alberdingk

❖ Solvent free Polyurethane dispersions ❖ Renewable Polyurethane dispersions ❖ Solvent free Waterborne UV dispersions ❖ Veryy Low VOC Self Crosslinking g multiphase p emulsions

Grow your market share through innovative products with the help of Greenability. www.BYK.com

Fielding Chemical Technologies Inc. is a leader in Chemical and Refrigerant repurposing and chemical procurement. Customers can rely on Cradle to Cradle® Care of Chemicals from global procurement, logistics management, customized solutions to repurposing spent chemicals, giving them new life and preserving precious resources. Connect with Fielding and bring The Science of Sustainability™ to your triple bottom line: www.fieldchem.com

www.AlberdingkUSA.com alberdingkusa.com/AC2403TechBulletin.pdf

“Welcome to Our World”

100 Eames St. Wilmington, MA 01887 ph: 978-988-0880 fax: 978-658-3366 www.allcoattech.com [email protected]

22

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AllUthane 30522 is a solvent-free, water-based aliphatic polyurethane dispersion. It has excellent adhesion to a variety of substrates making it suitable for formulating low-VOC coatings for metal, wood and plastic substrates. The polymer exhibits exceptional toughness and has superb abrasion and chemical resistance making it ideal for challenging interior or exterior applications. For product and application information call: Kurt Bimmler at 978-988-0880, ext-311 or email [email protected]

APRIL 2011 | W W W . P C I M A G . C O M

TM

COMPLETE SPECTRUM OF QUALITY RESINS For more than six decades OPC Polymers™ has provided customers in the coatings industry with a complete spectrum of quality resins, flexible manufacturing and innovative solutions.

Talk to us today about: 䡲 Alkyd Emulsions and Dispersions 䡲 New Advances in Compliant pliantt SSolvents olvent ents 䡲 100% Renewable Resins. s.. 800-848-1898 [email protected] m

Choose PAN Technology for your dispersions. • Go green with PanTINT® Zero VOC waterborne colorants and 100% solids chip dispersions for coatings, inks & adhesives. • Simplify your waterborne pigment dispersion applications with our new PanSPERSE 900 Zero VOC dispersing agent. Pan Dispersions…manufactured excellence.

The Shepherd Color Company

For more information: 800.722.3507 www.pantechnology.com

Shepherd Color brings an extraordinary leap forward in the science of coloration. DYNAMIX® Pigments are normally required to be processed with a large amount of energy to provide the appropriate level of color and strength. Not any more! A breakthrough in dry dispersion technology that has outstanding performance. Just stir them in!

www.shepherdcolor.com

Soyanol ™ Eco-Friendly Additives

High Performance, Sustainable Additive Solutions Multiple functions including coalescent, plasticizer, and dispersant Zero and Low-VOC Solutions for solvent and waterborne formulations Compatible with most resin systems Excellent Freeze / Thaw performance

For Sustainable Paints & Coatings

Rhodia is committed to helping formulators design more eco-friendly coatings that answer sustainability challenges without compromising performance.

GREEN SHOWCASES

Turn over a new leaf.

Soyanol™ is the perfect blend of high performance, versatility, and sustainability.

North America Phone: 1-800-973-7873 www.rhodia.com

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“Grafting” by definition, means to attach and grow new material onto an existing backbone or substrate. APS Scientists have utilized its patented and unique process of chemical grafting which allows the manufacturer to permanently add or improve the performance of a material while retaining its existing beneficial characteristics using safe, effective organic chemicals. The Process of chemical grafting involves the activation, attachment and polymerization of new desirable properties onto a backbone substrate using a specific graft initiator-monomer system. These properties attach themselves at the activated sites forming polymer chains linked by covalent bonds. New properties are permanently imparted to the substrate by attaching selected monomers with specific functionalities. Because a covalent bond is formed during grafting, a direct comparison between chemical vs. the weaker physical bond is established. All monomers used in formulations meet safety codes according to EPA, OSHA and FDA (if required) standards. APS’s proprietary process can be tailored to accommodate individual product requirements and production capabilities. Many materials can be improved through chemical grafting including metals, plastics, rubber, glass and cellulose. Some permanent properties are corrosion and abrasion resistance, nonflammability, conductivity, vapor barrier, solvent and resistance and improved adhesion to other materials.

For more information, please contact us.

ADVANCED POLYMER SOLUTIONS 99 Seaview Blvd Š Port Washington, NY 11050 Š Tel: (516) 621-5800 Š Fax: (516) 621-5850 Or visit our website: www.advancedpolymersolutions.com

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P A I N T & C O A T I N G S I N D U S11/10/09 T RY

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AN New ew E Environmentally nvironmentallly Friendly Friendly Wetting Wettingg Agent Agent for

Architectural Coatings

A

rchitectural coatings formulators must continually adjust to market-driven performance criteria, more stringent environmental standards and economic pressures. Most recently, paint manufacturers around the globe are promoting the elimination of alkyl phenol ethoxylate (APE)-containing products in their architectural paint formulations. In addition, VOCs are also being reduced or eliminated from today’s formulations. All of these actions help to promote environmentally friendly and greener formulations, but at what price to performance? Concerns regarding the environment and persistent toxic materials have forced customers to search for new additives with equivalent or improved performance at the same prices they are currently paying for traditional additives. A new, environmentally friendly wetting agent for architectural coatings has been developed that can be used as a drop-in replacement for simple and modified APEs. This new, APEfree surfactant offers efficient wetting of titanium dioxide during grinding, improved freeze-thaw and viscosity stability in the formulated paint, improved foam control, better scrub resistance, and improved flow and leveling, all without contributing additional VOCs to the paint formulation.

Background Most architectural paints are composed of a few basic ingredient types: an emulsion or latex, pigments and

FIGURE 1 | Generic architectural paint composition. Architectural Paint

Emulsion Polymer/Latex

Pigments

Additives

Acrylic Vinyl Acetate Copolymer Styrene/Acrylic

Inorganic Organic Extender

Surfactant/Grind Aids Dispersants Defoamers Rheology Modifiers Solvents Biocides

additives (Figure 1). Each material plays a vital role in the overall performance of the finished paint, so raw material selection is critical. Improper selection of any of these may drastically affect the paint properties. For example, choosing the wrong binder may result in poor durability, excessive dry times or lack of adhesion to the substrate. Similarly, a poorly chosen wetting agent or surfactant can lead to poor pigment dispersibility, resulting in loss of gloss and poor film aesthetics. For architectural paints, surface active agents, also known as surfactants, are used to lower surface or interfacial free energies of the aqueous phase to achieve good pigment wetting for efficient grinding and consistent substrate wetting for defect-free coatings. Good wetting performance in these applications is demonstrated by low dynamic surface tension values that occur when the surfactant can migrate rapidly to newly created interfaces created during manufacturing and application. Low dynamic surface tension promotes excellent wetting on multiple surfaces and efficient pigment grinding; this, in turn, leads to improved coverage and adhesion, reduced grind times and enhanced color development.

Surfactants A surface active agent, or surfactant, is a chemical that can be adsorbed onto the surface or at the interface of a system. Surfactants have a characteristic molecular structure incorporating a water-loving hydrophilic part and an oil-loving lipophilic (hydrophobic) part. Due to their amphiphilic nature, surfactants tend to accumulate at the air/water interface and reduce both surface and interfacial tension at low concentrations. Conventional surfactants have a hydrocarbon tail (hydrophobic part) connected to a polar or ionic head (hydrophilic part). In contrast, a Gemini surfactant has two hydrophobes and two hydrophiles on the same molecule. Half of the Gemini surfactant, consisting of one hydrophile and one hydrophobe, is connected to a spacer, which in turn is connected to the other identical half of the molecule forming a Gemini structure (Figure 2). Due to their unique molecular structure, Gemini surfactants are typically orders of magnitude more surface active than the corresponding conventional surfactants. Acetylenic-diol-

By Jeanine M. Snyder, Sr. Development Chemist, and Paul C. Marcella, Sr. Principal Research Technician | Air Products and Chemicals, Inc., Allentown, PA 24

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APR IL 2011 | W W W . P C I M A G . C O M

based Gemini surfactants (2,4,7,9-tetramethyl-5-decyne-4-7-diol and its ethoxylates) are widely used in architectural applications for wetting and foam control.1 The conversion of solvent-based coatings to water-based systems has presented the additive manufacturer with a variety of challenges. Typical surface tensions of solvent-based systems are in the 25 to 35 mN/m range, mostly due to the solvents used in these systems. Water-based coatings, on the other hand, typically have surface tensions of 50 mN/m or higher, primarily due to the high surface tension of water at 72 mN/m. When painting a substrate with a surface energy of 35-45 mN/m with a water-based system, reduction in surface tension of the coating must occur.2 As seen in Figure 3, spontaneous wetting of a surface can only occur when the surface tension of the liquid is lower than the surface energy of the substrate. To accomplish this, surfactants or wetting agents are commonly used in water-based coating applications.

containing ethoxylates of alkylphenols, neutralized alkyl phenol sulfonates or from polymeric molecules such as amine-neutralized copolymers of poly(acrylic acid). Depending on the formulation, one additive may be used for both the wetting and stabilization process. Pigment type, application parameters and cost are all factors to consider when choosing a dispersing package.

New Surfactant Development Additives are used in architectural paints to not only wet out pigments and substrates but also to help with foam control,

FIGURE 2 | Conventional and Gemini surfactant structures.

Hydrophobe

Pigment Dispersion The process of preparing a pigment dispersion is typically defined as the sum of three distinct processes. The first process involves wetting the dry pigment to displace air and any other impurities from the pigment surface. Once the pigment particles are sufficiently wetted out, grinding occurs to reduce the large pigment aggregates and agglomerates to their primary particle size. The last step involves stabilizing the dispersion to enhance color and viscosity stability, as well as shock resistance and letdown compatibility. For waterborne coatings, the dispersion process presents a number of challenges. For example, the high surface tension of water and the interfacial tension between the continuous water phase and the pigment must be reduced to adequately wet the pigment particles, as shown schematically in Figure 4. To reduce the surface and interfacial tensions, pigment wetting surfactants are used. These additives adsorb onto the pigment surface, reduce the interfacial tension and prepare the pigment for further adsorption of dispersion-stabilizing molecules.3 When the surface and interfacial tensions are low, milling efficiency is improved. This results in shorter grinding times and lower energy demand to reach primary particle sizes, lower grinding temperatures and lower viscosities of the mill base, which can lead to higher pigment loadings. Traditional wetting agents include alkylphenol ethoxylates, which have excellent ability to wet out the pigment surfaces. Due to the growing concern that APEs are endocrine disrupters and that they could adversely affect health, there is a growing trend towards replacing these materials in coatings applications. Because of their hydrophilic nature, APEs tend to stabilize foam and can cause water sensitivity issues in the final film. Use of these surfactants also leads to the use of strong defoamers to control foam which, in turn, can cause defects in the final film. Choosing the right wetting agent for pigment wetting will not only provide the most efficient milling and color development, but may also aid in preventing foam generation during manufacture and application. Once the pigment aggregates and/or agglomerates have been broken down to their primary particle size, the particles must be stabilized to prevent re-agglomeration and flocculation. As seen in Figure 5, stability is usually achieved through steric and elecrostatic stabilization. Electrostatic stabilization is accomplished through electric double layers, which are formed due to the adsorbed molecules on the particle surfaces. Steric stabilization is accomplished by the interactions in the aqueous phase of hydrophilic segments of molecules adsorbed onto the particle surfaces.3 These stabilizing hydrophilic segments are often from surfactants

Hydrophile

Gemini Surfactant Monomeric

Surfactant

FIGURE 3 | Substrate wetting. Surface Tension < 39 mN/m

GOOD WETTING SPREADING

SPREADING

LIQUID COATING LIQUID SOLID SUBSTRATE COATING SOLID SUBSTRATE Surface Energy dynes Surface Energy ==40 40 mN/m

Surface Tension >> 40 mN/m

POOR WETTING

LIQUID LIQUID COATIN COATING G SUBSTRATE SOLID SOLID SUBSTRATE

Surface Energy = 40 mN/m Surface Energy = 40 dynes/cm

FIGURE 4 | Pigment wetting in the pigment dispersion process. Water Water

Surfactant Surfactant

Residue Residue Vapor Vapor Phase Phase

Pigment Pigment

Pigment Pigment

FIGURE 5 | Mechanisms of dispersion stabilization. Electric Double Layer + + +

+ +

– –

+

+ +

–

Steric Barrier Associated Solvent (water)

+

+ – + –

+

Anchor Groups

+

–

Particle Partic le –

+

– +

+

+

Particle Partic le

Solvated Chains

– – +

+

+

Charge Stabilization

Steric Stabilization

PA I N T & C O A T I N G S I N D U S T R Y

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25

A New Environmentally Friendly Wetting Agent for Architectural Coatings

TABLE 1 | Ultra-low-VOC interior eggshell formulation. Materials

Lb

Grind: Water Natrosol® Plus 330 (3% solution) KTPP Tamol™ 731 AMP-95 **Surfactant** Co-surfactant Defoamer Ti-Pure® R-706 Atomite® Optiwhite® Attagel® 50 Letdown: Vinnapas® EF-811 Natrosol Plus 330 (3% solution) Water Defoamer Texanol™ Total:

25.0 100.0 2.0 9.0 2.5 2.0 3.0 2.0 75.0 150.0 25.0 10.0 400.0 120.0 92.0 2.0 10.0 1029.5

*Formulation courtesy of Wacker Chemie AG.

TABLE 2 | Interior/exterior semi-gloss formulation. Materials

Lb

Grind: Propylene glycol Tamol SG-1 Water **Surfactant** AMP-95 Defoamer Ti-Pure R-900 Zinc oxide Letdown: Water Rhoplex™ AC2507 Texanol Propylene glycol **Surfactant** Kathon™ LX Defoamer Ammonium hydroxide Water Acrysol™ RM825 Natrosol 250MR (25% solution) Total:

Applications Testing Three model paint formulations were prepared to evaluate the new APE-free wetting agent. These formulations can be found in Tables 1-3. This new surfactant, designated as E2010, was benchmarked against two commercially available APE-containing surfactants designated as low-foam APE-containing surfactant (LFAPE) and hydrophobically modified APE (HMAPE). All additives were used at the recommended use level specified in the starting-point formulation. Physical properties of the surfactants tested can be found in Table 4. All paints were prepared following the manufacturer’s specified procedure and, following formulation, were applied using a 3-mil bird bar. Viscosity measure-

TABLE 4 | Comparitive properties of surfactants tested. APE containing % Activity HLB Pour point (°C) Viscosity (cps) DST (mN/m, 6 bubbles/sec)1 Cloud point (°C, 1 wt%) 40 CFR compliance 1

26

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58.0 7.7 5.5 3.0 3.0 1.0 245.0 25.0 29.0 530.0 24.3 37.0 1.2 2.0 1.0 1.0 72.0 18.0 10.0 1073.7

*Formulation courtesy of Air Products and Chemicals, Inc.

durability, block resistance, color development, washability or scrub resistance, and to help lower VOCs. A new, APE-free surfactant has been developed to improve these properties in a cost-effective manner while helping to minimize the VOC content of the final formulation.

Property

TABLE 3 | High-gloss, medium-white tint base formulation.

E2010

LFAPE

HMAPE

No 88 13.3 0 77 40 70 Yes

Yes 83 8 10 135 38 14 No

Yes 100 12.6 15 250 44 28 No

Measured using the Kruss BP-II Bubble Tensiometer, 0.1 wt%, 25 °C.

APR IL 2011 | W W W . P C I M A G . C O M

Materials

Lb

Grind: Water

50.0

Tamol 2001

3.42

**Surfactant**

2.0

Ammonium hydroxide (28%)

2.0

Defoamer Ti-Pure R-706

1.0 96.0

Letdown: Avanse™ MV-100

565.0

Water

146.0

Ammonium hydroxide (15%)

7.0

Dowanol™ DPM

18.0

Dowanol DPnB

10.5

Kodaflex™ TXIB

10.5

Sodium nitrite (15% solution)

9.0

Acrysol RM-8W

4.0

Total:

924.42

*Formulation courtesy of The Dow Chemical Company.

ments, an indication of paint stability, were determined using a digital Stormer Viscometer 24 hr after preparation and 2 weeks after aging at 50 °C. Blocking samples were prepared by coating the paint onto Leneta charts using a 3-mil bird bar, allowing the paints to dry for 24 hr at room temperature and then placing them face to face for 1 hr before pulling apart. Gloss and contrast ratios were measured using a BYKGardner Spectro-Glide 45/0 Glossmeter. To perform the rub-up test, the paints were tinted with the suggested tint base, coated onto a Leneta 1B chart with a 3-mil bird bar and allowed to rest for 1 min. Rubs were done on the coated section for 30 sec, and then the charts were dried for 24 hr under controlled temperature and humidity. Once the paint cured, color differences were measured between the rubbed and unrubbed areas on the chart. A Delta E value of less than 1 resulted in a “Pass” rating. Sag values were measured using a Leneta anti-sag meter, and leveling was determined by following ASTM D 4062 using a Leneta Leveling Test Blade. Foam tests were conducted by agitating a sample on a Red Devil Paint Shaker for 15 min and recording the density of the paint. To calculate the percent change in foam density, the difference between the density of the unagitated samples and the agitated samples was measured. A Washability and Wear Tester Model D10 was used to measure scrub resistance. Lastly, to determine the freeze-thaw stability, 300 g of paint were weighed into an 8 oz, lined can. The cans were placed in a freezer at 0 °C for 15 hr followed by a thaw at room temperature for 4 hr. The cans were then placed in a 25 °C water bath for 2 hr. Finally, the paints were stirred and a Stormer viscosity was taken. This process was

A New Environmentally Friendly Wetting Agent for Architectural Coatings

TABLE 5 | Performance results in ultralow-VOC interior eggshell formulation. Property Viscosity (KU, initial) Aged viscosity (KU, 2 wk @ 50 °C) Blocking (24 hr dry, 1 hr block, 0-10, 10 is best) Contrast ratio 60° Gloss Change in initial vs tinted viscosity (KU)* Yellow Blue Rub-up (ΔE<1)* Scrub resistance (cycles) Sag resistance (mils)

E2010

LFAPE

HMAPE

98 97 7 0.93 7.3

98 97 5 0.92 7.1

98 97 5 0.92 7.3

Δ4 Δ3 Pass >2000 >24

Δ4 Δ5 Pass >2000 >24

Δ4 Δ5 Pass >2000 >24

*Paints tinted at 8 oz/gal of Engelhard Options E and C colorants.

TABLE 6 | Performance results in interior/exterior semi-gloss formulation. Property

E2010

LFAPE

HMAPE

Viscosity (KU, initial) Aged viscosity (KU, 2 wk @ 50 °C) Leveling (Scale 1-10, 10 is best) Contrast ratio Freeze-thaw stability (# cycles passed) Color acceptance (ΔE<1) % Change in foam density Scrub resistance (cycles) 60° Gloss

88 94 9 0.98 5 Pass -11.2 1150 47

93 99 6 0.98 5 Pass -13.4 900 47

99 100 4 0.98 5 Pass -11 900 47

FIGURE 6 | Leveling results of interior/exterior semi-gloss formulation.

Better Leveling

10

Leveling

8 6 4 2 0 E2010

LFAPE

HMAPE

FIGURE 7 | Scrub testing results for the interior/exterior semi-gloss formulation.

repeated five times or until the viscosity could no longer be measured. The last cycle at which a viscosity could be measured is the reported value.

Results and Discussion Some notable features seen in Table 4 illustrate the ease of use of the newly developed APE-free surfactant. With a pour point of 0 °C, E2010 is much easier to handle in cold environments. The cloud point of E2010 is also significantly higher than the other two surfactants tested. Lastly, due to its composition, E2010 will be compliant with 40 CFR regulations, making it ideal for agricultural coatings and applications. Evaluations of the ultralow-VOC interior eggshell formulation show excellent performance of the E2010 sample compared to the two APE-containing surfactants. As a replacement for the LFAPE-, or for HMAPEcontaining surfactants, E2010 showed numerous benefits in the resultant coating (Table 5). These benefits include excellent gloss control, improved opacity and tint strength, as well as enhanced color acceptance and viscosity stability in tinted systems. E2010 also offers excellent scrub resistance and improved blocking resistance. All formulations exhibited excellent flow and leveling properties and equivalent foam control. Table 6 illustrates the performance of the surfactants tested in the interior/exterior semi-gloss formulation. Coating evaluation showed that E2010 surfactant achieved improved leveling (Figure 6), enhanced scrub resistance, comparable gloss, opacity, color acceptance and tint strength, competitive foam control and comparable freeze-thaw stability performance over the APE-containing surfactants. Figure 7 illustrates the scrub testing results of the semi-gloss formulation formulated with E2010 surfactant on the right and with the HMAPE surfactant on the left. When used in this formulation, the E2010 surfactant provided an improvement of 27% in scrub resistance over the APE-containing surfactant. When evaluated in the high-gloss, medium-white tint base, E2010 imparted numerous benefits as compared to the same formulation using the LFAPE surfactant (Table 7). Most notably, a significant improvement was seen in freeze-thaw stability when E2010 was used. The paint formulated with E2010 passed five freeze-thaw cycles compared to only three for the APE-containing paint. Also, as seen in Figure 8, E2010 offers enhanced foam control over the LFAPE-containing formulation, thus allowing the formulator to decrease the amount of defoamer used in the paint, leading to reduced overall formulation cost. Improved scrub resistance as well as comparable leveling, color acceptance, gloss and tint strength were also seen with the E2010-containing paint.

VOC Measurements

Hydrophobically modified APE

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E2010

APR IL 2011 | W W W . P C I M A G . C O M

The VOC contribution of E2010 to the formulated coating was measured following EPA Method 24. To perform this test, a commercially marketed, zero-VOC architectural paint was used. To this paint, 1% of the E2010 surfactant was added and the paint was subjected to the Method 24 test. The test results indicated that E2010 contributed zero VOCs to the paint.

A New Environmentally Friendly Wetting Agent for Architectural Coatings

TABLE 7 | Performance results in high-gloss, medium-white tint base formulation.

% Foam

FIGURE 8 | Enhanced foam control with E2010 surfactant. High-Gloss, Medium-White Tint Base % Foam

20 18 16 14 12 10 8 6 4 2 0

E2010

LFAPE

Property

E2010

LFAPE

Viscosity (KU, initial) Aged viscosity (KU, 2 wk @ 50 °C) 60° Gloss % Change in foam density Leveling (Scale 1-10, 10 is best) Rub-up (ΔE<1) Freeze-thaw stability (# cycles passed) Scrub resistance (cycles) Sag resistance (mils)

106 106 88 -8.9 10 Pass 5 1800 22

106 108 88 -18.9 10 Pass 3 1600 >24

Conclusion

References

The choice of wetting agents used in architectural coatings can have a significant impact when formulating low- to zero-VOC paints. A new, environmentally friendly, APE-free surfactant has been developed to assist in the formulation of these coatings while offering improved performance properties over conventional APEcontaining surfactants. E2010 surfactant offers efficient wetting of titanium dioxide during grinding, improved freeze-thaw and viscosity stability in the formulated paint, improved foam control, better scrub resistance, and improved flow and leveling, all while contributing no additional VOCs to the paint formulation. 䡲

1

2

3

Chan, S.Y.; Snyder, J.M.; and Stout, W. New Gemini Surfactants for WaterBased Graphic Arts Applications, Ink Maker 2004, January/February. Snyder, J.M.; Meier, I.K.; and Whitehead, J. New Additive Technologies for Fountain Solutions, Presented at the NPIRI Technical Conference, 2006. Galgoci, E.C.; Yacoub, K.; Misdrahi, M.F.; Peck, K.M.; Stout, W. P.; and Chan, S.Y. High-Performance Pigment Dispersant Additives Improve Pigment Wetting and Dispersion in Waterborne Coatings,” Journal of Coatings Technology, 2007, May.

The paper was presented at the 2010 Southern Society for Coatings Technology Annual Meeting in Daytona Beach, FL.

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APR IL 2011 | W W W . P C I M A G . C O M

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Environmentally Progressive

Polyurethane Coating Technologies

C

oatings and adhesives ad dhe hesiive vess are ar widely wi used in many industries, including building construction, industrial and automotive, metal protection and footwear. A significant portion of these products are still solvent-based. (Architectural coatings are the only exception, where waterborne products account for more than 80%.) Roughly, solventborne coating and adhesive products contribute several million tons of solvents to air pollution. One of the solutions is to increase the use of waterborne products. For example, aqueous acrylic emulsions have been used to make architectural paints since the early 1960s. Several million tons of aqueous emulsion-based paints are sold to end users and contractors annually. These paints are able to provide sufficient performance to protect and decorate buildings. With aqueous products, use of solvents in architectural coatings is significantly reduced.1,2

FIGURE 1 | Process for making water-dispersible polyisocyanate. Catalyst

Polyurethane (PU) is widel widely ely y us used sed d iin n in industrial ndu dustrial coatings and adhesives due to its outstanding mechanical strength, elongation, wear resistance and toughness. However, a significant portion of PU products are still solvent-based. To reduce the VOC level of these products, waterborne technologies like PU dispersions (PUDs), PU/ acrylic hybrid dispersions and waterborne 2K products (OH functionalized acrylic or PU dispersions, water dispersible polyisocyanates) have been developed. In some aspects, these technologies are able to provide comparable performance at much lower VOC levels as compared to solvent-based technologies. Due to their environmental friendliness, these technology platforms attract significant attention from academic and industrial research organizations. Yantai Wanhua Polyurethanes Co. Ltd. is a leading manufacturer of MDI in China. In recent years, the company has invested in the research of aliphatic isocyanates and waterborne PU technology platforms including PUD, PUA and waterborne 2K. In this article, waterborne technologies developed by Wanhua are described, and their application in architectural and industrial coatings, as well as adhesives, is discussed.

Synthesis Technology Platforms PUDs

Trimer

Polyether

T ºC/Time

Water-dispersible polyisocyanate

FIGURE 2 | Process of dispersing hydrophilically modified polyisocyanate in water: 1) pour hydrophilically modified polyisocyanate into water; 2) hydrophilically modified polyisocyanate self disperses in water; 3) stir with a glass rod; 4) uniform polyisocyanate dispersion.

The pre-polymer process is used to prepare PUDs. First, aromatic or aliphatic isocyanates react with polyols to form pre-polymers. Then, dimethylolpropionic acid (DMPA) is added using N-Methyl-2-pyrrolidone (NMP) as solvent. DMPA provides stability for PUDs in water when the pH is greater than 6.0. Thirdly, butanediol (BDO) is added to extend molecular chains. If viscosity appears high, acetone is added. In the fourth step, triethylamine (TEA) is added to neutralize the carboxylic acid-containing PU chains. In the fifth step, the mixture is dispersed in water under high shear. During shear, ethylenediamine (EDA) is added to further extend PU chains. In the last step, acetone is removed. The critical factors determining the performance of PUDs are types of isocyanates and polyols, and proportion of soft and hard segments. In order to prepare PUDs for different applications, it is necessary to understand application needs. For example, exterior architectural coatings usually require good durability, alkaline resistance, elon-

By Jiakuan Sun, Technical Director for Advanced Surface Technologies; and Weiqi Hua, Vice President and CTO | Yantai Wanhua Polyurethanes Co. Ltd., Shandong, China 32

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APR IL 2011 | W W W . P C I M A G . C O M

TABLE 1 | Physical properties of PUDs prepared for leather finishing.

gation and strength. To meet these needs, polyether polyol and aliphatic isocyanates with low levels of hard segments are recommended.

Aliphatic Aromatic

Type

PU Acrylic (PUA) Dispersions Acrylics have good weatherability, resistance to water and chemicals, and low cost. PU has good balance of strength and elongation as well as outstanding wear resistance and toughness. PUA combines the advantages of these two chemistries at lower cost in comparison with PUD. In addition, PUA has improved compatibility with acrylic dispersions. The process for preparing PUA is similar to that for PUD in the initial steps. After PU chains are extended with BDO, acrylic monomers are added to the pre-polymer. Then this mixture is neutralized with TEA followed by dispersion in water under high shear. The resulting product is used as monomer emulsion and gradually added into the reactor. Simultaneously, initiator is gradually added into the reactor to start emulsion polymerization. In the last step, acetone is removed. The resulting emulsions have a hybrid structure of acrylic and PU chemistries.

Product

Appearance

Cosolvent (wt% NMP)

pH

Solids (wt%)

Viscosity at 23 ºC (mPa·s)

PUD-base PUD-middle PUD-top PUD-base PUD-middle PUD-top

Translucent Milky white Milky white Translucent Translucent Translucent

1-2 1.5-3 1.5-3 1-2 1-2 1-2

7-8 7-8 7-8 7-8 7-8 7-8

~30 ~30 ~30 ~30 ~30 ~30

10-200 10-200 10-200 10-200 10-200 10-200

are used: solution radical polymerization for making secondary acrylic dispersion;3 and emulsion polymerization for making acrylic emulsions containing OH groups.4 To make OH containing acrylic dispersions, monomers with OH functionality like hydroxyethyl methacrylate (HEMA) are used in radical polymerization. The other type of OH-functionalized dispersions are PUDs. The process for making this special type of PUD is similar to that for conventional PUD. The major difference is that OH-containing diols are added in the first step. This OH-containing diol imparts OH functional groups on the PU chains.

Waterborne 2K Technology

Application Examples Leather Finishing

Figure 1 shows the process for making water-dispersible polyisocyanate. HDI trimer is modified with hydrophilic polyether with end OH functionality under the effect of a catalyst. Figure 2 shows that the hydrophilically modified HDI trimer has good dispersibility in water. In typical 2K formulations, there are two major components: OH-functionalized dispersions, which may be acrylics or PUDs; and water-dispersible polyisocyanates. To make OH-functionalized acrylic dispersions, two methods

Table 1 lists the physical properties of PUDs prepared for leather finishing. These PUDs have different hardness through adjusting the ratio of soft/hard segments. Table 2 shows the performances of these PUDs in leather finishing applications. It is clear that these PUDs with different compositions and soft/hard segment ratios can meet the requirements of base, middle and topcoats on genuine leather surfaces.

TABLE 2 | Performance of coatings based on PUDs for leather finishing. Property Touch feeling Gloss Strength Water resistance Cold crack resistance Adhesion Abrasion resistance Cut through resistance Plate release Embossibility Yellowing

Base

Aromatic Middle

Top

Base

Aliphatic Middle

Top

Soft Fair Fair —

Medium hard Good Good Good

Hard Better Better Excellent

Soft Fair Fair —

Medium hard Good Good Good

Hard Better Better Excellent

Excellent

Excellent

Good

Excellent

Excellent

Good

Excellent Excellent

Good Excellent

Good Excellent

Excellent Excellent

Good Excellent

Good Excellent

Good

Better

Better

Excellent

Excellent

Excellent

Good Good Yes

Better Good Yes

Excellent Good Yes

Good Good No

Better Good No

Excellent Good No

TABLE 3 | Physical properties for wood coatings. Product Wanhua PUD Wanhua PUA WC001 acrylic dispersion WDIso161 water-dispersible trimer Wanhua PUD (formaldehyde absorption) Wanhua PUD (antimicrobial)

Appearance

Cosolvent (wt%)

pH

Translucent Milky white Milky white Clear, viscous liquid Milky white Milky white

2.4 NMP 1.7 NMP SN4/BG4 — 0.8 NMP 1.7 NMP

7-8 7-8 7.5-8.5 — 7-8 7-8

Solids NCO Content on (wt%) Solids (wt%) ~35 ~35 ~45 100 ~35 ~35

— — — ~17.5 — —

OH Content on Solids (wt%) — — 3.3 — — —

PA I N T & C O A T I N G S I N D U S T R Y

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33

Environmentally Progressive Polyurethane Coating Technologies

TABLE 4 | Performance of wood coating formulations. PUD Formulation

PUA Formulation

2K Formulation

Good 92 ≤20 ≤3 ≥HB Good Good Good Good Better Good Good Pass Pass Non-yellowing

Good 83 ≤20 ≤3 ≥HB Good Good Good Good Good Better Good Pass Pass Non-yellowing

Good 89 30 ≤7 ≥2H Better Good Better Better Better Better Good —— —— Non-yellowing

Property Appearance Gloss 60° Tack-free time (min) Hard dry time (h) Pencil hardness Taber abrasion Cross-cut test Water resistance (24 h) 50% Ethanol (1 h) Black tea (1 h ) Vinegar (1 h) 1.4% Ammonia (1 h) Storage stability Freeze-thaw stability Yellowing

TABLE 5 | Model wood coating formulations. Ingredient

Part by Weight PUD PUA

Supplier

1K Binder Defoamer Wetting agent Coalescing agent

Resin BYK®-028 BYK-346 DOWANOL™ DPM

85 0.3 0.3 1.5

84 0.3 0.3 2

Wanhua BYK Chemie BYK Chemie Dow

Coalescing agent

DOWANOL DPNB

4.5

5

Dow

Water Tego® Glide 410 BYK-531 H3551

3 0.2 3 0.2

3 0.2 3 0.2

Evonik BYK Chemie Haichuan

Leveling agent Wax Thickener

2K Part 1 Leveling agent Wetting agent Thickener Thickener

WC001 (OH Acrylic Dispersion) Surfynol® 104 BC BYK-346 Baysilone® paint additive 3468 BORCHI® GEL PW 25 Water

Part 2 Crosslinker Co-solvent NCO/OH Ratio

WDIso 161 MPA NCO/OH

45.61

Wanhua

0.69 0.3

Air Products BYK Chemie

0.87

OMG

0.13 5.48

OMG

16.8 4.2 1.8

Wanhua Local Supplier

FIGURE 3 | Color comparison among solutions containing different chemicals.

Water+CH2O detecting agent

CH2O solution reacted with PUD film +CH2O detecting agent

CH2O solution +CH2O detecting agent

PUD film + CH2O solution

Wood Coating Table 3 shows the physical properties of PUD, PUA, OH acrylic dispersions and water-dispersible HDI trimer for wood coatings. Table 4 shows the performance of formulations based on PUD, PUA and 2K polymers. Table 5 shows the model formulations for wood coatings. It is clear that the formulations based on PUD, PUA and 2K polymers provide satisfactory application performance. In general, 2K formulations deliver improved resistance to wear, water and chemicals, as well as better hardness in comparison with 1K formulations. In addition to conventional PUDs, functional PUDs with formaldehyde absorption and antimicrobial activity were prepared. Figure 3 shows that films prepared from formaldehyde-absorbing PUD can effectively react with formaldehyde. Tube number 1 contains water. After a formaldehyde indicator solution is added, its color does not change and retains its original brown color. Tube number 3 contains formaldehyde solution. Once a formaldehyde indicator agent is added into tube 3, its color changes to purple from brown. Tube number 2 contains supernatant solution from the vial shown in Figure 3, which is filled with formaldehyde solution and films prepared from the formaldehyde-absorbing PUD. This result confirms the effectiveness of the formaldehyde-absorbing PUD. Table 6 shows the antimicrobial results of the films prepared from PUDs treated with two different approaches. These two approaches are both based on silver ions, which are the safest way to provide antibacterial effects. PUDs treated with approaches A and B both show effective activity.

TABLE 6 | Antimicrobial results. Staphylococcus Sample No. Treatment Blank (0 h) No treatment Blank (24 h) No treatment WH-PUA-1 Approach A WH-PUA-2

Approach B

Escherichia coli

cfu/ Test Piece

Decrease of cfu [%]*

Value of Antimicrobial Activity**

cfu/ Test Piece

Decrease of cfu [%]*

Value of Antimicrobial Activity**

6×106 4.7×106 <20

----100%

---->6.5

1.5×106 <20 <20

----/

----/

<20

100%

>6.5

<20

/

/

* The number of cfu on the treated test piece after 24 h is compared with the number of cfu on the blank test piece after 24 h. ** = log 10 (cfu on blank test piece after 24 h/cfu on treated test piece after 24 h).

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APR IL 2011 | W W W . P C I M A G . C O M

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Environmentally Progressive Polyurethane Coating Technologies

TABLE 7 | Physical properties of 2K polymers for metal protection. Product OH acrylic dispersion

Cosolvent (wt%)

pH

SN4/BG4

7.58.5

—

—

WDIso 161 (waterdispersible trimer)

NCO Content on Solids (wt%)

OH Content on Solids (wt%)

~45

—

~3.3

100

~17.5

—

Solids (wt%)

TABLE 8 | Properties of formulations based on Wanhua’s 2K and commercial 2K system.

2K WB Wanhua

2K WB (Commercial Product)

<30min/3h

<30min/3h

Properties Drying time

T1/T3* Drying condition

80 ºC 30min

23 ºC 50% RH

80 ºC 30min

23 ºC 50% RH

Pendulum hardness test (s)

1D

336

309

349

338

7D

348

292

356

350

Pencil hardness

7D

>2h

>2h

>2h

>2h

Gloss (20°/60°)

1D

66.4/87.3

68.5/88.7

Cross-cut adhesion test**

1D

0

0

0

0

Cupping test (mm)

7D

10.40

10.30

9.80

9.73

Water resistance

7D

pass

pass

pass

pass

77.6/86.5 51.5/80.3

TABLE 11 | Comparison of physical properties and adhesive performance between Wanhua’s aqueous PUD and commercially available PUD. Physical Properties and Adhesive Performance

MDI- H12MDICommercial Commercial Based Based Product A Product B PUD PUD

Solids Content wt%

50±2

50±2

Appearance

Milky white

Bluish

Activation temperature/ºC

45-55

44-52

43-53

45-55

Medium fast

Fast

Medium fast

Fast

Initial peel strength*

2

3

2

2

One day peel strength*

5

5

4

5

Crystallization rate

45±2

50±2

In between bluish and Milky white white

*On 0 to 5 scale: 5 is the best and 0 is the worst.

Metal Protection

Impact test (kg cm)

7D

>120

>120

>50

>50

Xylene resistance (1 min/5 min)

7D

pass

pass

pass

pass

Acetone resistance (1 min/5 min)

7D

pass

pass

pass

pass

Table 7 shows the physical properties of 2K polymers prepared for metal protection application. Table 8 shows the application properties of a formulation based on Wanhua’s materials and a commercial 2K formulation for metal protection. These two formulations show comparable performance in terms of major properties like anticorrosion, adhesion, hardness and durability.

Salt spray resistance (500 h)

7D

pass

pass

pass

pass

Elastomeric Wall Coating

Alkaline resistance (72 h)

7D

pass

pass

pass

pass

500h

pass

pass

pass

pass

UV radiation resistance

*T1 tack-free time; T3 hard dry time. **0 indicates the best adhesion performance using cross-cut adhesion test.

TABLE 9 | Physical properties of elastomeric PUA for wall coatings. Sample

Appearance

Wanhua elastomeric PUA Milky white

Cosolvent (wt%)

pH

1.5-1.7 NMP ~8

Solids Tg (wt%) (ºC) ~50

-20

TABLE 10 | Performance comparison between coatings based on Wanhua’s elastomeric PUA and coatings from commercial products. Properties Tensile strength, MPa Elongation, % @ 23 °C @ -10 °C @ 23 °C after heat aging Dirt pick-up resistance, %

Formulation Based on PUA

Commercial Product A*

China National Standard

2.1

1.6

≥ 1.0

350 100 150 15

390 80 130 20

≥ 200 ≥ 40 ≥ 100 < 30

* Commercial product A is an elastomeric coating based on an acrylic polymer emulsion; PVC is ~35%.

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APR IL 2011 | W W W . P C I M A G . C O M

Table 9 shows the physical properties of PUA for making elastomeric wall coating formulations. Table 10 shows the application properties of a formulation based on PUA and a commercial elastomeric wall paint. Both formulations contain about 35% PVC (pigment volume concentration). The commercial paint is based on an acrylic dispersion. Table 10 shows that PUA provides better strength and low temperature elongation as compared to the acrylic dispersion.

Adhesives Two PUDs for adhesive applications were prepared and their physical properties are listed in Table 11. Table 11 also lists their application performance as adhesives. Peel strength was conducted using a simple method. Two pieces of flexible PVC films were prepared and a PUD sample was coated onto the surface of one piece. This piece was heated to a temperature above the heat activation temperature and held at that temperature for about 10 m. Then the sample was taken out and the other piece was adhered under a given level of pressure. The initial peel strength was evaluated 10 m after the two pieces were pressed together using a hand tear method. One-day peel strength was tested using the same method one day after the two pieces were pressed together. It is worth noting that the peel strength as well as the resistance to high temperature and water of Wanhua’s

H12MDI PUD can be significantly enhanced by blending a small portion of Wanhua’s water-dispersible HDI trimer. Results are not shown here. DSC tests were carried out according to the following protocol: the temperature was increased from 25 ºC to 180 ºC at a rate of 10 ºC /m; then the temperature was lowered to -100 ºC at a cooling rate of 10 ºC /m followed by equilibrium stage at -100 ºC for 10 m; finally temperature was raised to 180 ºC at a heating rate of 10 ºC /min. During the test, nitrogen was used to protect the sample from oxygen. Figure 4 shows that Wanhua’s H12MDI-based PUD does not have the crystallization peak at a temperature of ~0 ºC, as does the commercial product. One hypothesis is that during the cooling cycle, the amorphous phase in the commercial product did not have sufficient time to crystallize and directly changed to a solid, glassy phase due to its relatively lower mobility of molecular chains. This indicates that Wanhua’s H12MDI-based PUD has a capability of fast crystallization leading to good initial peel strength (shown in Table 11).

FIGURE 4 | DSC curves for H12MDI-based PUD and commercial product II. 2.0 1.5

Wanhua product commercial product

1.0 0.5 0.0 -0.5

Based on Wanhua’s H12MDI

-1.0 -1.5 -75

-50

-25

To reduce the VOCs used in PU-based coatings, Yantai Wanhua Polyurethanes Co. Ltd. developed waterborne technologies including PUD, PUA and waterborne 2K. Materials prepared with these technologies provide sufficient performance for applications in many areas like leather finishing, wood coatings, metal protection, elastomeric wall coatings and adhesives. In addition, these materials deliver extra functions like formaldehyde absorption and antimicrobial activity. 䡲

References 2

Linak, E. and Kishi, A. Acrylic Surface Coatings, CEH Marketing Research Report, December 2006. Linak, E. and Kishi, A. Urethane Surface Coatings, CEH Marketing Research Report, October 2007.

OxylinkTM The additive for better waterborne coatings

Buhler Inc. (NT) [email protected] USA / Canada: 512 - 466 8005 Europe / Asia: +49 (0) 681 - 394 6550 www.buhlergroup.com

25

50

75

100

125

150

175

Temperature/ºC

Summary

1

0

3

4

Munzmay, T., etc. Aqueous Secondary Polymer Dispersions for the Production of Coatings, US Patent Application: US 20090105409A1, April 23, 2009. Kelly, M., etc. Binder Composition, European Patent Application: EP 2071066A1, June 2009.

Acknowledgements The authors want to thank Ms. Jie Zhang, Ms. Hong Zhang, Mr. Xuesun Ji, Mr. Longyue Zhang, Mr. Bo Liu, Mr. Weizu Sun, and Mr. Xiaodong Qiao for preparing and evaluating samples. This paper was presented at the Polyurethanes 2010 Technical Conference, sponsored by the Center for the Polyurethanes Industry of the American Chemistry Council, in partnership with UTECH North America, in Houston, Texas.

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37

Low-VOC Colorants for Solventborne Industrial Coatings

T

he coatings market is facing sustainability challenges due to tightening VOC regulations. This has led coatings formulators to re-evaluate their formulations and adapt them to meet new regulations by using “green” raw materials. In order to comply with market requirements, Colortrend USA LLC has developed Chroma-Chem® 846, a lower-VOC line of non-aqueous colorants for use in solventborne industrial applications. The colorants were developed using alkyl phenol ethoxylate (APE)-free surfactants, are aromatic free, and free of Hazardous Air Pollutants (HAPs). These colorants will allow formulation of tinted coatings that meet the required VOC regulations without compromising coating performance. Chroma-Chem 846 consists of 15 colorants that are volumetrically and gravimetrically dispensable for both depot and in-plant tinting of high-performance industrial coatings, i.e., acrylics, alkyds, cellulosic lacquers, chlorinated rubber, epoxies, polyesters, polyurethanes, melamine formaldehyde and vinyl paints. Their VOC content is below

TABLE 1 | Industrial maintenance VOC limit by agency. Agency

VOC (g/L)

National AIM Rule CARB SCQAMD OTC LADCO Environmental Canada

450 250 100 340 340 340

TABLE 2 | Colorant VOC levels compared to a standard - Chroma-Chem 844. Colorant White Quinacridone red Red oxide Burnt umber Yellow oxide Medium yellow Organic yellow Phthalo green Phthalo blue Lampblack Orange Bismuth vanadate Quinacridone violet Carbazole violet

Chroma-Chem 844

Chroma-Chem 846

331 g/L 529 g/L 503 g/L 452 g/L 525 g/L 444 g/L 484 g/L 525 g/L 497 g/L 596 g/L 516 g/L 516 g/L 548 g/L 571 g/L

188 g/L 210 g/L 195 g/L 168 g/L 148 g/L 198 g/L 195 g/L 211 g/L 206 g/L 222 g/L 200 g/L 176 g/L 215 g/L 223 g/L

250 g/L, allowing industrial coatings to be formulated at a reduced VOC level, while maintaining performance similar to the industry-known Chroma-Chem 844. The pigments used in Chroma-Chem 846 were chosen to provide a broad color space, good durability, lightfastness and chemical resistance, with tinting strength controlled to +/- 2% by volume and DE = 0.5.

VOC Issues There have been evolving changes on the allowable limits for industrial coatings, whether solventborne or waterbased. The impact of colorant on the VOC calculation occurs when it is added during in-plant production of the paint, but not when used to tint in distribution or commercial locations. However, proposed changes in legislation are to include the VOC contribution of colorant when used in commercial tinting. The VOC limit can be broken down by the type of coating, e.g., high-temperature industrial maintenance (IM) coatings 420 g/L, or zinc- rich IM primers 100 g/L. Further complicating this issue are the differences in limits by the various regulatory agencies, as shown in Table 1. Chroma-Chem 846 was developed to meet these and future VOC requirements by reducing the VOC to <250 g/L. A comparison of VOCs by EPA Method 24 shows that compared to the current technology, the VOCs can be reduced between 45% and 70%. This is based on the specific colorant, as shown in Table 2.

Colorant Evaluations In the development of a colorant there are three areas that need to be considered: 1. Colorant – selection of raw materials; 2. Quantifiable on colorant – the inherent properties of the colorant; 3. Quantifiable on paint – the impact of colorant on paint properties. Figure 1 highlights some of the key properties, though the overall evaluation was more extensive.

Colorant As already mentioned, APE-, aromatic- and HAPS-free materials were used with state-of-the-art pigments. The pigments were dispersed in a unique acrylic resin that provided excellent wetting and dispersing properties, allowing the colorant to have excellent compatibility with a range of coating chemistries. To lower the VOCs, a renewable resource-based proprietary polyester was blended with propylene glycol monomethyl ether acetate (PMA).

By Daniel Goldberg, Technical Director Colorants Americas | Colortrend USA LLC, Piscataway, NJ 38

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Quantifiable on Colorant Colorants are similar to coatings in that they are formulated products having inherent properties that must be consistent and stable. Some of these are shown in Figure 1, such as VOCs, dispensability, viscosity, shelf life (settling) as measured by oven aging, flash point and density. Others not shown, but just as important, are the grind or dispersability of the pigment.

Quantifiable on Paint After meeting any criteria related to the two points above, the colorant needs to provide the expected performance, in terms of color and strength, without having a negative impact on the coating. To determine the colorant impact, evaluations were conducted in 2K polyurethane, alkyd, nitrocellulose, 2K aliphatic acrylic urethane and 2K epoxy paint bases. The amount of colorant added per gallon was dependent on the paint base. Both alkyd and nitrocellulose were at 2 ounces, epoxy was at 8 ounces and the PUs were either 6 or 8 ounces, depending on the specific base. The coating thickness and substrate were dictated by the evaluation. For benchmarking purposes, Chroma-Chem 844 was used as a standard in each evaluation. Overall good results were obtained for all of the colorants in the test paint bases. As an example, results on the Burnt Umber colorant are provided below.

FIGURE 1 | Colorant and tinted paint properties. Quantifiable on Colorant VOC Density Content Dispensability Shelf Life Colorant Impact Resistance Color & Strength

Blocking Blocking was determined using ASTM D 4946-89. The coatings were applied using a 6 mil drawdown bar onto BYK-Gardner #AG-5303 chart. The drawdown was air dried for 7 days and placed face to face in an oven at 50 ºC, at a pressure of 1.8 psi over the specimen. After 30 minutes the specimens were removed from the oven, cooled down for 30 minutes at room temperature and peeled apart. The tackiness or block of Chroma-Chem 846 was the same as obtained for the standard. Adhesion Crosshatch adhesion was conducted by ASTM D 3359. The coatings were applied using a 3 mil drawdown bar onto aluminum substrate and air dried for 7 days. As shown in Table 3, Chroma-Chem 846 had a rating of 5 in all bases, meaning there was no loss of adhesion, and it was comparable to the standard. Hardness Pendulum hardness was conducted by ASTM D 4366. The coatings were drawn down on glass substrate using a 6 mil drawdown bar, air dried and evaluated after 7 days. A comparison of the oscillations shows that, depending on the base, Chroma-Chem 846 provided a slight to higher

APE-free Surfactant Package Solvent Additives Pigments

Compatibility

Hardness Adhesion Blocking Viscosity

Gloss

Quantifiable on Paint

TABLE 3 | Adhesion of Chroma-Chem 846. Paint Base Alkyd

Compatibility Compatibility was determined by rub-up and conducted on BYK-Gardner Drawdown Chart #AG-5303, using a 6 mil drawdown bar. Upon becoming tacky the coatings were rubbed, and after drying the rubbed to non-rubbed areas were compared visually for color differences. Excellent compatibility was obtained for all colorants in all of the paint bases.

Flash Point

2K PU

2K Aliphatic PU

2K Epoxy

Burnt Umber

Rating

Base alone

5

844-1352

5

846-1352

5

Base alone

5

844-1352

5

846-1352

5

Base alone

5

844-1352

5

846-1352

5

Base alone

5

844-1352

5

846-1352

5

TABLE 4 | Pendulum hardness of Chroma-Chem 846. Paint Base Alkyd

2K PU

2K Aliphatic PU

2K Epoxy

Burnt Umber

Oscillations

Base alone

33

844-1352

38

846-1352

40

Base alone

45

844-1352

64

846-1352

64

Base alone

55

844-1352

78

846-1352

73

Base alone

109

844-1352

117

846-1352

112

PA I N T & C O A T I N G S I N D U S T R Y

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Ask the Expert Charlie Hegedus Research Associate

Low-VOC Colorants for Solventborne Industrial Coatings

TABLE 5 | Impact resistance of Chroma-Chem 846. Paint Base

Burnt Umber

Alkyd

2K PU

Q

How can I formulate a highperformance, low-VOC, APE-free coating for multiple surfaces, including difficult surfaces like plastics?

2K Aliphatic PU

2K Epoxy

Forward/Reverse (in-lbs)

Base alone

68/12

844-1352

62/10

846-1352

76/8

Base alone

68/2

844-1352

78/2

846-1352

78/2

Base alone

80+/80+

844-1352

80+/76

846-1352

80+/80+

Base alone

80+/6

844-1352

62/4

846-1352

74/2

TABLE 6 | Summary of Chroma-Chem 846 evaluations. Paint Base

A

During painting applications on lowenergy surfaces such as plastics, wood, and dirty metal, complete coverage can be difficult, resulting in coating defects. Many surfactants reduce surface tension, but not during paint mixing and application, and they also create and stabilize foam, another source of defects. Research has shown that EnviroGem® 360 surfactant, a low-foam dynamic wetting agent, is an excellent solution due to its ability to migrate rapidly and effectively to the surface for a defect-free coating. Additionally, it is a coalescing surfactant that reduces minimum film formation temperature (MFFT) without increasing VOC or detracting from coating properties, and it is also free of hazardous air pollutants (HAPs) and alkylphenol ethoxylates (APEs).

Alkyd 2K PU 2K Aliphatic PU Epoxy

Compatibility Adhesion Blocking Hardness 0 0 0 0

0 0 0 0

© Air Products and Chemicals, Inc., 2009 (31516) B82

coating hardness (Table 4). This was consistent with the increased hardness provided by the standard.

Impact Resistance Both forward and reverse impact resistance were measured using ASTM D 2794. The coatings were drawn down on cold rolled steel using a 6 mil drawdown bar, air dried and evaluated after 7 days. The impact resistance was similar for both forward and reverse, though in some bases an improvement over the base and the standard was observed (Table 5). In Table 6, a summary of the above results is given. What this shows is for all 15 colorants, in the bases used, acceptable paint properties were obtained across the board. In addition to these evaluations, oven stability to determine the impact on viscosity, settling and compatibility were conducted. After 30 days at 50 °C good stability was maintained for these properties. Additional evaluations conducted included gloss retention and sag resistance, which were equivalent to the standard.

Color and Strength In terms of color and strength, ChromaChem 846 is different compared to the standard colorant. This is due to utilization

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0 0 0 0

Impact Resistance (F/R) +/0 0/0 0/+ +/0

0 No Impact, + Improvement

tell me more www.airproducts.com/ surfactants

0 0 0 0

APR IL 2011 | W W W . P C I M A G . C O M

of different resin and solvents to obtain lower VOCs. The result is some of the colorants, while at similar pigment loading, provide higher strength. The benefit is that less colorant is needed to obtain similar strength, and formulas are readily available through the use of Portfolio of Color®.

Summary The use of Chroma-Chem 846 allows coatings manufacturers to be compliant with stricter and ever-tightening VOC regulations, without sacrificing performance, for industrial solventborne coatings. As shown, these colorants provide performance that is equivalent to the current industry standard, at a VOC <250 g/L. Also, the colorants meet other environmental needs through the use of a renewable resource-based proprietary polyester, and additives that are APE-, aromatic-, and HAPs-free. With its broad compatibility, the addition of high-performance pigments to improve durability, and its broad color offering, Chroma-Chem 846 provides options to coatings formulators to meet both their customer and regulatory requirements. 䡲 The author would like to acknowledge Yamini Patel, David Rivera, Mier Gu and Jadel Baptista from Colortrend USA LLC for their contributions and data.

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1.877.203.0045 | [email protected] www.univarcorp.com

A New Substrate Wetting Additive for

Low-VOC Aqueous Adhesive Products

C

omplete substrate wetting must occur in order to obtain a strong adhesive bond. Effective wetting additives reduce the surface tension of the adhesive, enabling complete coverage of the substrate. Effective wetting additives are especially important for lowenergy surfaces, which would otherwise resist coverage. In addition, if a substrate is contaminated, low-energy contaminant particles repel the adhesive, resulting in surface defects and a weakened bond. When an effective wetting additive is present, adhesives will wet any contaminants and/or low-energy substrates, thus creating a strong, unimpeded bond. Troy Corp.’s multifunctional Troysol™ LAC provides excellent wetting of low-energy and contaminated surfaces, resulting in strong adhesive bonding. However, due to government regulations and consumer demand for environmentally compliant, green products, Troy has introduced Troysol ZLAC to fill the gap. HAPs-free, alkyl phenol ethoxylate (APE)-free ZLAC is a zero-VOC version of the traditional LAC product. It offers the same optimum substrate wetting performance as traditional LAC, but also enables the formulation of low-VOC aqueous adhesives products. ZLAC is a multifunctional, silicone-free wetting additive that improves substrate wetting, system flow and leveling, adhesion, gloss and color uniformity in aqueous coating, emulsion polymer, ink and adhesive applications.

Reducing Surface Tension High surface tension makes water inherently poor at wetting most substrates. A good example of this high surface tension is when a metal pin floats on the surface of water.

FIGURE 1 | Troysol ZLAC effectively reduces the surface tension of water.

Troysol ZLAC was first evaluated for its ability to reduce surface tension, which is essential to enable complete wetting over low-energy substrates. Figure 1 shows how ZLAC was able to reduce the surface tension of water with

TABLE 1 | Surface tension of common solvents.

TABLE 2 | Surface energy of common substrates.

Surface Tension (dyne/cm) Water Ethylene glycol Propylene glycol Xylene Dipropylene glycol monomethyl ether Toluene Propylene glycol n-butyl ether Butanol

72.7 48.4 40.1 36.0 29.0 28.4 26.3 24.6

Surface Energy (dyne/cm) Polyester Polyester, treated Polyvinyl chloride Polyethylene Polyethylene, treated Oriented PP Oriented PP, treated

Formulations A: Tackified acrylic copolymer PSA.

% by Weight Flexbond® 165 Aquatac® 6085 Mergal® K10N (preservative) Troykyd® D11 (defoamer) Water

79.0 15.0 0.2 0.3 5.5

B: Tackified acrylic copolymer PSA with urethane thickener.

Surface Tension, dynes/cm

% by Weight

80

Synthebond™ E 2050 Tacolyn™ 3179 H-C Acrysol™ 2020NPR Mergal K10N (preservative) Troykyd D11 (defoamer)

70 60 50 40

C: Acrylic copolymer PSA.

30 20 10 0

% by Weight

0

0.1

0.3

0.5

Acronal® A 220 Collacral® VAL Mergal K10N (preservative) Troykyd D11 (defoamer)

% ZLAC in Water By Peter Sheridan, Director, Performance Additives | Troy Corporation, Florham Park, NJ 42

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83.7 14.6 1.2 0.2 0.3

APR IL 2011 | W W W . P C I M A G . C O M

98.3 1.2 0.2 0.3

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A New Substrate Wetting Additive for Low-VOC Aqueous Adhesives Products

FIGURE 2 | Troysol ZLAC enables complete wetting over low-energy sub-

FIGURE 4 | 180° peel strength of PSA Formulation B.

strates.

7

180° Peel Strength, lbs/linear inch

6 5 4 Troysol ZLAC Troysol LAC

3 2 1

Complete wetting with Troysol ZLAC

0

Crawling was evident with ethoxylated acetylenic diol

FIGURE 3 | 180° peel strength of PSA Formulation A.

6

5 4 Troysol ZLAC Troysol LAC

3 2

180° Peel Strength, lbs/linear inch

180° Peel Strength, lbs/linear inch

0.4

7

6

5 4

Formulation A

3

Formulation B

2

Formulation C

1

1

0

0 0

0.2 0.3 Use Level %

0.4

use levels as low as 0.1%. Table 1 lists the surface tension values of typical solvents used in adhesives formulations. Conventional adhesive technology is based on solvents with low surface tensions. Conversely, aqueous adhesives require wetting additives to reduce the surface tension. The use of wetting additives enhances the coverage of substrates with low surface energy (Table 2). An adhesive with a high surface tension in the liquid phase will have poor wetting over low-energy substrates, resulting in craters and/or severe crawling. ZLAC, however, effectively reduces the surface tension of water to 25 dynes/cm, enabling aqueous adhesives to spread over low-energy substrates. Figure 2 shows a wetting test over a siliconized film. The formulation containing ZLAC provides complete coverage, while another formulation containing ethoxylated acetylenic diol, a commonly used wetting additive, showed severe crawling at equal concentrations.

Peel Strength Test Peel strength tests are valuable for determining the strength of the adhesive bond between two materials. In order to evaluate the adhesive strength imparted by the wetting performance of Troysol ZLAC and LAC, peel strength tests were performed using three typical pressure-sensitive adhesive (PSA) formulations (see sidebar). The following procedure was used for peel strength evaluation (180º Peel by PSTC 101 Test Method D): • Apply the adhesive over untreated polyethylene terephthalate (PET) substrate; • Apply the coated substrate on stainless steel panels after 24 hours of dwell time; • Use ChemInstruments TT-1000 tensile tester to measure peel strength. Troysol ZLAC was evaluated alongside LAC in formulations A

䡲䡲䡲

0.2 0.3 Use Level %

FIGURE 5 | 180° peel strength of PSA Formulations A, B and C.

7

44

0

APR IL 2011 | W W W . P C I M A G . C O M

0

0.05 0.1 0.2 Troysol ZLAC Use Level %

and B. ZLAC was also evaluated separately at very low use levels, from 0.05-0.2% (weight additive based on total formulation), in formulations A, B and C to determine the lowest concentrations at which maximum peel strength was obtained.

Results and Conclusions Test data show that substrate wetting imparted by ZLAC increases the peel strength in PSAs, and is the equivalent of the optimized performance offered by the traditional LAC product (Figures 3 and 4). Both additives enhanced substrate wetting and increased peel strength, thereby imparting greater adhesive bonding and better film integrity. In addition, concentrations as low as 0.05-0.1% ZLAC provided a substantial increase in adhesion for formulations A, B and C (Figure 5). The use of zero-VOC Troysol ZLAC wetting additive has shown excellent substrate wetting efficacy equivalent to that of Troysol LAC when used in PSAs applied over low-energy substrates. ZLAC addresses the need for more environmentally friendly substrate wetting in adhesives and sealants. It can help formulators achieve defect-free films with excellent surface appearance and optimum adhesion performance, without VOC contribution. 䡲 For more information, visit www.troycorp.com. Robert Miller, Dale Lyman and Sheila Belding of Troy Corp. contributed to this article. Flexbond® is a trademark of Ashland Inc.; Aquatac® is a trademark of Arizona Chemical; Synthebond® is a trademark of Hexion; Tacolyn® is a trademark of Eastman; Acrysol® is a trademark of The Dow Chemical Co.; Acronol® and Collacral® are trademarks of BASF Corp; and Troysol™, Mergal® and Troykyd® are trademarks of Troy Technology. This article originally ran in the February 2011 issue of Adhesives and Sealants Industry magazine.

breathe easy.

Have you looked at vinyl-based resin technology lately?

Find the balance you’re looking for. Contact us. www.EcoVAE.com [email protected] Brian Duke 973-443-4014

When we introduced our new EcoVAE emulsions last year, we told you that VAE (vinyl acetate ethylene) technology would be the foundation for a new generation of consumer pleasing, eco-friendly paints. After just over a year in the market, formulators of all types of paints have found that EcoVAE strikes the balance that everyone has been looking for in making high quality, high performing, peoplefriendly products. They’ve discovered that formulating with EcoVAE is uncomplicated. That the paints they make with it show excellent scrub, stain resistance and touch-up performance. And that EcoVAE technology is suitable for a broad range of interior paints – from premium brands to contractor flats.

If you’ve already found EcoVAE, thanks for your support. If you haven’t…maybe it’s time you discovered the next generation low VOC emulsion that everyone in the North American paint industry is talking about.

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formulate.

manufacture.

market.

paint.

live.

Novel Silicone-Modified Polyurethane

Advanced Coating

M

anufacturers and consumers place increasingly stringent demands on both the appearance and functional properties of surfaces. Often, these demands cannot be met by the material alone; rather, the manufacturers turn to innovative and functional coatings to offer the solution. Surfaces such as wood, metal, ceramic, leather and plastics require coatings that give a variety of protective and decorative properties. Besides the aesthetic aspect, these coatings may need to impart corrosion resistance, scratch and mar resistance, clarity, gloss, UV and weathering stability, chemical resistance, nonstick or easy cleaning, and even soft feel properties. For substrates such as wood, leather and plastics, traditional coatings technology includes acrylics, alkyds, polyesters, nitrocellulose and urethanes. As with every situation, strengths and weaknesses can be seen with each choice. One of the technologies of interest when con-

FIGURE 1 | Typical synthesis of a conventional polyurethane dispersion. HO

R

OH + OCN

OCN

OCN

NCO

R´

NCO + HO

I. Polyaddition

COOH [R3´´ N ] OCN

NCO

II. Neutralization

-

COO

NCO COO-

COOH NCO

COOH

OCN

OH

1. H2O 2. Polyamine

COO-

COOCOOPartially Crosslinked Polyurethane Urea

III. Emulsifying & Crosslinking

sidering wood, leather and plastics is urethane dispersion chemistry. Coating the substrate with select urethane dispersions can help manufacturers achieve a formidable combination of properties: flexibility, toughness, chemical resistance, clarity and one-component air-drying.1 By advancing traditional urethane dispersions and reacting with silicone, Evonik has developed a novel modified resin system: SILIKOPUR® 8080 silicone-modified polyurethane dispersion, which combines the strengths of a urethane dispersion with the hydrophobic nature of silicones. The silicone reacted in the urethane backbone shows improvement with regard to nonstick properties, improved surface cleaning, soft feel and increased mar resistance without sacrificing the advantages of traditional urethanes.1,2

Conventional and Silicone-Modified Polyurethane Dispersion Synthesis Manufacturing conventional polyurethane dispersions (PUDs) typically takes place in a series of steps, as shown in Figure 1. A polyester polyol, an additional diol and dimethylolpropionic acid (DMPA) are reacted with an acid group and two OH groups, as well as a diisocyanate such as isophorone diisocyanate (IPDI). The reaction is engineered so that the DMPA does not react with the diisocyanate through its acid group but, instead, is built into the developing polymer chain. The acid group is neutralized in the subsequent step and acts as a stabilizer for the polymer in the aqueous medium.1,3 Unlike conventional PUD synthesis, Evonik’s novel method uses a silicone building block, dihydroxy alkyl polymethylsiloxane, which carries two terminal OH groups, as seen in Figure 2. The choice of the correct silicone building block is essential to the successful development of this dispersion. If the selected silicone chain is too short, the dispersion will have little if any effect on properties. If the selected silicone chain is too long, incompatibility issues may occur, resulting in matte and cloudy films. The SILIKOPUR 8080 dispersion synthesis consists essentially of three steps, as seen in Figure 3.

By Christopher Howard, Markus Hallack and Wernfried Heilen | Evonik Industries Coating Additives, Hopewell, VA 46

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APR IL 2011 | W W W . P C I M A G . C O M

Dispersion Technology for

Systems First, a polyaddition of the diols is carried out with the isocyanate and the DMPA. In this reaction step, the integration of the silicone in the polymer chain requires accurate and precise mixing ratios due to its incompatibility. DMPA is used to stabilize the molecule, which has been made hydrophobic by the silicone modification, in water. The result of the polyaddition reaction step consists of a molecule with terminal isocyanate functionality that also contains acid groups. In the second reaction step, these compounds are neutralized with a tertiary amine, which leads to the formation of carboxyl groups. This is the amine neutralized prepolymer step. In the third and final step, the prepolymer is emulsified with an amine in water. Because the isocyanate groups are more inclined to react with the amine than water, the result is a molecule with a high molecular weight that is present in a stable, aqueous dispersion due to the neutralized carboxyl groups. This step is a “chain-lengthening” process.1,4,5

FIGURE 2 | Typical synthesis of conventional vs. silicone-modified polyurethane dispersions. Conventional Polyurethane Dispersion Diol HO

R

COOH Silicone-Reinforced Polyurethane Dispersion HO OH HO Si(CH3)2O Si(CH3)2O Si(CH3)2 OH HO OH OCN

Experimentation provided supporting evidence of this innovative new coating technology’s ability to maintain flexibility over a wide range of temperatures and conditions. When working with leather, SILIKOPUR 8080 dispersions can be applied at temperatures from -30 ºC to over 100 ºC without losing flexibility. As seen in Figure 4, the glass transition temperature (Tg) of this technology is lower than -50 ºC. This interesting property helps to minimize the long-term cracking and squeaking of the leather substrate over time. Leather sofas, shoes, chairs and clothing could benefit from maintaining the hydrophobic, soft feel and flexibility, while retaining their release properties.4,6

Nonstick: Automotive When considered for coatings on plastics and leather in automotive applications, the SILIKOPUR 8080 dispersion works well with substrates used in dashboards, steering wheels, car seats and even with ethylene-propylene-diene-

I. Polyaddition II. Neutralization III. Emulsifying & Crosslinking

FIGURE 3 | Synthesis of silicone-modified polyurethane dispersion. HO OH HO Si(CH3)2O Si(CH3)2O Si(CH3)2 OH

HO

OH OCN NCO COOH

Polydimethylsiloxane chain = PDMS

I. Polyaddition

OCN

II. Neutralization

PDMS

NCO

COOH +

Prepolymer

OCN

PDMS

NR3

NCO

COO - NHR3+ III. Emulsifying and Chain extension Crosslinking

1. H2O 2. Polyamine

COO - NHR3+

Silicone-Modified Polyurethane Dispersion

PDMS -

PDMS

PDMS -

+ 3

COO NHR3+

COO NHR

n

FIGURE 4 | Relationship between glass transition temperature and flexibility.

DSC

0.6 Heat Flow (W/g)

Flexibility and Feel: Furniture and Clothing

NCO

COOH

Polydimethylsiloxane chain = PDMS

Results and Discussion The SILIKOPUR 8080 dispersion technology was selected based upon its positive effects with leather, plastics and wood coatings. Furthermore, this novel technology provides manufacturers with a one-component, waterborne N-methyl2-pyrrolidone-free (NMP-free) coating with the ability to air dry. Furthermore, the SILIKOPUR 8080 formulation maintains hydrophobic properties, as well as excellent flexibility at low temperatures, chemical resistance, mar and scratch resistance, easy-to-clean nonstick properties, and a “soft feel.”

I. Polyaddition II. Neutralization III. Emulsifying & Crosslinking

Isocyanate DMPA OH + OCN R` NCO + HO OH

0.4 0.2 0.0 -0.2 -0.4 -50

0

50 100 Temperature (ºC)

150

200

PA I N T & C O A T I N G S I N D U S T R Y

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Novel Silicone-Modified Polyurethane Dispersion Technology for Advanced Coating Systems

TABLE 1 | Formulations for multilayer clearcoat on wood. Ingredients Conventional polyurethane dispersion SILIKOPUR 8080 Acrylic emulsion A Acrylic emulsion B TEGO® Wet 251 TEGO Foamex 830 Associative thickener Water Total by weight

Formula 1

Formula 2

Formula 3

20% 20% 70%

70%

0.3% 0.5% 0.3% 8.9% 100%

0.3% 0.5% 0.3% 8.9% 100%

Formula 4 20%

20% 70% 0.3% 0.5% 0.3% 8.9% 100%

70% 0.3% 0.5% 0.3% 8.9% 100%

TABLE 2 | Chemical resistance of common household items. Spot Test (DIN 68 861)

Formula 1 2 Mils DFT*

Formula 2 2 Mils DFT*

Formula 3 2 Mils DFT*

Formula 4 2 Mils DFT*

Chemical 1 hour spot 1 hour spot 1 hour spot 1 hour spot Beer 1 2 1 2 Red wine 2 3 2 4 White wine 1 1 1 1 Concentrated ammonia 1 2 2 2 Acetic acid 2 4 3 4 (1 mole) Ketchup 1 1 1 1 Mustard 4 5 4 5 Rating: 1- Excellent, 5 – Poor

* Dry Film Thickness (DFT)

rubber (EPDM) components. These EPDM parts are widely used in areas such as door and window moldings on cars. The SILIKOPUR 8080 dispersion offers dramatic benefits for EPDM components due to its superior flexibility over a wide range of temperatures, nonstick properties and the ability to reduce squeaking associated with the “stick-slip” effect. The traditional technology used for these EPDM coatings was fluorine-based, thus having potential adverse effects on the environment. In contrast, NMP-free SILIKOPUR 8080 dispersions offer an eco-friendly substitute for the fluoropolymers.

Chemical and Abrasion Resistance: Flooring and Furniture Our experiment next investigated the performance of SILIKOPUR 8080 dispersions with wood substrates, focusing on chemical resistance and abrasion. Because of its hydrophobic behavior, the modified dispersion provides short-term protection against typical household chemicals such as beer, red wine, white wine, acetic acid, ammonia, mustard and ketchup. As shown in Table 1, four different formulations were used to evaluate the chemical resistance of common household items. Formulas 1 and 2 utilized Acrylic Emulsion A: blended with the SILIKOPUR 8080 product in Formula 1; and, with a conventional PUD in Formula 2. As apparent from chemical resistance test results in Table 2, the formulation with the SILIKOPUR 8080

improved the chemical and stain resistance in 1 hour spot tests. Formulas 3 and 4 used a different acrylic with a higher glass transition temperature: blended with SILIKOPUR 8080 product in Formula 3; and, with conventional PUD in Formula 4. The results illustrate a trend similar to that in Formulas 1 and 2, with the SILIKOPUR 8080 blend showing substantial improvements compared with the conventional PUD blend. Abrasion and scratch resistance are key performance parameters when formulating coatings for wood flooring and furniture. Taber abrasion studies proved that 30%-by-total-weight SILIKOPUR 8080 dispersion blended with acrylic emulsions (Table 3, Formulation 3) significantly improves mar and abrasion resistance (Figure 5). It should be noted that when using greater than 30% blends of the urethane dispersions, as seen in Figure 5 data, the additional content does not increase abrasion resistance but actually decreases the effect. However, at the 30% blend mark, the SILIKOPUR 8080 modification shows significant benefit compared to the conventional PUD. Figure 5 provides a graphical analysis of the Taber Abrasion at both 500 cycles and 1000 cycles using a CS-17 wheel with a 1000-gram weight. As seen in Figure 6, the SILIKOPUR 8080 dispersion provides a significant improvement in abrasion resistance with only 32 mg of weight loss at 500 cycles and 64 mg at 1000 cycles.4,7

Conclusion The development of the SILIKOPUR 8080 dispersion, with its novel chemistry associated with silicone modification of urethane dispersions, shows benefit in a number of different applications such as wood, leather and plastics. When

TABLE 3 | Formulations for wood coatings. Increasing Levels of SILIKOPUR 8080

Increasing Levels of Conventional Polyurethane Dispersion

Ingredients Acrylic emulsion SILIKOPUR 8080 Conventional polyurethane dipserision Water ACEMATT® TS100 Texanol NH4OH Associative thickener Water

No.1

No. 2

No. 3

No. 4

No. 5

No. 6

No. 7

No. 8

703.0

624.9

546.8

468.7

703.0

624.9

546.8 468.7

100.0

200.0

300.0

400.0

--

--

--

--

--

--

--

--

87.9

175.8

263.6

263.6

21.9

--

--

--

34.0

24.2

14.5

4.2

13.1

13.1

13.1

13.1

13.1

13.1

13.1

13.1

7.0 0.9

7.0 0.9

7.0 0.9

7.0 0.9

7.0 0.9

7.0 0.9

7.0 0.9

7.0 0.9

4.2

4.2

4.2

4.2

4.2

4.2

4.2

4.2

149.9

149.9

128.0

106.1

149.9

149.9

149.9

149.9

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FIGURE 5 | Improvement in abrasion resistance with increasing levels of SILIKOPUR 8080 as compared with increasing levels of polyurethane dispersion. mg

mg

180 160 140 120 100 80 60 40 20 0

200 180 1000 U 160 140 120 100 80 60 40 500 U 20 0

No. 1

No. 2

No. 3

No. 4

No. 5

Increasing Levels of SILIKOPUR 8080

No. 6

No. 7

No. 8

Increasing Levels of Conventional Polyurethane Dispersion

FIGURE 6 | Abrasion resistance with increasing levels of SILIKOPUR 8080 as compared with increasing levels of conventional polyurethane dispersion (Taber – 1 kg CS 17). Taber Abrasion Taber Abrasion in mg/500 U in mg/1000 U Fn No. 1 80 154 No. 2

74

156

No. 3

32

64

No. 4

43

83

No. 5

69

153

No. 6

73

187

No. 7

72

155

No. 8

82

160

Fn

References 1 Hare, C. Protective Coatings: Fundamentals of Chemistry and Composition, Technology Publishing Company: 1994. 2 Kukackova, A. Using the Si-O Strength. European Coatings Journal 2007, Vol.6, 54-59. 3 Hare, C. Paint Film Degradation: Mechanisms and Control, The Society for Protective Coatings, 2001. 4 Hallack, M. Silicone-Reinforced Polyurethane Dispersions Create Functional Surfaces, Elements Science Newsletter, Vol. 24, p. 22-27, 2008. 5 Heilen, W. Silicone Resins and Their Combinations, Vincentz Network GmbH, 2005. 6 Tego Chemie Service GmbH: Tego Journal, 2007, 115-121. 7 Shen, W. Characterization of Mar/Scratch Resistance of Polymeric Coatings: Part I, CoatingsTech 2006 March, 54-60.

This paper was presented at the 37th Annual Waterborne Symposium, New Orleans, 2010.

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Acrylated Products Designed for Formability

Direct-to-Metal

T

his work investigates and reports on acrylated monomer and oligomer performance results when subjected to typical end-use tests designed to measure the flexibility and adhesion characteristics of coatings. Oligomers having adhesion-promoting characteristics were tested alone or in combination with monomeric acid-functional adhesion promoters to determine the best type of oligomer to use for a given substrate. Also the correct adhesion promoter level of addition was determined to obtain optimum performance results. In addition, moisture resistance as it relates to oligomer type was explored. Another significant development in the canmanufacturing industry has involved the elimination of Bisphenol A (BPA) from coatings that are intended for food packaging applications. The performance benefits of polyester acrylate oligomers are highlighted, compared and contrasted to those of Bis A epoxy acrylate oligomer. Each of the formulations used in this study are in fact BPA free.

Experimental An application area has emerged over the last several years that entails the use of radiation-curable coatings applied to a variety of metal surfaces. The usual standards of scratch and abrasion resistance are required. But the task is made more difficult as these coatings are required to adhere when applied to a variety of metal substrates having differing surface properties that can negatively impact

TABLE 1 | Adhesion promoters tested. Acrylated Acrylic Oligomers

Acid Functional Monomers

APO 20=CN820 APO 21=CN821 APO 22=CN822

AFM 50=CD9050 AFM 51=CD9051 AFM 53=CD9053

TABLE 2 | Importance and logic of oligomer selection (BPA-free). Oligomer Type Functionality Viscosity @ 25 °C Viscosity @ 60 °C Modulus, psi Tensile, psi % Elongation Tg °C by DSC

Polyester Acrylate

Epoxy Acrylate

4 70,000 cps 2,000 cps 160,000 6,800 15.0 31.2

2 850,000 cps 4,625 cps 212,000 8,400 1.5 20.9

adhesion. In addition, if these coatings are used for cans and rigid packaging, not only is adhesion required, but a degree of flexibility is needed to withstand the rigors of the manufacturing process that result in the finished metal container. Heat and moisture resistance are also factors when considering the retort process associated with food packaging or for pipe coating that will be used outdoors. Two groups of proprietary products have been developed to meet these difficult standards. The first is a series of phosphate acid ester monomers that are best used on an additives basis. They range in functionality from mono to tri with differing levels of acid content. For discussion purposes they are described as acid functional monomers or AFMs. The second group is best described as high-molecular-weight functional acrylic oligomers that have an adhesion promoter reacted into the backbone. The oligomers are di-functional, and for best adhesion results should comprise from 30-50% of the final composition. For discussion purposes these are called adhesion-promoting oligomers or APOs. Table 1 provides a listing of these components.

Application and Cure Conditions The conditions selected represent those that are commonly used in the metal decoration industry. Ideally the film thickness should be kept to a minimum in the interest of cost, but at the same time be thick enough that performance properties are not compromised. This is attained at the nominal film thickness indicated below. In addition, the curing conditions cited are fairly common for these applications as a thin clear is applied, negating the need for special fill bulbs. The radiometer type and results attained are also reported to avoid any variance in conditions that would affect film performance, thus ensuring consistency of the end-use test results. The application cure conditions were as follows. • Coatings applied with a zero bar to yield a film thickness of 0.2-0.3 mils (5-7 microns). • Cured using a 400 w/in medium-pressure mercury arc lamp at a conveyor speed of 100 fpm (350 Mj/sq.cm UVA, Power Puck radiometer trade mark).

BPA-Free Formulation Selection BPA is a chemical building block that is used primarily to make epoxy resins. Bisphenol A epoxy di-acrylate has

By William Schaeffer and Robert Kensicki | Sartomer USA, LLC, Exton, PA 52

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APR IL 2011 | W W W . P C I M A G . C O M

and Adhesion Enhancement in

Applications

Components

Weight Percent

Tetra-functional polyester acrylate

50.0

3EO TMPTA

14.9

DPGDA

14.9

TPGDA

14.9

Polymeric alpha hydroxy ketone photoinitiator

5.0

BYK371 (surfactant from BYK Chemie)

0.3

FIGURE 1 | Percent adhesion as it relates to AFM type, level and substrate. 100 90 80 70 60 50 40 30 20 10 0

Aluminum CRS

53 AF

M 10

%

AF

M

53

53 M 7%

51

AF

3%

AF

M 10

%

AF 7%

M

51

51 M

50

AF

M

3%

50 M

AF

10

%

AF

M

M

50

TPS

7%

All metal test panels used were obtained from Q-Panel. Prior to coating, the panels were washed with solvent

TABLE 3 | Base formulation used, unless otherwise stated.

AF

Substrates and End-Use Tests

As a family these products can best be described as acid esters. AFM50 is a mono-functional adhesionpromoting monomer that provides exceptional adhesion to metal substrates. AFM51 and AFM53 are tri-functional versions of AFM50. They offer the same

AF

For the obvious benefits cited, a PEA was selected as the major component for this formulation (Table 3). The monomers selected for this study consisted of tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate DPGDA), and 3-mole ethoxylated trimethylolpropane triacrylate (3EO TMPTA). TPGDA was selected as a lowvolatility and low-viscosity monomer that is commonly used for cost reasons in free radical polymerization. DPGDA is also an economical reactive monomer that can replace hexane diol diacrylate (HDDA). It has good viscosity-reducing properties and is more user friendly, having a Primary Irritation Index (PII) of 2 compared to 5 for HDDA. Ethoxylated TMPTA was also selected for its low skin irritancy, and it offers the added benefits of higher crosslinking and enhanced surface cure. The photoinitiator used for these formulations is a polymeric alpha hydroxyl phenyl ketone blended with 2-hydroxy-2 methyl-1-phenyl-1 propanone. The surfactant was used to ensure proper wetting of the substrate. The viscosity of the base formulation is 300 cps @ 25 °C.

Acid-Functional Monomers (AFM)

No

Formulation

(MEK) to remove surface contamination. Substrates that are commonly used and thus selected for testing include aluminum, tin-plated steel (TPS) and cold rolled steel (CRS). The tests conducted on cured films are as follows: • Cross-Hatch Adhesion – ASTM D 3359- Using 610 tape; • Reverse Impact Resistance – ASTM D 2794; and • Solvent Resistance – ASTM D 5402. Cross-hatch adhesion was selected as it relates the affinity of a given coating to a substrate. Reverse impact is interesting, as it relates not only adhesion but coating flexibility and provides an indication of the forming capabilities. MEK resistance gives a quick indication of how well the coating is cured.

3%

been the workhorse oligomer of the coatings industry for many years because of its exceptional combination of toughness, adhesion, formability and chemical resistance. The National Institute of Environmental Health Sciences recently conducted a study and expressed some concern regarding the long-term health effects of exposure to BPA. Hence, the can producers and formulators to the food packaging industry are moving toward BPA-free systems. A family of oligomers that meets the BPA-free criteria is polyester acrylates (PEAs). Table 2 offers a comparison of physical properties between a PEA and an epoxy, and highlights the benefits of going to a BPA-free alternative. Besides being BPA free, the PEAs offer these benefits: 1. Faster cure, tetra functionality as compared to difunctional; 2. Greater ease of handling, as the viscosity of the PEA is dramatically lower; 3. Greater formulation latitude is also observed as more of the PEA can be used in the final formulation without adversely affecting viscosity; 4. As tough as epoxies with better flexibility; 5. Better yellowing resistance than BPA-based oligomers.

PA I N T & C O A T I N G S I N D U S T R Y

䡲䡲䡲

53

Acrylated Products Designed for Formability and Adhesion

FIGURE 2 | Reverse impact testing (lbs of force) as it relates to AFM type and level

80 70 60 50 40

53 M

53 10

%

AF

M

53 M

AF 7%

51 3%

AF

M

51 10

%

AF

M

51 M 7%

AF

50

AF

M 3%

10

%

AF

M

50

AF

M 7%

AF

AF

3%

No

50

30 20 10 0

M

Pounds of Force

on tin-plated steel.

adhesion-promoting properties; however, owing to their tri-functionality, they provide faster cure response and greater hardness. Due to their high acid values these products are not recommended for use in formulations containing tertiary amines. Usage levels of 3% to 7% by weight are recommended. Acid values range from 120195 mg KOH/g. Table 4 relates the physical properties of the monomers.

AFM Adhesion Testing Each monomer was added to the base formulation at 3, 7 and 10% levels. Once thoroughly mixed, the coatings were applied onto each metal substrate and cured as prescribed. Upon curing, the test panels were allowed to equilibrate at room temperature for one hour before conducting crosshatch tape adhesion testing. The “Control” formulation contained no adhesion promoter. The trend is consistent with each AFM. As the concentration of AFM increases, the adhesion improves. The results also indicate that it is relatively easy to adhere to aluminum. Adhesion to CRS is more difficult, and adhesion to TPS is the most difficult. When adhesion performance of each AFM is examined, AMF53 yields the best overall results. The optimum level of addition is between 7% and 10%. Figure 1 details the test results.

AFM Reverse Impact Testing In addition to adhesion, the ability of the coating to withstand the rigors of processing is critical. Adhesion to a flat stock is relatively easy. However the metal sheets are ultimately shaped into a can body, can end or closure for a plastic or glass container. Reverse impact (RI) testing is a viable method to predict forming performance after cure. Figure 2 indicates the results. RI was tested on TPS panel as this substrate proved to be the most difficult to adhere to. As the name implies, reverse impact testing entails dropping a weight on the reverse side of the coated test panel. As the height from which the weight is dropped increases, the impact force and the deformation of the test panel and coating also increases. The impacted area is then inspected for signs of cracking or adhesion loss of the coating. The highest force at which no coating damage is detected is reported. The data shows that as the concentration of AFM increases the force also increases. AMF53 yields the best overall performance, exhibiting the greatest RI value on the most difficult substrate.

Adhesion-Promoting Oligomers (APOs) APOs can be described as high-Mw acrylate-functional acrylics. Being of a high Mw, they are higher in viscosity ranging from 3,000 cps to 8,000 cps @ 60 °C. These APOs contain adhesion-promoting materials that are reacted into the backbone of the oligomer structure; thus, they are less impacted by moisture sensitivity. APOs are not to be used as additives but should comprise from 30-50% of the final formulation. As they are not acid functional, they can be used in combination with amines unlike the AFMs. Another obvious difference between the oligomers is the color. APO 20 has a Gardner color of 4 while APO 21 and 22 has APHA colors of 34 and 70 respectively. Table 5 lists the physical properties of the APOs tested.

APO Adhesion Results Each of the APOs was added to the base formulation at concentrations ranging from 10 to 50%. Tin-plated steel (TPS) was selected for the test substrate as it has been shown to be the most difficult substrate for adhesion. The coatings were applied and cured under the conditions

TABLE 4 | Physical properties of acid-functional adhesion-promoting monomers. AFM Tested

Functionality

Viscosity @ 25 °C

Color

Density (g/cm3)

RI

Surface Tension (dynes)

Tg by DSC

Tensile Stress (psi)

% Elong.

1% Modulus (psi)

AFM50

1

20 cps

340 APHA

1.132

1.4513

33.2

-63.0 °C

341

6.3

5,556

AFM51

3

250 cps

5 Gardner

1.187

1.4696

36.24

41.0 °C

4,951

4.2

41,309

AFM53

3

725 cps

201 APHA

1.210

1.4711

38.7

27.0 °C

1,524

10.0

41,789

TABLE 5 | Physical properties of acrylated acrylic adhesion-promoting oligomers. APO Tested

54

䡲䡲䡲

Functionality

Viscosity @ 25 °C

Viscosity @ 60 °C

Color

Density (g/cm3)

Refractive Index

Tg by DSC

APO20

2

38,750 cps

3,312 cps

4 Gardner

1.03

1.4814

28.0 °C

APO21

2

54,600 cps

3,718 cps

34 APHA

1.04

1.4703

56.23 °C

APO22

2

424,000 cps

7,675 cps

70 APHA

1.05

1.479

63.5 °C

APR IL 2011 | W W W . P C I M A G . C O M

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Acrylated Products Designed for Formability and Adhesion

TABLE 6 | Moisture resistance testing on mill-finished aluminum. Formulation Variable

A

B

C

D

E

Oligomer Wt. % Di-functional Aliphatic UA APO Level AFM 53 DPGDA PEA

40

20

20

20

20

0

20 APO20

20 APO22

30 APO22

15 15 25

5 25 25

30 APO20 Monomer Wt. % 5 20 20

5 25 25

5 20 20

previously outlined. MEK resistance, reverse impact and cross-hatch adhesion were tested. Figure 3 shows the performance as it relates to APO concentration. The data related is typical for each APO. Adhesion and reverse impact performance improves as APO level increases. Optimum level of addition for good adhesion is 30%. Reverse impact continues to rise as more APO is added.

Moisture Resistance Testing

120

Another important requirement for DTM applications is the ability of the coating to maintain its properties when exposed to water. This exposure may occur during the processing phase of packaging or in outdoor use. The coating must maintain adhesion, while exhibiting no signs of softening or surface erosion. Table 6 illustrates the formulations used for this testing. In this case the APOs were tested in combination with a urethane acrylate oligomer. The APO used was either APO 20 or APO 22 at 20 and 30% levels of addition. The “Control” is formulation A and it contains no APO. Each coating was applied to mill-finished aluminum at a film thickness of 12 microns and cured as earlier described. Upon curing, adhesion was tested initially and after 1 hour and 2 hours submersion of the test panels in water at 100 °C. When APO 20 was added at the 30% level, adhesion immediately after cure and after 1 hour in 100 °C water was excellent. After 2 hours the adhesion dropped to 75%. APO 22 seemed to have better adhesion overall and excellent adhesion after 2 hours submersion in 100 °C water. The control formulation with no APO had only 20% adhesion initially and no adhesion after water exposure. Results are shown in Figure 4. Another measure of how well a formulation or an individual component will resist moisture degradation is to conduct accelerated weathering testing. In this case the “neat” oligomers were placed in a QUV test chamber. The cured panels were tested right after cure and at 100-hour intervals out to 500 hours QUV exposure. The yellowness index (YI) and gloss retention were recorded. The YI measures the degradation of the coating upon exposure to sunlight, while gloss retention measures the material’s resistance to microcracking (heat and light effects) or surface erosion related to the effects of moisture exposure. Table 7 details the cycling conditions for the QUV test chamber along with specifications for the measuring devices used and the test methods employed.

100

QUV Test Panel Preparation

(PI Used 5.0% Esacure KIP 100F)

TABLE 7 | QUV testing of acrylated acrylic adhesion-promoting oligomers. QUV Cycle Conditions

Gloss and Yellowness Index Measurements

UVA 340 from Q-Panel, 300-400 nm centered @ 340 nm Compares favorably to natural sunlight in this region 8 hours UV radiation @ 60 °C Followed by 4 hours dark condensation @ 40 °C Lamps replaced every 400 hours to ensure constant UV intensity

BYK Gardner, Micro-Tri-Gloss Meter @ 60º Angle, ASTM D 523 BYK Gardner, Yellowness Index, Model 6830, ASTM E 31

FIGURE 3 | Typical adhesion and RI results on TPS relative to APO concentration. MEK rub resistance > 200 regardless of APO level. 50% APO 30% APO 20% APO

Reverse Impact, in/lbs % Adhesion

10% APO NO APO 0

50

100

150

FIGURE 4 | Moisture resistance testing relative to type and level of APO used — mill-finished aluminum.

80

Adh. @ Ambient

60

Adh. after 1 h in water bath

40

Adhesion after 2 h 100 ºC water bath

20 0 No APO

56

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20% APO20

30% APO20

20% APO22

30% APO22

APR IL 2011 | W W W . P C I M A G . C O M

This testing differs from the previous conditions outlined, as the individual components are tested alone, not as additives to the base formulation. This will give a better indication of how the base oligomer performs. To enhance the ability to measure the YI, the oligomer containing only a photoinitiator (PI) was applied to a white basecoated panel at a film thickness of 1.5-1.75 mils. The curing conditions were also altered to better match the wavelength absorbency characteristics of the PI. Table 8 details the exact conditions. QUV test results (Figure 5) show that the APOs in terms of yellowing resistance perform very well when compared

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Acrylated Products Designed for Formability and Adhesion

to the control urethane acrylate (UA). This UA has in fact passed five years Florida exposure, inland south facing at a 5 degree angle. Although none of the oligomers yellowed significantly, APO 20 does show a dramatic loss of gloss after 100 hours QUV exposure (Figure 6). Visual inspection showed that this is not due to micro-cracking as noted with highly

FIGURE 5 | QUV testing of acrylated acrylic adhesion-promoting oligomers. Yellowness Index versus hours of exposure. 1 0.8 0.6 0.4 0.2 0 -0.2 YI -0.4

0

100

200

300

400

500

Aliphatic UA APO20 APO21 APO22

-0.6 -0.8

Conclusions/Observations BPA-Free This investigation has shown that improvements can be made to the formulation by using a PEA in place of a BPA-containing epoxy acrylate. Besides the obvious advantage of being a BPA-free formulation, it provides greater formulation latitude and enhanced performance benefits by having: 1. Dramatically lower viscosity, thereby increasing the ease of handling and eliminating the need to heat the oligomer to transfer from one container to another; 2. Greater formulation latitude by allowing more highmolecular-weight oligomer to be added to the formulation to improve performance without adversely impacting blending ease or increasing application viscosity; 3. Faster UV cure, as the PEA is tetra-functional versus difunctional for the epoxy acrylate; 4. Better yellowing resistance when compared to epoxy acrylates.

Acid-Functional Monomers, AFM

-1 Hours of Exposure

FIGURE 6 | QUV testing of acrylated acrylic adhesion-promoting oligomers. Gloss retention at 60° versus hours of exposure. 100 90 80 70 60 Gloss @ 60 50 40 30 20

Aliphatic UA APO20 APO21 APO22

10 0 0

100

200

300

400

500

Hours of Exposure

TABLE 8 | QUV test panel preparation, cure and application conditions. Clear Coats: •Neat oligomers •Photoinitiator: TPO at 3%

Substrate: •Cold rolled steel with E.coat/primer and white basecoat

UV Energy: Combined UVA, B, C and V Regions, Power Puck Radiometer, 4.5 J/cm2 •600 W/inch Fusion V lamp @ 25 fpm – in air •600 W/inch Fusion H lamp @ 25 fpm - N2

Film Thickness: 1.5-1.75 mils 58

functional urethanes, but is rather a loss of gloss related to surface erosion from moisture exposure.

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APR IL 2011 | W W W . P C I M A G . C O M

These components offer several advantages including: 1. Ability to promote adhesion to a variety of metal substrates, including aluminum, cold-rolled steel and tinplated steel; 2. Not limited to metal adhesion, as these monomers have been added to formulations that are applied on other substrates, such as wood and plastic with positive adhesion results; 3. Low level of addition required to impart good adhesion. Testing has shown that the optimum level is approximately 7%, resulting in minimal impact on other performance properties; 4. Testing has also demonstrated that these materials not only improve adhesion to the base substrate, but in applications such as wood where multiple coats are applied, greater intra-coat adhesion was noted. It should be noted again that AFMs should not be used with amines, as instability may result.

Adhesion-Promoting Oligomers, APOs These oligomers work best when they are the major or one of the main components of the formulation. Testing has demonstrated that the APO should comprise between 30 to 50% of the formulation. They do however offer the following benefits: 1. Improved moisture resistance as demonstrated by the water submersion test, resulting in 100% cross-hatch adhesion and in QUV exposure offering comparable yellowing resistance and gloss retention to that of an aliphatic urethane acrylate that has passed 5 years exposure in Florida; 2. Improved formability as demonstrated by higher reverse impact values on TPS; 3. No amine sensitivity as with the AFM. 䡲 This paper was presented at the RadTech 2010 Technology Expo and Conference, Baltimore, MD, www.radtech.org.

Mason Color’s high performance pigment technology for coatings provides the ultimate in heat resistance, UV durability, and chemical resistance. Our mixed metal oxide pigments meet the most exacting color and durability requirements of the defense, architectural, stove and heating products, and roofing industries. These pigments add vibrant color to building facades, stove equipment, exhaust parts and outdoor furnishings and equipment. These advanced technology pigments can be incorporated into any coating platform including powder coatings, electrocoat, high solids and waterborne paints.

Mason Color Works, Inc. A History of Pigment Technology Excellence Mason Color Works has been manufacturing high temperature, inorganic pigments since 1842. For more than 40 years Mason Color has been a global supplier of high performance pigments to all sectors of the ceramic industry including pottery, artware, bricks, sanitaryware and roofing materials. In the last 45 years, Mason Color has expanded into the high technology Investment Casting Industry. Our ISO Compliant Cobalt Aluminate products are integral in the manufacturing jet turbine blades and medical devices. In the 1990s heralded the emergence of the fireplace gas log industry and Mason Color's participation as a supplier of high quality, high temperature pigments for this use. Soon thereafter, the Swimming Pool and Spa colorant industry embraced Mason's pigment technology. Our high quality pigment exceed the demands for resistance to punishing UV energy and the aggressive chemicals used in swimming pools. Our fully outfitted Powder Coating Laboratory and skilled technicians will help you choose the perfect color for your most demanding requirements.

P RODUCTS 䡲 Blenders

CHARLES ROSS & SON CO.: V-Blenders are most often used for the dry blending of free-flowing solids. Materials being blended are constantly being split and intermixed as the shell rotates. Standard features include: intensifier bars for delumping; type-316 stainless-steel parts; 150-grit exterior finish; mirror finish on internal surfaces; manually operated butterfly discharge valves; safety railings and stainless-steel support stands; and fully integrated motors and controls. E-mail [email protected].

䡲 Oven

䡲 Emulsion

is an electrically heated oven available in NFPA 86 Class A or Class B configuration. A compact design features two independent oven chambers, each with separate controls and sharing a single dampered exhaust system. The oven is capable of reaching and maintaining a maximum temperature of 650 °F. E-mail [email protected].

for exterior coatings that offers excellent outdoor durability, good color retention and low dirt pickup in formulated paints. Mowilith VAE emulsions are the preferred choice of formulators for low-odor, lowVOC coatings with outstanding durability. Visit www.celanese-emulsions.com.

PRECISION QUINCY: Model #49C-650D

䡲 Flowmeter

KROHNE INC.: OPTISONIC 6400 portable

ultrasonic flowmeter for liquids measures flow velocity, current volumetric flow and a variety of diagnostic values. Users attach the sensor rail to the pipe, plug in the cables to the handheld OPTISONIC 6400, set up a few parameters, and begin reading instantaneous flow results. Results are stored in the integrated memory for data logging. Data can also be transferred via a USB stick to external evaluation systems for further review. E-mail [email protected].

䡲 Thickness Gauge

ELCOMETER: Elcom-

eter 456 is available in a range of models for measuring dry film thickness on ferrous and non-ferrous metal substrates. Features include: 2.4” color display, clear menu structure and large buttons; impact resistance and seal against dust and water; memory capacity of up to 75,000 readings in alpha-numeric batches; interchangeable probes and output to ElcoMaster 2.0™ software; measurement capability to ±1% on smooth, rough, thin and curved surfaces; and measuring speed of more than 70 readings per minute. E-mail [email protected]. 60

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CELANESE: Mowilith LDM 1865 is a VAE

䡲 Additives for UV Coatings

NANOPHASE: NanoArc® aluminum oxide dispersion additives are designed for UVcured coatings used on electronics and wood, and in a variety of graphic arts applications. Featuring various-sized nano and sub-micron alumina dispersed in commonly used monomers, they are active at low loading levels and do not negatively impact the application process or the mechanical properties of the coating. E-mail [email protected].

䡲 Instrument Catalog

BROOKFIELD ENGINEERING: The expanded 2011 catalog presents Brookfield’s complete line of viscometers and rheometers (both laboratory and in-line), texture analyzers, and powder flow testers. Typical applications are presented for various industrial markets. All Brookfield instruments are shown with their features, a list of what’s included with each instrument as well as available accessories. Visit www.brookfieldengineering.com.

䡲 Color-Matching Algorithms

DATACOLOR®: MatchCOM is a compre-

hensive suite of color-matching algorithms designed for seamless integration into the software platforms of leading paint, plastics, coatings, ink and textile companies. With more than 160 features, MatchCOM covers a wide range of color-matching functions including multiple calibration techniques, matching and correction

APRIL 2011 | W W W . P C I M A G . C O M

methods, load calculations, product-line management, sorting, and ingredient maintenance. Visit www.datacolor.com.

䡲 Thickener

ASHLAND INC.: Natrosol™ HE 3KB highefficiency, biostable cellulosic thickener is specifically engineered to provide outstanding in-can feel, brushability, and flow and leveling for waterborne decorative paints. Visit www.ashland.com.

䡲 Pump

WILDEN®: The Pro-Flo

X™ Air Distribution System offers operational flexibility in many diverse applications. With the Efficiency Management System (EMS™) optimizing the Pro-Flo X for actual operational parameters, regardless of the application demands or pump size, the operator uses an integrated control dial to select the efficiency point and flow rate that best suits the application. Visit www.wildenpump.com.

䡲 Resin

DSM NEORESINS+

NeoRad™ U-6288 is a 100-percent UV-curable resin that offers broad formulating latitude and high matte efficiency, working with most common matting agents. Matte coatings and varnishes produced with this resin do not burnish, and exhibit superior chemical and abrasion resistance. Because of its low viscosity, the resin has improved flow and more effective pigment wetting. Visit www.dsmneoresins.com.

䡲 Laboratory Dispersator

NETZSCH PREMIER TECHNOLOGIES, LLC,: The Model 50 Laboratory Disper-

sator produces repeatable dispersions through faster mixing action and improved motor performance. This highperformance, high-speed unit ensures constant mixing speed regardless of product weight, viscosity or other variables. Visit www.netzsch-grinding.com.

䡲 Pigment

THE SHEPHERD COLOR CO.: Blue 10F545 is approved for indirect food contact use by the U.S. FDA. Approval covers the intended use in all polymers, at a maximum loading of five percent by weight. It is insoluble in virtually all solvents and resins, will not bleed or migrate, and has good hiding power, opacity and tinting strength. Visit www.shepherdcolor.com. 䡲

www.coatingsconference.com

Coatings Trends & Technologies provides a global, resource-rich environment where attendees can engage with industry experts to learn about new products and developments that will improve coatings formulation.

98%

This affordable, 1-1/2 day, live event allows formulators to customize their educational and networking experience through concurrent technical sessions and an interactive exhibit hall.

97%

of attendees said they would recommend the 2011 event to a colleague or co-worker Source: 2010 Attendee Survey

of 2010 attendees were satisfied/extremely satisfied with the conference Source: 2010 Attendee Survey

2010

Sold out weeks in advance. Don’t miss your opportunity to attend!

SEPTEMBER 13-14, 2011 ■ OAK BROOK, IL CALL FOR PAPERS

Papers are now being accepted in the following areas: Additives Resins and polymers Pigments Solvents Nanotechnology Renewable raw materials Low-VOC technology UV-curing technology Powder coatings Waterborne systems Solventborne systems Green technology Improvements in adhesion Legislation and regulatory issues Test methods, materials characterization and performance evaluation Accelerated weathering SUBMIT YOUR ABSTRACT BY APRIL 15, 2011

PRODUCERS

CURRENT EXHIBITORS

WHO ATTENDS – Coatings formulators – Chemists – Technical managers – R&D personnel – Applicators/raw material suppliers – Quality control personnel – Analytical testing personnel – Technicians – Technical directors – Purchasing directors

C LASSIFIEDS RECRUITMENT SERVICES

EQUIPMENT

EQUIPMENT

Specializing in paint/coatings industry. Seeking passionate, high-impact professionals for nationwide positions. Send your resume in confidence to: Spencer M. Hermann

www.grindingmediadepot.biz

SEARCHLIGHT PARTNERS 28052 Camino Capistrano, Suite 209 Laguna Niguel, CA 92677 (949)429-8813 • [email protected]

Paint & Coatings Industry Executive Search Recruitment & Org. Consulting

www.bladedepot.biz

800-726-1366 [email protected]

www.thomasbrooke.com THOMAS BROOKE INTERNATIONAL Contact Nicola James [email protected]

888-896-3330 ext. 22

EQUIPMENT

Stainless IT

Stainless ITT

CONN Blade®s

The Most Efficient & Aggressive Available

PRODUCTS AND SERVICES Custom Pigment Dispersions Reitech Corporation

UHMW Poly

www.connblade.com

(814) 723-7980

Let us solve your Color Match Puzzle with our Aqueous products. 37+ years of technical expertise. www.reitechcorporation.com (610) 929-9451

HOCKMEYER

EQUIPMENT CORPORATION A leader in the grinding and dispersion industries

To place your classified ad, contact

New & Used Equipment Dispersers • Mills • Mixers • Tank & Tote Washers • Particle Size Analysis • Vessels

Andrea Kropp

Visit us at www.hockmeyer.com or call us at 252-338-4705 Wanted to purchase: Used Dispersers & Mixers

www.pcimag.com/classifieds

Ph: (810) 688-4847 Fax: (248) 502-1048 Email: [email protected]

PA I N T & C O AT I N G S I N D U S T RY

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63

C LASSIFIEDS POSITIONS AVAILABLE

POSITIONS AVAILABLE

ACCOUNT MANAGERS NEEDED Privately held, regional specialty chemical distributor has two openings for experienced Account Managers, selling to customers in the Paint & Coatings, Sealants & Adhesives, Plastics and Graphic Arts Industries. These positions will be responsible for developing new business in their geographic territories, as well as maintaining existing accounts. 3-5 years sales experience is required. Some overnight travel will be necessary. Positions available in Central Ohio and Minnesota. Salary and benefits commensurate with experience.

POSITIONS AVAILABLE

PRODUCT MANAGER NEEDED

SEEKING CHEMIST Ranbar seeks a senior chemist with resin and coatings experience. Knowledge of UL or electrical varnish testing beneficial.

Privately held, packaging supplier has an opening for an experienced Product Manager, selling plastic pails, steel pails, paint cans and related items to custom-ers in the Paint & Coatings, Sealants & Adhesives, Graphic Arts and Food Industries. Responsibilities of this position will include product manage-ment, sales management and direct selling. Salary with large bonus potential bases on P&L performance. 5+ years experience required.

Contact: Randy Russell

[email protected] (724)864-8200 www.ranbar.com

Insider News

Sign up for your free copy of PCI’s weekly e-mail newsletter at

Respond c/o PCI Ad #42 [email protected]; Fax: 248-502-1048

Respond c/o PCI Ad #41 [email protected]; Fax: 248-502-1048

www.pcimag.com.

AD INDEX Advanced Polymer Solutions . . . . . .23

Fielding Chemical Technologies . . .22

www.advancedpolymersolutions.com

www.fieldchem.com

Acme-Hardesty Co. . . . . . . . . . . . . . . .22

GEO Specialty Chemicals . . . . . . . . .21

www.acme-hardesty.com

www.geosc.com

Air Products . . . . . . . . . . . . . . . . . 35, 40

Heubach. . . . . . . . . . . . . . . . . . . . . . . . .43

www.airproducts.com/surfactants

www.heubachcolor.com

Alberdingk Boley, Inc. . . . . . . . . . . . .22

ISP Performance Chemicals . . . . . . . . 2

www.AlberdingkUSA.com

www.ispcoatings.com/water

AllCoat . . . . . . . . . . . . . . . . . . . . . . . . . .22

Jyoti Ceramic Industries. . . . . . . . . . . . 3

www.allcoattech.com

www.jyoticeramic.com

Arch Chemicals . . . . . . . . . . . . . . . . . .22

Kinesys Automation, Inc. . . . . . . . . .50

www.archbiocides.com/proxelbzplus

www.KinesysAutomation.com

Arkema Emulsion Systems . . . . . . . . . . . . 48-49

KW Container. . . . . . . . . . . . . . . . . . . . 57

www.arkemaemulsionsystems.com

Ashland Distribution Corp. . . . . . . . . . 4 www.ashland.com

BASF Corporation . . . . . . . . . . . . . . . .29 www.basf.us/coatingsindustry

Brenntag North America. . . . . . . . . . . 7 www.brenntagnorthamerica.com

Buhler Inc. . . . . . . . . . . . . . . . . . . . . . . 37 www.buhlergroup.com

Bway Corporation . . . . . . . . . . . . . . . . 55 www.bwaycorp.com/less-waste

BYK USA Inc. . . . . . . . . . . . . . . . . 11, 22 www.byk.com

CDC Microtron USA Inc. . . . . . . . . . .50 www.microtronusa.com

Celanese Emulsion Polymers . . 21, 45 www.EcoVAE.com www.Celanese-Emulsions.com

CINIC . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 www.cinic.com

Conn and Co. . . . . . . . . . . . . . . . . . . . . 16 www.connblade.com

Cytec Industries Inc.. . . . . . . . . . . . . . 51

www.kwcontainer.com

LANXESS Corporation . . . . . . . . . . . . 31 www.mpp.us.lanxess.com

Mason Color Works, Inc. . . . . . . . . . .59 www.masoncolorpigments.com

Munzing. . . . . . . . . . . . . . . . . . . . . . . . .68 www.munzing.com

OPC Polymers . . . . . . . . . . . . . . . . . . . .22 www.opcpolymers.com

Pan Technology, Inc. . . . . . . . . . . . . .23 www.pantechnology.com

Pilot Chemical . . . . . . . . . . . . . . . . . . .30 www.pilotchemical.com

Rhodia . . . . . . . . . . . . . . . . . . . . . . . . . .23 www.rhodia.com

Ross, Charles & Son. . . . . . . . . . . . . . .19 www.mixers.com

Sartomer . . . . . . . . . . . . . . . . . . . . . . . . 10 www.sartomer.com

The Shepherd Color Company . . . . .23 www.shepherdcolor.com

Siltech Corporation . . . . . . . . . . . . . . . . 6 www.siltechcorp.com

Soy Technologies, LLC . . . . . . . . . . . .23 www.soytek.com

www.cytec.com

Specialty Polymers, Inc.. . . . . . . . . . .50

Dow Coating Materials. . . . . 13, 15, 20

www.specpoly.com

www.dow.com/hiding www.dowcoatingmaterials.com/additives

Taminco. . . . . . . . . . . . . . . . . . . . . . . . .22

Elcometer . . . . . . . . . . . . . . . . . . . . . . . 18

Troy Corporation. . . . . . . . . . . . . 20, 67

www.elcometer.com

www.vantex-t.com www.troycorp.com

Elementis . . . . . . . . . . . . . . . . . . . . . . . 27

Unimin Corp. . . . . . . . . . . . . . . . . . . . .12

www.elementis.com

www.BrilliantAdditions.com

EMI . . . . . . . . . . . . . . . . . . . . . . . . . . . . .50

Univar. . . . . . . . . . . . . . . . . . . . . . . . . . .41

www.EMImills.com

www.univarcorp.com

Evonik Degussa . . . . . . . . . . . . . . . . . . 17

Yuron Chemical Industry . . . . . . . . . 61

www.evonik.com/colotrend

www.yulongchem.com

Visit ads.pcimag.com 64

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APRIL 2011 | W W W . P C I M A G . C O M

P U B L I S H I N G / S A L E S S TA F F Publisher/ East Coast/Europe/ Far East Sales Midwest/ West Coast Sales

Donna M. Campbell Tel: 610/650.4050 • Fax: 248/502.1091 E-mail: [email protected] Lisa Guldan Tel: 630/882.8491 E-mail: [email protected] China Media Rep. Arlen Luo 0086-10-88579899 E-mail: [email protected] Inside Sales Manager Andrea Kropp Tel: 810/688.4847 E-mail: [email protected] Production Manager Brian Biddle Tel: 248/244.6434 • Fax: 248/244.3915 E-mail: [email protected]

E D I T O R I A L S TA F F Editor Kristin Johansson Tel: 248/641.0592 • Fax: 248/502.2094 E-mail: [email protected] Technical Editor Darlene R. Brezinski, Ph.D. E-mail: [email protected] Associate Editor Karen Parker Tel: 248/229.2681 E-mail: [email protected] Art Director Clare L. Johnson

O P E R AT I O N S S TA F F Single Copy Sales Ann Kalb E-mail: [email protected] Reprint Manager Jill L. DeVries 248/244.1726 E-mail: [email protected] For subscription information or service, please contact Customer Service at: Tel: 847/763.9534 or Fax: 847/763.9538 or e-mail [email protected]

JUNE 7-8, 2011 THE WESTIN COLUMBUS COLUMBUS, OH Produced By

Powder Coatings Forum is a 2-day workshop and symposium that provides the basics of powder coating formulation, emerging technologies and trends, and networking with leading industry providers to discuss best practices.

WWW.POWDERCOATINGSFORUM.COM

We offer flexible registration packages to help you meet your educational needs. Join us for both days or choose to attend 1-day.

Register Today & Save!

Day One – Formulation Basics & Live Lab Demonstration 8:30am - 9:15am

Introduction & Nomenclature

9:15am - 10:00am

Chemistry & Performance

10:00am - 10:15am

Networking Break

10:15am - 11:00am

Special Effects

11:00am - 11:30am

Application Technology

11:30am - 12:15pm

Troubleshooting for Performance

12:15pm - 1:15pm

Networking Luncheon

1:30pm - 4:30pm

Live Laboratory Demonstration

Early bird rates expire April 29 Send the team for significant savings –

Buy 2 Get 50% off all additional

- Part One: Powder Coating Manufacturing – Formula to Finish Coat • Presented by: - Part Two: Evaluating Powder Coating Film Performance • Presented by: 4:30pm - 6:00pm

Networking Reception & Sponsor Exhibits

Day Two – Emerging Trends & Technologies 8:30am – 9:15am

Renewable and Bio-Based Resin Systems for Coatings with a Focus on Powder Coatings

9:15am – 10:00am

The Pure Chrome Effect – The Dawn of a True Metallic Look Powder Coating

10:00am – 10:15am

Networking Break • Sponsored by:

10:15am – 11:00am

Going Green… then Why UV Powder?

11:00am – 11:45am

The High Performance of Copolymer Polyethylene Powder Coatings

11:45am – 1:00pm

Networking Luncheon & Sponsor Exhibits

1:00pm – 1:45pm

The Latest Developments in Fast Color Change Powder Coating Application

1:45pm – 2:30pm

Advancements in Fluoropolymer Powder Coatings

2:30pm – 2:45pm

Networking Break

2:45pm – 3:30pm

Nano Preatreatment for AAMA and Mixed Metal Substrates

3:30pm – 4:15pm

Powder Coating of Architectural Fiberglass

4:15pm – 5:00pm

Colored Pigments in Powder Coatings: Their Chemistry & Performance

Leverage your Brand & Build Sales Leads with your Target Audience Contact Donna Campbell, Publisher PCI magazine, at 610-650-4050 or [email protected]

Istanbul The Bridge Between East and West

Coatings Show Eurasia 4th International Coatings, Inks, Adhesives, Insulation, Sealants, Construction Chemicals Raw Materials and Production Technologies Exhibition

6-8 October

Istanbul Expo Center Media Partner

Organized by

www.turkcoat.com www.artkim.com.tr This exhibition is organized under the permission of TOBB according to the law 5174

The new Z-line of performance additives aims to provide improvements to customers developing environmentally sustainable green coatings. As the demand for "green" coatings continues to rise at a furious pace, Troy’s Z-line offers formulators enhanced performance in making greener coatings possible without adding undesirable components such as VOCs or HAP’s. With the Z designed products, Troy continues its commitment to assist industry in addressing the need for performance products that are environmentally responsible and yet economically viable. Contact your Troy Sales Representative for information on the Z-line of Troy performance additives or visit www.troycorp.com.

Troy Corporation, 8 Vreeland Road, Florham Park, New Jersey USA 07932 • Telephone: +1 973-443-4200 • Fax: +1 973-443-0258

Relentlessly working for YOUR perfect solution

Münzing. Solving your foam issues by providing the broadest range of defoamer chemistries and unlimited technical assistance to the coatings and printing ink industry. While we may deal in complex science, what we do is very simple. We make your job easier. By conducting unlimited, rigorous testing with the broadest range of defoamer chemistries, we’ll develop precisely the defoaming additive that solves your problem. It’s this kind of unyielding commitment to the needs of coating and printing ink formulators everywhere that has gotten us to where we are today. Practically on speed dial at some of the largest, and smallest, coating and printing ink R&D labs around the world.

The Industry Standard in Defoamers DEE FO® XRM-1537A DEE FO® XRM-1547A DEE FO® 3010E/50 DEE FO® 97-3 DEE FO® PI-12

DEE FO® PI-30 DEE FO® PI-35 DEE FO® PI-40 DEE FO® PI-45 DEE FO® PI-75

AGITAN® 299 AGITAN® 350 AGITAN® 760 AGITAN® 771

To try our AGITAN and DEE FO defoamers and take advantage of our unlimited technical service, call

1-800-524-0055

www.munzing.com I [email protected]