Paint & Coatings Industry 2010,03

V IEWPOINT

Uncertainty As hard as I try to maintain optimism and really look in all the nooks and crannies for signs of a major turnaround – it is still tough out there. When you have been in the industry as long as I have it is so frustrating and sad to see a lack of growth, R&D budgets severely curtailed and in some cases cut completely, and an industry that you love continue to shrink. It is difficult to talk to young people in the schools and encourage them to pursue the sciences as a career choice. You wonder if they will be able to find a job. How do you jumpstart an economy that has moved offshore? As we continue to offshore jobs, we reduce the bluecollar and middle-class job growth. Reports indicate consumer spending is up a bit, and 4th quarter reports for many chemical companies and coatings manufacturers were optimistic. But for all the money the government has dumped into the system, consumer demand is still down and the country is immersed in a

Will your coatings stand the test of time? ACT Test Services is your one stop shop for testing the corrosion resistance of coatings. From the application of your coatings on our standardized test substrates through testing and reporting of results, our knowledgeable staff will be there for you every step of the way.

quagmire of debt and unemployment. GDP for 4th quarter might be up a bit – BUT is it really because we hit a wall and there had to be some production as inventories had dried up? Is this just an adjustment? The global economy is not offering much in the way of a glimmer of hope. As of today, Greece is in serious trouble and may need a bailout from the EU, Germany or someone else; Greece once was the cradle of Western Civilization and democracy. Spain and Portugal are not far behind – all of these countries, and others as well, are experiencing high unemployment, extraordinary government debt, high taxes and frozen wages. And the United States is mirroring the same problems. It has become rather accepted that we do not run a balanced budget in the country. You simply cannot run forever on this sort of thinking in the country, in your company or in your household. When you get so far in debt you have to either default a large portion of it away or inflate it away. We are facing a serious debt implosion. In general, people have a false notion about inflation – it is NOT rising prices and wages. These are the effects of inflation and they are damaging. Inflation is an increase in the supply of money – so the government can print more money and increase the supply to finance the deficits resulting from out-of-control spending. But all that means is that all the money in circulation becomes less valuable – the water-downed dollar will have less purchasing power. It is an insidious form of taxation. The result is that companies have to raise their prices and workers then need higher wages to be able to support families, and a downward spiral ensues. Only the government can stop inflation. And only the government can stop the spending. We need to get people back to work – any increases in taxation, or green taxes will only further take us down in my opinion. Look back in history and just study California – between government regulations and increased business taxes is it any wonder that the jobs have left and the state is in significant debt? So far the coatings industry has weathered the roller coaster ups and downs as best as we can but for how much longer? I am hoping that we have a great turnout at the AC Show – maybe the enthusiasm that is usually predominant at these shows will spread and generate some excitement.

Contact us today for detailed information on all our services! www.acttestpanels.com - 517.439.1485 Visit ads.pcimag.com 6

䡲䡲䡲

006 Viewpoint.indd 6

By Darlene Brezinski, Ph.D. / Editor

MARCH 2010 | W W W . P C I M A G . C O M

2/16/10 3:56:45 PM

I NDUSTRY NEWS

New MPI Program Showcases Paint Raw Materials PITTSBURGH – The Master Painters Institute (MPI), an institute that establishes architectural paint standards and quality assurance programs in North America, has launched its Starting Point program for paint raw materials suppliers. Since the year 2000, when the U.S. government dropped its federal paint standards and replaced them with the MPI system, MPI has published an Approved Products List of paints that pass its performance standards. Now, under the new Starting Point program, MPI will invite paint raw materials suppliers to submit wet samples of their starting point (guide) formulas that feature their

new or strategic materials. “We believe this program could make it easier for our listing paint manufacturers to adopt new technologies to meet MPI performance standards,” said President Barry Law. “The push towards ‘greener,’ more environmentally safe products has brought a lot of new technology to the market, and paint suppliers don’t always have the

lab time, personnel time or resources to thoroughly evaluate everything they’re shown,” continued Law. “We think this program could save paint suppliers valuable time and resources in their work, and that will help them get new products to market faster and speed up acceptance at the end-user level. There’s potential here to move the whole industry forward more quickly to higher performance and environmentally friendly technology.” The program is ideally suited for suppliers of resins, additives, solvents or non-color pigments who target commercial and architectural coatings applications.

Courtesy of The Paint Quality Institute.

SME and ASTM Develop First Additive Manufacturing Standards DEARBORN, MI – Additive manufacturing now has a universal name and a universal language, thanks to a collaboration between the Society of Manufacturing Engineers and ASTM International. “Rapid prototyping has meant different things to different manufacturers. It means quick prototyping to one and layered manufacturing to another. Now it’s called additive manufacturing,” explained Brent Stucker, a member of SME’s Rapid Technologies and Additive Manufacturing (RTAM) community and an Associate Professor of Mechanical and Aerospace Engineering at Utah State University. In an effort to eliminate the confusion over terminology, design, testing methods, materials and processing differences, SME’s RTAM community approached ASTM to develop the industry’s first-ever standards. ASTM, in turn, formed the Committee F42 on Additive Manufacturing, including members of the RTAM community, to write new standards. The initial result is the publication, “Standard Terminology for Additive Manufacturing Technologies,” now available for purchase online. Stucker, who is also the Chairman of Committee F42, says that terminology standards will help clarify communications, especially in industries like medical manufacturing and aerospace where consistency is a must. According to ASTM, these new standards will let manufacturers compare and contrast the performance of different additive processes and will give researchers and process developers the ability to provide repeatable results. In addition to terminology, Committee F42 will also develop other key industry standards. ASTM’s Committee F42 is looking for additional members to help draft these standards. For information about participating in RTAM, visit www.sme. org/rtam. For information about the Committee F42, contact Pat Picariello at [email protected]. 8

䡲䡲䡲

008 IndustryNews.indd 8

ASSE Works to Add Safety to “Green” Initiatives DES PLAINES, IL – As businesses, schools and communities go “green,” the American Society of Safety Engineers’ (ASSE) occupational safety and health professional members are working with their organizations to incorporate safety practices in line with “green” initiatives. A recent ASSE Hospitality Branch report noted, “While ‘greening’ efforts eliminate or reduce some traditional risks, they may increase existing risks or introduce new ones for workers.” To address this issue, the ASSE Chicago chapter is providing educational work-safety programs. ASSE Chicago members Allen Borzych and Neil Silins, through the chapter’s Outreach Committee, are providing safety, health and environmental (SH&E) training to students in the Chicagoland Green Collar Jobs Initiative, an organization that works to develop a skilled workforce ready to serve the “green” marketplace. The ASSE Chicago chapter also works with the local Economic and Employment Development Council, where ASSE members provide an Introduction to Safety presentation.

The EPA Initiates Chemical Action Plans WASHINGTON, DC – The U.S. Environmental Protection Agency (EPA) has released the first set of Chemical Action Plans (CAPs). The plans are part of a previously announced plan for enhancing chemicals management under the Toxic Substances Control Act (TSCA). The four chemicals included in the plans are phthalates, short-chain chlorinated paraffins, polybrominated diphenyl ethers (PBDEs) and perfluorinated chemicals, including PFOA. The EPA stated in a press release, “For the first time, EPA intends to establish a Chemicals of Concern list and is beginning a process that may lead to regulations requiring significant risk reduction measures to protect human health and the environment. The agency’s actions represent its determination to use its authority under the existing Toxic Substances Control Act (TSCA) to the fullest

MARCH 2010 | W W W . P C I M A G . C O M

2/16/10 3:59:42 PM

I NDUSTRY NEWS extent possible, recognizing EPA’s strong belief that the 1976 law is both outdated and in need of reform.” The EPA’s action plans will: summarize available hazard, exposure and use information; outline the risks that each chemical may present; and identify the specific steps the agency is taking to address those concerns. Commenting on the EPA’s announcement, the American Chemistry Council (ACC) expressed concern over issues of transparency in the selection process and uncertainty in the scientific basis of the selection of chemicals. The EPA also announced that benzidine dyes and pigments, and bisphenol A are currently in the action plan development process.

for the specialty chemicals business of Dow Corning, to serve as Vice Chairman of the 2010 International Board of Directors. His two-year term began January 1. Yarosh is currently Vice Chair of ASTM International Committee C24 on Building Seals and Sealants, and he also serves on Committees D14 on Adhesives, E06 on Performance of Buildings and E60 on Sustainability.

Missouri S&T Coatings Institute Offers Courses ROLLA, MO – The Missouri S&T Coatings Institute of the Missouri University of Science and Technology, formerly known as the University of Missouri – Rolla, is offering several short courses this spring and summer. Basic Composition of Coatings will be offered March 29 to April 2, 2010, in Rolla, MO. Introduction to Paint Formulation will take place May 17-21, 2010, in Rolla, MO. Coatings for People in General Industry, Sales and Marketing will be held

ASTM Elects New Member to Board of Directors MIDLAND, MI – The American Society for Testing and Materials (ASTM) has elected Ken Yarosh, Global Service Line Manager

K-KAT XK-614 & DBTDL Comparison Gloss (Photos) and Hardness (Graph)

Pendulum Hardness (Cycles)

New K-KAT® XK-614 is a zinc complex catalyst ideally suited for a variety of coating applications offering:

100 90 80

x x x

70 60 50

K-KAT XK-614

30

DBTDL

20

No Catalyst

10 0 0

2

4

6

HORSHAM, PA – The technical committee of the Philadelphia Society for Coatings Technology Inc. has announced its May symposium, “Current Trends in Extenders and Functional Fillers for Coatings and Related Materials.” The symposium will take place May 4, 2010, at The Williamson in Horsham, PA. Presentation topics include: Incorporating Filler Pigments into Environmentally Friendly Coatings, Green Formulating Solutions Using Engineered Functional Fillers, Coated Calcium Carbonate and Talc for Coatings Applications, Kaolin Applications in Coatings, A Primer for Primers – Formulating with Corrosion Inhibitors, Silica Applications in Coatings, Organic Fillers, and Functional Fillers in UV Floor Coatings. Visit www.psct. org for additional information.

We’ve got an ADD for that !

DBTDL Aged 2 Hours

40

Philadelphia Society for Coatings Technology Offers May Symposium

Trying to formulate a 2K WB Acrylic Urethane without using DBTDL?

®

K-KAT® XK-614 Aged 4 Hours

July 19-21, 2010, in St. Louis, MO. For details, visit http://coatings.mst.edu.

8

x x

F ilm A ge ( D a ys )

New K-KAT® XK-614 Non-tin, Mercury-free Catalyst for Urethanes Attend “New Tin Free Organometallic Catalysts for Urethanes” ACS Conference - 11:30 AM - April 14 - Session 15.5

Excellent hydrolytic stability Excellent pot life Selective catalysis of the polyol/isocyanate reaction in the presence of moisture Better hardness development Excellent film properties

To find the perfect ADD for your APP...Visit: www.kingindustries.com or King Industries - Booth #2515 at the American Coatings Show Science Road Norwalk, CT 06852  (203) 866-5551  [email protected]

Visit ads.pcimag.com 10

䡲䡲䡲

008 IndustryNews.indd 10

MARCH 2010 | W W W . P C I M A G . C O M

2/16/10 4:00:01 PM

I NDUSTRY NEWS Sink or Swim 2010 Set for May CLEVELAND – Sink or Swim 2010 will be held May 18-19, 2010, at the University of Akron. The event will feature a strong technical program as well as a short course. Exhibits will be held on Tuesday, May 18, from 12:30 p.m. to 3:30 p.m. A poster ses-

sion and poster competition will also be offered this year. For additional information, visit www.clevelandcoatingssociety.org.

ISO Revises Standard for Particle-Size Analysis MALVERN, UK – The International Organi::: Intelligence in Rheometry

Rheometry Focusing on Solutions

zation for Standardization (ISO) has released ISO13320:2009, a newly revised standard for laser-diffraction particle-size analysis. Building on a knowledge base that has advanced significantly over the preceding decade, ISO13320:2009 is an essential resource for instrument manufacturers and users alike. Malvern’s Masterclass series of ondemand webinars covers the majority of topics raised in the new standard and provides a starting point for those wishing to adopt best practices that are in line with the guidance in ISO13320:2009.

SSCT Issues Call for Papers for Annual Meeting DAYTONA BEACH, FL – The Southern Society of Coatings Technology (SSCT) has issued a call for papers for its upcoming 2010 Annual Meeting & Technical Conference, held Sept. 26–29, 2010, at the Hilton Resort, Daytona Beach, FL. The emphasis of the conference is promoting new technologies in the coatings industry, and the theme is “Racing to New Technology in Coatings.” If you are interested in presenting at the meeting, e-mail Randy Waldman at randy. [email protected]. Details of the conference can be found at www.ssct.org.

Organizations Team up to Offer Spray Finishing Training TOLEDO, OH – DeVilbiss, Binks and Owens Community College have teamed up to present a Spray Finishing Technology workshop. The three-day program is scheduled May 19-21, 2010, in Toledo, OH. Classes include both classroom and handson sessions. Topics for the workshop include: equipment types and selection; equipment setup, operation and maintenance; surface preparation and defect analysis; material selection; and safety and regulatory concerns. For additional information, visit www.owens.edu/ workforce_cs/spray2010.pdf.

Fully automated, robotically operated: The HTR High Throughput Rheometer from Anton Paar. ³ Automatic sample filling and cleaning of measuring systems ³ Processes up to 96 samples in a single run up to 24 hours

Short Course on Underground Corrosion Offered Anton Paar® USA

³ Modular setup, flexible to individual applications ³ All standard MCR 301 test types, configurations and accessories apply

800-722-7556 [email protected] www.anton-paar.com

Visit ads.pcimag.com

䡲䡲䡲

PCI03094ANTN.indd 1

12

008 IndustryNews.indd 12

MARCH 2010 | W W W . P C I M A G . C O M

MORGANTOWN, WV – The 55th annual Appalachian Underground Corrosion Short Course will take place May 18-20, 2010, at West Virginia University, Morgantown, WV. The short course provides technical information about the causes and prevention of corrosion on underground structures. For registration and additional information, visit www.aucsc.com. 䡲

2/3/09 9:55:41 AM

2/16/10 4:00:12 PM

C ALENDAR Meetings, Shows and Educational Programs Coatings and Paint Technology www.emich.edu/cri

29-31 Middle East Coatings Show www.coatings-group.com

22-25 AFS Annual Conference www.afssociety.org/spring2010

29-April 2 Basic Composition of Coatings http://coatings.mst.edu/index.html

MARCH 16-18

APRIL 8-10 CISILE 2010 www.cisile.com.cn/en

T

12-15 American Coatings Show & Conference www.american-coatings-show.com

®

H E Patented blending/dispersing blade design makes radical improvement over old saw tooth designs

13-16 PaintExpo www.paintexpo.de 18-20 ASC Spring Convention www.ascouncil.org 20-22 Emulsion Polymerization and Waterborne Coatings www.emich.edu/cri 20-22 Logichem 2010 www.logichemeurope.com 30 Understanding Coating Raw Materials www.emich.edu/cri

MAY 4 POLY

STAINLESS

*

Most efficient and aggressive blending/dispersing blade available.

*

Provides proper combination of pumping action and shear/ dispersion essential for fast consistent results.

* * * * *

Built in pumping action cuts processing time.

*

Philadelphia Society for Coatings Technology May Symposium www.psct.org 4-6 ELECTROCOAT 2010 www.electrocoat.org 4-6 Particles on Surfaces: Detection, Adhesion and Removal www.mstconf.com

Longer life due to heavier gauge construction. Less heat due to shorter required running time. Excellent for high or low speed and high or low viscosity. Supplied with hubs or mounting holes required to retrofit and upgrade present equipment. Pumping blades without teeth are available and are excellent for gentle blending and agitation.

5-6 Basics of Polyurethane Coatings www.emich.edu/cri 12-14 NW Coatings Fest 2010 www.pnwsct.whomedia.com/symposium-ncf 17-21 Introduction to Paint Formulation http://coatings.mst.edu/index.html

DESIGNERS AND MANUFACTURES OF INDUSTRIAL MIXING EQUIPMENT

Since 1948

CONN CO., L.L.C. AND

www.connblade.com

Stirrers Or Complete Units For: PAINTS URETHANE FOAMS ADHESIVES SLURRIES INKS GROUTS CEMENTS ETC. . . .

11 SOUTH MARION STREET • WARREN, PENNA. 16365 • PHONE 814/723-7980 FAX (814) 723-8502

s r

r

TM

18-19 Sink or Swim 2010 www.clevelandcoatingssociety.org 18-20 Appalachian Underground Corrosion Short Course www.aucsc.com 18-20 Advanced Topics in Polymers and Coatings www.emich.edu/cri

Visit ads.pcimag.com 14

䡲䡲䡲

014 Calendar.indd 14

MARCH 2010 | W W W . P C I M A G . C O M

2/16/10 4:02:33 PM

N AMES IN THE NEWS 䡲 JNS Smithchem LLC has appointed Doug

䡲 Michael F. Hilton has been named Nordson Corp.’s new President and Chief Executive

Bennett to the newly created position of Regional Sales Manager, New England. Bennett will be responsible for expanding the company’s customer and supplier base in New England.

䡲 Pamela R. Butcher has been appointed President and Chief Operating Officer of Pilot Chemical Co. Reporting to Chairman and Butcher CEO Paul Morrisroe, Butcher has responsibility for the supervision and direction of all functions and operations at Pilot.

Officer. Hilton, who will also join the Nordson Board of Directors, will succeed retiring President and CEO Edward P. Campbell. Nordson Corp. also announced the appointment of Anne M. Pombier as the company’s Director of Corporate Development.

Hilton

䡲 Jim Martin has joined Gaco Western as Area Sales Manager in

䡲 The HallStar Co., a specialty chemical company headquartered

the Commercial Coatings division for the Georgia, North Carolina and South Carolina territory. Gaco Western also announced the retirement of Irene Schwechler, Vice President of Manufacturing.

䡲 BASF has appointed Dirk Elvermann Director of Legal and Tax

䡲 Tennant Co. has appointed Donald Leo Mulligan to its Board of Directors. Mulligan has extensive experience in international financial management and operations.

in Chicago, has appointed James R. Conaty, Robert B. Covalt and James N. Hallene to its Board of Directors.

Asia Pacific. Elvermann joined the Central Legal Department of BASF SE in 2003, where he focused on mergers and acquisitions.

䡲 Daniel Grasset has been appointed President, Total Resins. He succeeds Bernard Pinatel who is now President, Total Adhesives (Bostik).

䡲 Jukka Havia has been appointed Tikkurila’s CFO and mem-

ber of the Management Board. He will report to Erkki Järvinen, President and CEO of Tikkurila Oy.

䡲 Koch Membrane Systems has hired Hamid R. Rabie as Senior Vice President of Technology. Rabie will manage all research and development activities within the company. 䡲 National Coatings Corp.

has announced the appointment of Micah Smith as Technical Sales Representative. Smith will be responsible for field technical support, inspections and the warranty program in the western states region. 䡲

Visit ads.pcimag.com 16

䡲䡲䡲

016 Names.indd 16

MARCH 2010 | W W W . P C I M A G . C O M

2/16/10 4:05:56 PM

C O M PA NY NEWS

ADM Receives Grant to Develop Advanced Biofuels DECATUR, IL – The U.S. Department of Energy has awarded Archer Daniels Midland Co. (ADM) a $24.8 million grant to develop and construct a facility that will convert biomass into renewable fuel. The ADM Advanced Biorefinery project will produce fuel ethanol and ethyl acrylate, a compound used to make plastics, adhesives, coatings and a range of other materials. The technology used to begin breaking down the biomass, a step called pretreatment, will also be applicable in ADM’s ongoing efforts to commercialize biocrude, a renewable product that can

be refined into drop-in transportation fuels at existing petroleum refineries. Sustainable collection and transportation of biomass is an essential step on the path to large-scale commercialization of advanced biofuels. Toward that end, ADM is collaborating with Deere & Co. and Monsanto Co. to develop a sustainable supply of corn stover, the stalks, leaves and cobs of corn plants that are usually left on the field. The companies are working together to identify environmentally, agronomically and economically sustainable methods for the harvest, storage and transport of corn stover.

AkzoNobel’s Ningbo Plant Starts Production NINGBO, China – Production has started at AkzoNobel’s chelates facility located at the company’s new site in Ningbo, China. The new plant, which will help to optimize the company’s global supply chain, will produce most of the basic chelates in AkzoNobel’s Dissolvine® product range. This will include the company’s new biodegradable chelating agent, Dissolvine GL. The startup of the first activities in Ningbo means that AkzoNobel is now the only major producer of chelates with plants in Europe, North America and Asia. New ethylene amines and ethylene oxide factories are also due to begin production at the site in 2010, followed by an organic peroxides facility.

WACKER ACADEMY’s motto is “Learning from the past for the future.” The academy will work to integrate the group’s knowledge and expertise into a unique concept for specialized training courses. The emphasis remains on comprehensive constructionchemicals training, which, in addition to polymer chemistry, now also covers subjects related to silicone applications. The expanded program has more interdisciplinary training such as seminars on energy-efficient building and masonry protection. In addition, specialized chemistry courses for other sectors, such as the cosmetics and paint industries, will be offered. The course program is rounded out by an introduction to business administration, intercultural cooperation and the productive use of e-business tools.

Sensient Technologies Announces China Expansion MILWAUKEE – Sensient Technologies Corp. has opened new facilities in China, located in Guangzhou and Shanghai. The facility in Guangzhou includes an office and laboratory building, a manufacturing plant and a separate fragrance building. These facilities will produce colors, flavors, pharmaceutical coatings and fragrances primarily for the Chinese market. Sensient’s technical center and sales office in Shanghai, China, will feature the latest lab equipment and an ultra-high-temperature process pilot plant.

WACKER Broadens Scope of International Training Programs MUNICH, Germany – WACKER is expanding the curriculum of its international training and competence centers and will offer more interdisciplinary courses this year. The ongoing content-specific and strategic changes are reflected in the centers’ new name: the WACKER ACADEMY. These centers are not only an ideal platform for advanced training, but also offer sector-specific networking between customers, distribution partners and WACKER specialists. WACKER ACADEMY sites have already opened in Germany, Russia, China and India, with more to follow in 2010. 18

䡲䡲䡲

018 Company News.indd 18

NETZSCH’s New Bead Mill Available for U.S. Testing EXTON, PA – NETZSCH Fine Particle Technology’s latest ZETA® RS stirred media mill is now installed in its technical laboratory in Exton, PA. Engineers and researchers are invited to NETZSCH’s Technical Center to test the upgraded mill, which is ideal for fine grinding and mild dispersion down to the nano range.

Evonik Offers New Tools for the Industrial Coatings Market PARSIPPANY, NJ – Evonik Degussa Corp. has introduced an allinclusive color reference book for the industrial coatings market. The new Portfolio of Color® features over 2,760 colors at two sheen levels and the supporting formulations. Portfolio of Color provides industrial coatings producers with the freedom to create customized color-selection sales aids. The CHROMA-CHEM® Color Identifier™ is a handheld device that speeds the process of color selection in the field. It reads the target or substrate color and then locates the closest acceptable color match in the Portfolio of Color book. The unit displays three potential matches (good, better or best) for the user to choose from.

MARCH 2010 | W W W . P C I M A G . C O M

2/17/10 2:32:04 PM

Ask the Expert Jim Reader Lead Research Chemist

Q

My coating needs a silicone defoamer, but everything I try results in craters or fisheyes! How can I achieve powerful defoaming without causing surface defects?

A

Air Products’ Surfy¯nol® DF-178 defoamer was developed to provide the defoaming strength of a silicone-based defoamer but with the superior system compatibility needed in higher gloss and clear coat applications. As a result, this 100% active liquid defoamer is suitable for use in a large number of different resin systems. For polyurethane dispersion, polyurethane/ acrylic hybrid, and two-component epoxy formulations, Surfy¯nol DF-178 defoamer should be the first choice of the formulator because it enables the production of foam-free, defect-free clear and pigmented coatings. Strong performance in two-component polyurethane, water-based alkyd, acrylic and styrene-acrylic systems, as well as in pigment dispersions, has also been observed. Surfy¯nol DF-178 defoamer also acts as a deaerator to provide strong defoaming and microfoam control in spray applications. Recommended use levels of Surfy¯nol DF-178 defoamer in coatings vary from between 0.1–0.75 wt % on finished systems.

tell me more www.airproducts.com/ surfactants © Air Products and Chemicals, Inc., 2010 (32145) B41

Visit ads.pcimag.com 20

䡲䡲䡲

018 Company News.indd 20

C O M PA NY NEWS Cognis Opens New Affiliate in Malaysia MONHEIM, Germany – Cognis has opened a new affiliate, Cognis Malaysia Sdn. Bhd., in Selangor, Malaysia, The new affiliate is a wholly owned subsidiary of the Cognis Group. The founding of a dedicated Malaysian affiliate is in keeping with the company’s focus on high-growth markets. It represents a significant milestone in Cognis’ activities in the Malaysian market, which has experienced rapid growth in recent years. Cognis Malaysia will employ technical and commercial managers to work on behalf of all three of the company’s strategic business units: Care Chemicals, Nutrition and Health, and Functional Products. The Asia-Pacific region is now Cognis’ third-biggest market after Europe and North America.

DSM and Novomer to Develop CO2-Based Resin HEERLEN, The Netherlands – Royal DSM N.V., Heerlen, The Netherlands, and Novomer Inc., Waltham, MA, have signed an agreement to jointly develop a coating resin using carbon dioxide (CO2) as a raw material. The project will combine DSM’s technologies and market access with the CO2 polymerization technology of Novomer. The chemistry and process technology for producing polymers from CO2 and propylene oxide will be developed by Novomer, while DSM will convert the polymers into resins and formulate them for target applications such as coatings, adhesives and graphic arts.

Labelmaster Provides MarinePollutant Regulatory Markings CHICAGO – As of Jan. 1, 2010, the International Maritime Dangerous Goods Code (IMDG) requirements for marine pollutant markings are mandatory for all applicable shipments. The DOT requirements for the use of the new marking were in effect as of Jan. 14, 2010. Labelmaster, Chicago, IL, currently carries the revised marine pollutant marking and has on-staff experts for any questions regarding the new classification regulations.

Sherwin-Williams Awarded Navy Contract CLEVELAND – Sherwin-Williams Protective & Marine Coatings has been awarded a $24 million, five-year U.S. Navy contract to supply marine coatings per just-in-time (JIT)

delivery to four U.S. Navy shipyards. The company was one of two low bidders in the first national comprehensive JIT coatings contract awarded by the Fleet and Industrial Supply Center (FISC), Norfolk, VA. The overall value of the contract, awarded over five years, is approximately $34.5 million. Previous U.S. Navy JIT contracts had been awarded for individual shipyards.

Mercedes Approves AkzoNobel Coating System for China AMSTERDAM, The Netherlands – AkzoNobel Automotive Plastic Coatings (APC) has garnered a win for its primerless waterborne basecoat system. Daimler Benz has approved the system for use on plastic bumpers and rocker panels produced by China-based supplier JJ/Minghua. According to AkzoNobel APC’s Director of Marketing & Sales, Thierry Paulhan, Daimler set the bar quite high with its strongly stated preference for a two-layer coating system consisting of a waterborne basecoat and clearcoat. AkzoNobel APC is the first coatings supplier to win approval of a primerless system.

Archway Sales to Distribute for BioBased Technologies® ST. LOUIS, MO – BioBased Technologies® has chosen Archway Sales, St. Louis, MO, to be the authorized distributor for Agrol® in the United States. Products offered by BioBased Technologies include Agrol® biobased polyols and BioBased Insulation®, biobased spray polyurethane foam insulation.

Clariant Enhances Distributor Network CHARLOTTE, NC – Clariant has expanded its North American distribution network for biocides and preservatives used in the paint, coatings and construction chemicals markets. Dowd and Guild Inc., San Ramon, CA, is distributing Clariant’s biocides product line in the western United States, covering the 11 states west of the Rocky Mountains.

DSM Invests in Green Chemistry Company HEERLEN, The Netherlands – DSM Venturing, the corporate venturing unit of Royal DSM N.V., has made an equity investment in U.S.-based green chemistry company Segetis Inc., Golden Valley, MN. Segetis Inc. has developed renewable chemistry that enables the use of nonfood agricultural and forestry feedstock

MARCH 2010 | W W W . P C I M A G . C O M

2/17/10 3:35:13 PM

for production of sustainable materials. The company produces versatile, cost-effective chemical building blocks (monomers) called levulinic ketals, which can be used to make new classes of chemicals and plastics.

Miller Paint to Acquire ICI Paint Stores in Oregon PORTLAND, OR – Miller Paint has entered into a definitive agreement with Akzo Nobel to acquire the business operations and related assets of two ICI paints stores located in Portland, OR, and Salem, OR. Miller plans to operate the Portland store as a new Performance Coatings Center and consolidate the ICI Salem store into an existing Miller Paint store in Salem. In addition, Miller Paint and Akzo Nobel have established a new strategic alliance. Miller Paint has acquired the exclusive rights to distribute the full range of Glidden Professional, Dulux and Devoe Coatings products. Initially, the distribution will be through 10 additional Miller Paint locations in the extended Portland/ Salem market.

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

BASF Sells Special-Effects Films Business

registration issues.

FLORHAM PARK, NJ – BASF has sold its special-effects films business, marketed by BASF under the trade name Aurora®, to RMS Packaging Inc., Peekskill, NY. The divestiture of this product line includes the sale of manufacturing equipment currently housed in Peekskill. As part of the agreement, BASF will transfer 12 employees to RMS Packaging Inc. BASF will retain ownership of the Peekskill facility, where the company also manufactures pigments, and will lease the building where the special-effects films are manufactured to RMS Packaging Inc., which will continue to produce the products in Peekskill.

Our in-depth expertise and high-performance specialty chemicals will help you 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.

RPM Acquires Coatings and Construction Products Business MEDINA, OH – RPM International Inc. has acquired the Universal Sealants Limited group of companies, a United Kingdombased supplier of coatings and construction products and services for bridges and large infrastructure projects. Universal Sealants is headquartered near Newcastle, England, and has sales of approximately $55 million. It will operate as a standalone industrial business in the RPM Performance Coatings Group. 䡲

Visit us at RadTech 2010

Baltimore, MD; May 24-26, Booth 309

Visit ads.pcimag.com PA I N T & C O AT I N G S I N D U S T RY

018 Company News.indd 21

䡲䡲䡲

21

2/17/10 2:32:14 PM

Light Stabilization Toolbox U Tunable Protection from UV to Near Visible

V protection of coatings is today often regarded as a mature and well-established technology. This may be true of certain traditional applications; however, the increasing use of materials requiring coverage or enhanced protection at specific wavelength ranges, along with novel resin technologies or low film builds, has resulted in a variety of new light stabilizer developments that now allow tunable protection from the UV to the near-visible range. Today, a wide range of light stabilizers provides solutions both for water- and solvent-based technologies, enabling paint companies to

adjust the level of protection needed to achieve top performance in their specific applications. Following a short summary of the various UV absorber chemistries developed over the years, both the absorption and the transmission characteristics of the various classes (including combinations thereof) are discussed below. Depending on the application and, in particular the sensitivity of the substrate used, suitable spectral coverage, as well as sufficiently high extinction at certain wavelengths (among other aspects), need to be recognized as important criteria in the selection of stabilizers.

Conventional UV Absorbers for Coatings FIGURE 1 | General composition of conventional UV absorbers. R1 H N

R4

O O

R3

H O

R1

N

R2

N

N H

N

Oxanilide

R2 Hydroxyphenyl benzotriazole

R1

R5

N

N

O H

N R4

R2 R3

Hydroxyphenyl triazine

The stabilization of coatings has for many years been a challenge for the paint industry. More than three decades ago it became evident that HALS (Hindered Amine Light Stabilizers) play a key role in the stabilization of polymers. Typically, these products are derivatives of 2’,2’,6’,6-tetramethylpiperidine and act – once activated by UV-light and oxygen with formation of the nitroxyl radical – as radical scavengers, thereby preventing UV-light-induced degradation (cracking) of the polymer (coating). The mode of action of HALS products is largely independent of the film build applied; however, they do not absorb light at wavelengths above 250 nm. Therefore, in many applications, combined use with UV absorbers is essential to filter out the harmful components of UV light.

By Dr. Adalbert Braig | BASF SE, Basel, Switzerland 22

䡲䡲䡲

022 BASF FT.indd 22

MARCH 2010 | W W W . P C I M A G . C O M

2/16/10 8:26:16 PM

Driving Forces for UV Absorber Innovation Hydroxyphenyl benzotriazoles and hydroxyphenyl triazines developed during the 1980s and 1990s meet the requirements of the majority of traditional applications. Challenges beyond these applications include optimization of film builds (i.e., thin film applications) and increasing use of water-based coatings requiring compatible UV absorbers without compromising on performance as well as of materials light sensitive at wavelengths not covered by conventional UV absorbers.

Advanced Hydroxylphenyl Triazine UV Absorbers for Thin Film Applications As shown in Figure 2, conventional BTZ and HPT UV absorbers exhibit fairly similar extinction, except in the 300 nm range. Adequate UV protection at low film builds can therefore only be achieved through significantly

FIGURE 2 | UV absorption spectra of UV absorber classes and of a HPT/BTZ combination (1) oxanilide; (2) BTZ; (3) HPT; (4) HPT/BTZ (1:1); c = 10 mg/L in CHCl3 (path = 1 cm).

Absorbance

0.8 0.7

oxanilide

0.6

hydroxyphenyl triazine

0.5

hydroxyphenyl benzotriazole hydroxyphenyl triazine / hydroxyphenyl benzotriazole (1:1)

0.4 0.3 0.2 0.1 0.0 280

300

320

340

360

380

420

FIGURE 3 | UV transmission spectra of UV absorber classes and of a HPT/BTZ combination (1) oxanilide; (2) BTZ; (3) HPT; (4) HPT/BTZ (1:1); c = 10 mg/L in CHCl3 (path = 1 cm). 100

Transmittance (%)

90

oxanilide

80

hydroxyphenyl triazine

70

hydroxyphenyl benzotriazole

60 50

hydroxyphenyl triazine / hydroxyphenyl benzotriazole (1:1)

40 30 20 10 0 280

300

320

340

360

380

400

420

Wavelength (nm)

FIGURE 4 | Comparative UV absorption spectra of advanced hydroxyphenyl triazine (3) UV absorber versus conventional UV absorbers (1, 2) at equal concentrations. 3.5 3 2.5 2

Hydroxyphenyl benzotriazole (state of the art) (1) Conventional hydroxyphenyl triazine (state of the art) (2) Advanced hydroxyphenyl triazine (3)

1.5 1 0.5 0 285 295 305 315 325 335 345 355 365 375 385 395 405 Wavelength (nm)

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

022 BASF FT.indd 23

400

Wavelength (nm)

Absorbance

UV absorbers predominantly protect the underlying substrate, which can be a colored basecoat or plastic or wood. In contrast to HALS, the efficacy of UV absorbers depends (according to the Lambert-Beer law) on the molecule-specific extinction coefficient ε, the concentration used and the film thickness applied. Additional crucial properties include low volatility, high photo stability, good compatibility and – depending on the spectral sensitivity of the particular substrate – adequate spectral coverage. Between the early 1970s and the 1990s a variety of UV absorber classes and chemistries were developed and introduced to the market. The general structures of these chemistries are shown in Figure 1. In the late 1970s, oxanilide UV absorbers were already almost entirely replaced by various hydroxyphenyl benzotriazoles (BTZ), which became the dominant UV absorber class during the 1980s and continue to be so for a variety of traditional applications. These materials were already characterized by much broader spectral coverage and much better photo stability. In spite of the dominant position of the hydroxyphenyl benzotriazoles, there are still requirements that cannot be satisfactorily met with these products due to certain technical limitations of their chemistry. These include limited absorption at shorter wavelengths, interaction issues with certain metal (e.g., Al-based) catalysts, leading to significant yellowing, as well as inadequate protection of the substrate at reduced film build. Development efforts in the 1990s resulted in the introduction of the first generation of hydroxyphenyl triazine (HPT) UV absorbers (general structure in Figure 1). Generally speaking, hydroxyphenyl triazines exhibit much less tendency to interact with certain metal catalysts and even better photo stability than hydroxyphenyl benzotriazoles, as well as high absorption at shorter wavelengths. These features make this UV absorber class highly versatile in terms of both traditional and advanced applications such as UV curing. Furthermore, combinations with BTZ allow broader spectral coverage than HPT alone, along with superior protection at short wavelengths versus BTZ alone. The comparative UV absorption spectra of the above classes as well as of a BTZ/HPT combination (example 1:1 ratio) are shown in Figure 2 and the corresponding UV transmission spectra in Figure 3.

䡲䡲䡲

23

2/16/10 8:26:27 PM

Light Stabilization Toolbox

higher dose levels, which in turn may compromise the secondary properties of the paint film. The more recent development of advanced chromophores based on hydroxyphenyl triazine chemistry has allowed up to 3.5 times higher extinction than the

FIGURE 5 | UV remission (i.e., reflectance) spectra of 2K clearcoats over silver metallic basecoat before and after 54 months Florida exposure. 100 90 Remittance (%)

80 70 60 50

BTZ (unexposed); DFT: 40 μm

40

BTZ (54 months Florida); DFT: 40 μm

30 Advanced HPT (unexposed); DFT: 20 μm

20

Advanced HPT (54 months Florida), DFT: 20 μm

10 0 280

300

320

340

360

380

400

420

440

460

480 500

Wavelength (nm)

FIGURE 6 | 54 months Florida results of 2K clearcoats over different basecoats: 40 μm standard film build versus reduced film build (20 μm). State-of-the-art UV absorber (40 μm)

State-of-the-art UV absorber (20 μm)

Advanced HPT (20 μm)

state of the art. This extremely high extinction (Figure 4) allows the application of thin films along with superior UV protection at comparatively low dose levels. The position of the absorption maximum in the 320-330 nm range also makes these chromophores interesting candidates for the protection of substrates sensitive at this wavelength range, e.g., polycarbonate. As mentioned earlier, the efficacy of a UV absorber depends both on its absorption characteristics and on its secondary properties, such as photo stability, which needs to be very high. This is particularly important in thin film applications, where the product’s inherent stability rather than the internal filter effect (i.e., UV absorber molecules protecting each other) plays the dominant role. Figure 5 shows the UV remission (i.e. reflectance) spectra of 2K clearcoats applied over silver metallic basecoat at film builds of 20 µm and 40 µm respectively. The spectra were recorded before and after 54 months Florida exposure. Despite the higher film build applied, essentially zero absorption is recorded for the hydroxyphenyl benzotriazole after long-term exposure. The spectra for the advanced hydroxyphenyl triazine (HPT), however, are essentially identical, which in turn can be interpreted as a result of its superior photo stability. The results of 54-month Florida tests with 2K clearcoats (40 µm standard film build versus reduced film build; 20 µm) over both violet and silver metallic basecoats are summarized in Figure 6. The results clearly show that only the advanced hydroxyphenyl triazine technology allows superior protection at low film builds, whereas delamination is observed in the presence of conventional UV absorbers.

Red-Shifted UV Absorbers

State-of-the-art UV absorber (40 μm)

State-of-the-art UV absorber (20 μm)

Advanced HPT (20 μm)

FIGURE 7 | Comparative UV absorption spectra of conventional hydroxyphenyl triazine (mono-resorcinol triazine) versus red-shifted tris-resorcinol triazine (TRITA); c = 10 mg/L in CHCl3 (path = 1 cm). 0.8 R 0.7 O 0.6 H (1) N N R R N 0.5 (2) R R 0.4 (1): R1, R2 = CH3 0.3 (2): R1 = OR'; R2 = OH 0.2 0.1 0.0 285 295 305 315 325 335 345 355 365 375 385 395 405 415 1

Absorbance

2

1

Wavelength (nm) 24

䡲䡲䡲

022 BASF FT.indd 24

2

1

The spectral coverage as such, as well as the position of the absorption maximum, are determining factors in UV stabilization of substrates sensitive at wavelengths that are not, or not sufficiently, covered either by conventional or advanced chromophores. These wavelengths extend from the ≥ 360 nm range to the visible and slightly above. A shift in the absorption spectrum of the UV absorber can be achieved to a significant extent through specific substitution patterns; however, there are obviously limitations both in terms of chemistry and color. The more the spectrum is shifted towards the visible, the higher the risk of bringing in too much color. This in turn means that a proper balance needs to be achieved between the spectral coverage and the product’s inherent color.

Red-Shifted UV Absorbers for Wood Protection As described in previous publications1,2, both UV and visible light lead to decomposition of the lignin structure of wood, resulting in discoloration/darkening of pale woods in particular. In order to filter out the UV light component as far as possible, broader spectral coverage is needed than can be achieved with conventional UV absorbers. Figure 7 shows the comparative UV absorption spectra of a conventional hydroxyphenyl triazine (mono-resorcinol triazine) versus a red-shifted tris-resorcinol triazine (TRITA). Modification of the substitution pattern at the triazine moiety in this case allows a significant shift of the absorption maximum from 290 nm to 360 nm.

MARCH 2010 | W W W . P C I M A G . C O M

2/16/10 8:26:41 PM

Light Stabilization Toolbox

FIGURE 8 | Spectral sensitivity of pine wood; chromophore formation during XeWOM exposure and prevention thereof by the combined use of red-shifted UV absorber and lignin stabilizer. Relative intensity at 1730 cm-1

3 Pine

2.5

Pine with lignin stabilizer (1)

2 R

N O

1.5

(1)

1 0.5 0

Without GG 320 GG 385 filter

TRITA

GG 400 GG 435 GG 475 GG 495

FIGURE 9 | UV protection of pine wood; clear coat: 2K PU (wb); exposure: 1000 h Xenon-WOM (CAM 0 cycle). Unstabilized

Pretreatment: none CC: TRITA stabilized

Pretreatment: lignin stabilizer CC: TRITA stabilized

FIGURE 10 | Determination of the spectral sensitivity by means of cut-off filters principle. 100

Transmittance (%)

90 80 70

Filter GG 385 = 50% transmittance at 385 nm

60 50

F ilter G G 385

40

F ilter G G 400

30

F ilter G G 435

20

F ilter G G 475

F ilter G G 420 F ilter G G 455

20 0 300

325

350

375

400

425

450

Wavelength (nm) 26

䡲䡲䡲

022 BASF FT.indd 26

475

500

As indicated above, the decomposition of the lignin structure leads to formation of colored chromophores. Figure 8 shows the relative intensity of the carbonyl signal at 1730 cm-1 determined by FTIR analysis of pine samples. The relative intensity is the intensity measured after Xenon-WOM exposure relative to the intensity prior to exposure and correlates with the formation of new chromophores, i.e., the higher the value, the more extensive the decomposition of the lignin. Cutting out the UV light either by cut-off filters (which allow a certain wavelength range to be selectively cut out, i.e., a filter labeled GG 320 excludes all wavelengths below 320 nm, a filter labeled GG 385 excludes all wavelengths below 385 nm, etc.) or by the red-shifted tris-resorcinol triazine (TRITA) UV absorber in lieu of a filter can greatly reduce the formation of colored chromophores (Figure 8). Since such species, however, are also being formed in the visible range, sufficient protection can scarcely be achieved by the UV absorber alone. In order to fully prevent their formation, spectral coverage as far out as > 450 nm would be needed (Figure 8), which in turn would result in a major color impact by the UV absorber. Therefore, a modified concept involving specific costabilization was developed. Such co-stabilizers, which are chemically based on free nitroxyl radical chemistry (Figure 8), are typically used for pretreatment purposes. Such materials can trap the radicals formed on the wood surface by the visible light, thereby preventing photooxidation of lignin. Figure 9 shows how the above concept is applied to clear-coated pine wood. After 1000 h Xenon-WOM exposure, the non-stabilized sample exhibits severe darkening. UV stabilization of the clear coat with TRITA can already greatly reduce the discoloration observed. If combined with lignin stabilizer, discoloration is further minimized.

Highly Red-Shifted UV Absorbers for Protection of CFRM and Epoxy Matrix Novel substrates such as carbon-fiber-reinforced materials (CFRMs) are increasingly being used in a variety of applications, including automotive parts and hang-on parts for motor bikes, sports items such as bikes, the aerospace industry and rotor blades for wind turbines. CFRMs are characterized by low weight and superior mechanical properties. In order to achieve these properties, the carbon fiber is typically embedded in an aromatic epoxy matrix. Systems or composites based on aromatic polymers (e.g., CFRMs) are inherently light sensitive, unless covered by pigmented coatings. The application of exposed carbon fiber, for example as a design element (CFRM coated with clearcoat only), is therefore highly challenging from a UV protection point of view. Fundamental studies conducted by means of cut-off filters (Figure 10), which allow certain wavelength ranges to be selectively cut out, show that the critical wavelengths include both the UV (i.e., 280 – 380 nm) and the 400 nm range. Figure 11 shows the results of the determination of the spectral sensitivity of CFRMs by means of cut-off filters. In the experiments, the substrates were coated with 2K PU clearcoats stabilized with HALS only. The specimens were

MARCH 2010 | W W W . P C I M A G . C O M

2/16/10 8:26:50 PM

Conclusion The range of UV absorbers available today includes both conventional and advanced UV absorber technology. In traditional applications conventional hydroxyphenyl benzotriazoles as well as hydroxylphenyl triazines will certainly continue to play an important role. These products, however, do not meet the requirements for thin film applications or for applications requiring enhanced or specific protection at certain wavelengths. Development work has led to an extension of the available product range beyond conventional technologies, thereby allowing applications previously considered difficult or even impossible. Advanced hydroxyphenyl triazines are closing the gap for thin film applications or applications where enhanced protection at shorter wavelengths is necessary. Superior protection of wood substrates can be achieved by a specific concept, i.e., the combined use of red-shifted triazine-based UV absorbers and lignin stabilizers. Protection of systems or composites based on aromatic epoxies can be considered the biggest challenge in terms of the UV absorber properties needed. Today this can be realized through novel red-shifted UV absorber technology, which combines comparatively low color with broad spectral coverage reaching into the near visible. Furthermore, the application of the various products as such or combinations thereof allow paint companies to adjust the protection to the level needed. In waterbased coatings – although not further discussed in this paper – this is achieved through specific water- compatible product forms. 䡲 1

2

Schaller C.; Rogez, D. J. Coat. Technol. Res. 2007, 4 (4) 401409. Braig, A.; Schaller C. European Coatings Show and Congress, 2007, Nuremberg.

FIGURE 11 | Determination of the spectral sensitivity of CFRMs by means of cut-off filters: 2K PU clearcoat (stabilized with HALS only) over CFRM substrate; exposure: 4000 h Xenon-WOM followed by humidity exposure (96 h; 40 °C at 98% r.h.) and adhesion test. 500 h exposure

4000 h exposure

No UV filter (delamination)

Coverage up to 360 nm (delamination)

4000 h exposure 4000 h exposure

Coverage up to 390 nm (discoloration)

clearcoat (DFT: 2 x 60 μm) over glass plates. 100 90 80 70 60 50 40 30 20 10 0 280

1% RUVA 2% RUVA 3% RUVA Concentrations based on total solids

300

320

340

360

380

400

420

440

460

480

500

Wavelength (nm)

FIGURE 13 | UV protection of CFRM; comparison of conventional UV absorbers and RUVA 2K PU clearcoat (DFT: 2 x 60 μm); exposure: Xenon-WOM (CAM 180 cycle). State-of-the-art UV absorbers

RUVA*

2,000 h Xe-WOM

State-of-the-art UV absorbers

RUVA*

5,000 h Xe-WOM

*RUVA = red-shifted UV absorber

This article is based on the presentation “Light Stabilization Toolbox – tunable protection from UV to near visible,” given at the European Coatings Congress, 2009, in Nuremberg, Germany, by Adalbert Braig, BASF SE.

For AC Show coverage visit: www.pcimag.com/ac_show Or follow our coverage on Twitter using hash tag: #ACS PA I N T & C O A T I N G S I N D U S T R Y

022 BASF FT.indd 27

Coverage up to 405 nm (unchanged)

FIGURE 12 | UV transmission spectra of RUVA at different concentrations; 2K PU

Transmittance (%)

subsequently exposed for 4000 h in the Xenon-WOM, followed by humidity and adhesion tests. The results clearly indicate that spectral coverage as far out as ~400 nm is mandatory in order to prevent degradation of the underlying epoxy matrix. UV protection of such substrates requires UV absorbers (RUVA) with pronounced absorption into the visible (along with minimal color impact), sufficiently high extinction in the 400 nm range and superior photo stability. Figure 12 shows the UV transmission spectra recorded at different dose levels and a film build typical for coated CFRM. The results indicate that the critical wavelengths can be fully covered at dose levels between 1 and 2% based on the solids content of the clearcoat. This has been confirmed in independent and comparative experiments conducted with RUVA-containing clearcoats versus conventionally stabilized clearcoats (Figure 13). The application of conventional UV absorbers results in early failure (delamination) after only 2000 h Xenon-WOM exposure due to the insufficient spectral coverage provided. In the presence of RUVA, however, superior protection is achieved. No signs of delamination or discoloration are observed even after 5000 h XenonWOM exposure. This in turn opens the door for new applications, e.g., the use of CFRMs as a design element.

䡲䡲䡲

27

2/16/10 8:27:00 PM

Best Paper Award – Coatings for Plastics Symposium

Breaking the Performance Barrier in

Automotive Interiors

T

he U.S. automotive industry has gone through huge transformations in the t ti ith the th struct pastt 30 years, starting with ture of the industry, where the dominance of the Big Three has been challenged by global players. Improvements in on-the-road performance have made exponential step changes as well. The performance improvements cover multi-dimensional aspects like fuel efficiency, robustness, safety features and comforts to name a few (Table 1). Interior automotive design has also undergone broad changes to improve ergonomics, functionality and appeal. Not the least of these is the expanded use of durable plastic materials, which now account for the majority of the human-contact surfaces. In this article, we focus on the needs of interior car coatings. These coatings are driven by three criteria: look, feel and functionality. While look and feel are a function of fashion trends and are relatively short lived, the demands in functionality are usually step changes in terms of physical and chemical resistance properties which, in turn, are intended to preserve the look and feel of the coating.

Automotive Interiors: A Pleasurable Ride Interior automotive surfaces like door trim panels, instrument panels, dashboards and center consoles are often exposed to a broad array of chemicals as a result of daily use. Just considering the ingredients found in food and

TABLE 1 | Some significant changes in the U.S. automotive industry. Structure of industry Median age 60,000 mile car perception Average gas mileage (mpg)

1970s

Today

Big 3 5.1 Highly used 12

Little 10 8.9 Just breaking in 17.1

personal care items, cleaners and dressings, deodorizers and pet products; interior surfaces must be resistant to h i l which hi h can b l hili or h d hili acidic idi chemicals, be oleophilic hydrophilic; or alkaline; and solvents like alcohols, glycol ethers and hydrocarbons. Chemicals particularly harsh to interior surfaces include sun tan lotion, mosquito repellant (DEET: N,N-diethyl-meta-toluamide) and the freshness fragrances that make driving a more pleasurable experience. Now let’s raise the degree of difficulty by requiring protection at sub-zero and elevated temperatures to 140 ºF! All global automotive players have defined standards for interior coatings so that they retain their look and feel in the face of these extreme conditions. For example, General Motors has developed the Global Approved Paint on Plastic Systems based on GM 14867 specification. These are usually one-component systems. On the other hand Volkswagen’s TL-226 specification has another set of stringent standards that typically use two-component systems in Europe.

Defining the Innovation Need Coating suppliers to the interior automotive plastics market are often large multinational corporations or regional players who form global alliances in order to supply the OEMs across the planet. Local regulations and growing consumer sustainability awareness make the use of lowVOC waterborne systems a prerequisite for many of the surface protection coating systems. Subsequently, coatings need to have good atomization during application providing the “appearance” prescribed by the designer, high adhesion to ABS and PC-ABS plastics and protective properties to resist chemical and abrasion attack. The GM Global Specification and VW TL-226 specifications for interior automotive plastic coatings have particularly defined the need to address the DEET/sun lotion attack on the coating systems. Both require resis-

By Jim Bilancieri, Ad van Dorst, Rijoy Putatunda and Derrick Twene | DSM NeoResins, Wilmington, MA 28

䡲䡲䡲

028 DSM FT.indd 28

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 9:03:55 AM

Breaking the Performance Barrier in Automotive Interiors

FIGURE 1 | Traditional manufacture of a waterborne polyurethane dispersion. Low-molecular-weight prepolymer 2 HO containing diluent (NMP) to regulate viscosity

NCO + HO

OH + 4 OCN

OH COOH

OCN

Neutralize OCN

Disperse in water Spontaneous Particle Formation Increase in Mw u

u

u

u u u NCO add COOH hydrocarbon base residue of u u u u u u NCO diisocyanate + COO HN R3 urethane group NCO ended prepolymer emulsion u chain extension +H2 NNH2 urea group uu

u

u

u

u

KEY polyol segment

uu uu u COO- HN+R3

u

u

FIGURE 2 | Plasticized polyurethane particle. Water-rich regions HNR3+

HNR3+ OOC

COOCOOH

OOC HNR3+

COO C OO COO HNR 3++ C OO - HNR 3+ HNR 3 HNR + 3

C OOH COOH C OO -COO

HNR HNR 33++ C OO - COO

HNR 3++ HNR 3

-OOC HNR3+

COOHNR3+

COOH

Plasticization of polyurethane by water

COOHNR3+

FIGURE 3 | Driving coalescence by evaporation of water.

Evaporating water drives particles together.

FIGURE 4 | Segmental phase separation of polymer. Segmental phase separation

30

䡲䡲䡲

028 DSM FT.indd 30

tance to attack under 80 ºC temperatures. To meet these demands, this multinational team of developers chose a polyurethane-hybrid polymer system. For application areas where the requirements are at a high level, urethane polymer chemistry forms a good basis from which new performance barriers can be reached.

Polymer Design Various synthesis routes for high-molecular-weight polyurethane dispersions are common practice. Best know are the acetone process, the melt dispersion process, the ketamine process and the prepolymer mixing process. The first synthesis step of all these processes is the same, being a well-known polyurethane reaction in which diols or polyols are reacted with diisocyanates (Figure 1). Reaction product is then dispersed in water. In the case of anionic polyurethane dispersions, the prepolymer chains contain carboxylic acid stabilizing groups provided, for example, by dimethylol propionic acid (DMPA). The prepolymer acidity is then neutralized and transferred to water, where spontaneous particle formation occurs. Chain extension is then carried out resulting in the formation of a high-molecular-weight waterborne polyurethane polymer dispersion. The very nature of the process results in the formation of a polymer colloid, which is significantly different from that of emulsion polymers. They differ in terms of their colloidal, morphological and application characteristics. It is well understood that, in terms of particle and polymer morphology, polyurethane dispersions have a unique advantage over many other polymers in their ability to form coherent films. The degree of coalescence and the interpenetration of the polymer chains leading to further gradual coalescence of the particles are reported to be much higher for typical polyurethane than for a typical acrylic latex particle (Figure 2). Critical to the superior film formation are two factors. First is the presence of water within the particle. Moisture content of the particle plays the roll of plasticizer in that it softens the particle thus making it easier to coalesce, as shown in Figure 3. The second critical factor involves the nano-particle size of most polyurethane dispersions. During the coalescing process, particles are driven together by the evaporation of water from the coating. This “hydrostatic vacuum” forces the particles together the same way evacuating air between two surfaces binds them. The effectiveness of this process is relative to the surface area of particles. For a given mass of dispersed polymer, smaller particles will result in a greater surface area and a greater driving force. Moreover, polyurethanes “generate” performance enhancement due to their ability to form micro-phase morphology, where hard segments and soft segments (segment phase separation) are manipulated to achieve suitable polymer packing resulting in enhanced hydrogen bonding (Figures 4 and 5). In designing new polymers to meet the new performance criteria this performance enhancer is addressed with special care. Additionally, the inclusion of a polyurethane-hybrid design provided benefits that a polyurethane homopolymer or physical blend of resins could not. It is well under-

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 9:04:05 AM

Breaking the Performance Barrier in Automotive Interiors

TABLE 2 | GMW-approved paint on plastic systems (APOPS). Test Category

Test Method

Specification

Criteria

Cure

GMW14867 Sec 3.3

Adhesion Humidity/adhesion Oven age/adhesion

GMW14867 Sec 3.4 GMW14867 Sec 3.5 GMW14867 Sec 3.9

Double rub (EtOH) GMW14829 GMW14829 GMW14829

Sunscreen test

GMW14867 Sec 3.6

GMW14445

Impact resistance

GMW14867 Sec 3.11

ASTM D 3763

Film thickness

ISO2808 Method 5A

Scratch resistance

GMW14867 Sec 3.13.1

No film degradation ≥ 95% ≥ 95% ≥ 95% No paint removal Establish baseline 25 μm optimum No noticeable scratches

1 mm Hem/13N

TABLE 3 | VW TL-226 interior automotive plastics general performance requirements. Test Category Hydrolysis Adhesion (Gitterschnitt) Hand cream (PV-3964) Sun block (PV-3964) Humidity (DIN 6270-2)

Test

Criteria

3 days @ 90 ºC/96% RH. 4 h recovery Hydrolysis, sun block, humidity tests

No change in color or haptic characteristics ≥ 99% adhesion

24 h @ 80 ºC 24 h @ 80 ºC 240 h @ 40 ºC and 96% RH. 4 h Recovery

No change in color or haptic characteristics No change in color or haptic characteristics Pass Erichsen hardness: 10N

FIGURE 5 | Hydrogen bonding of PU polymer. Presence of H-bonding O N

O O

O

H O N

O

O

Meeting Performance Needs on Two Continents The GM World specification for interior automotive plastics (GMW14867) contains demanding performance requirements for adhesion, humidity and impact, but the most demanding requirement is the resistance to chemical attack at 80 ºC (Table 2). GMW14445 utilizes a chemical cocktail comprised of equal amounts of: DEET, octyl methoxycinnamate, octocrylene, and homosalate. Of equal difficulty is the VW TL-226 specification, which requires 24 h resistance to hand cream and sun block lotion at 80 ºC (Table 3). By means of intelligent raw material choices and proprietary polymerization techniques NeoRez R-4000 was developed to meet the resistance challenge of GMW 14867 and VW TL-226. NeoRez R-4000 is designed to be effective in both 1K and 2K coatings. Two-component coatings utilize a blend of hydrophilic and hydrophobic isocyanate adducts to achieve higher crosslink density that is required to meet the 24 h 80 ºC test. Performance test results are shown in Table 4.

O N

N

H

H

O

H

stood that many of the physical performance improvements found in a hybrid design over a physical blend can be attributed to the homogeneity of the dried films. The Atomic Force Microscopy (AFM) images, shown in Figure 6, are presented in the phase mode showing the hard and soft segment distribution of the polymer. The image on the left illustrates the incoherent phase distribution of two dissimilar polymers during film formation. The image on the right illustrates the homogeneous distribution of dissimilar polymer resulting from hybrid polymerization. A homogeneous distribution of these regions is important in maintaining the physical characteristics of the polyurethane. Nanophase hybrid technology is regarded as an excellent way to reinforce coatings and improve their performance.

Formulation

O

NeoRez R-4000 can be compounded to meet the appearance needs for clearcoats, solid colors with varying grades of gloss and, of course, metallic (silver being the most popular). Waterborne coatings also need a shelf life of about six months, which demands good compatibility of the binder with the pigment preparation and additive alike. Starting-point formulations are shown in Table 5. To ensure good compatibility, all formulations should be prepared using a high-speed dissolver with each additive being carefully incorporated to avoid shock or flocculation. For two-component formulations, a (1:1) ratio of hydrophobic combined with hydrophilic isocyanate was added to a set amount of the one-component finished formulation under agitation (Table 6). The final formula films where checked as drawdowns on glass for flocculation and incompatibility. The coatings were visually assessed then measured for gloss, haze and pigment float. The formulations were additionally stored at 50 ºC for 3 months and rechecked for quality and performance.

O N

N

N

H

H

H

FIGURE 6 | AFM images of blend and hybrid polyurethane dispersions.

Conclusion 0 Data type Z range 32

䡲䡲䡲

028 DSM FT.indd 32

1.00 μm Phase 72.4 de

0 Data type Z range

1.00 μm Phase 20.2 de

It is well known that the performance standards for interior automotive plastic coatings have dramatically changed since plastics first appeared in the automobile cockpit.

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 9:04:17 AM

Breaking the Performance Barrier in Automotive Interiors

Superior in Clear Coats MINEX ® delivers unique physical and photochemical properties ideally suited for clear coats. Its low refractive index is best utilized in transparent wood and furniture coatings, where MINEX can be loaded up to 20% without excessive haze to improve hardness, light stability and moisture resistance.

®

FUNCTIONAL FILLERS AND EXTENDERS

See us at the American Coatings Show, April 13-15, 2010, Charlotte, NC. Booth #937.

TABLE 4 | NeoRez R-4000 performance results in chemical attack as tested on ABS.

Test Result

1K Formulation 2K Formulation

GMW-14445 Cocktail 1h 80 º C 2/Pass 5-Finger scratch test 8N/Pass VW TL-226 Hydrolysis Resistance 3 days 90 º C @ 96% RH Pass After 4 h recovery 10N Pass PV3964 Sun block Fail 24 h 80 º C PV3964 Hand cream Fail 24 h 80 º C

2/Pass 8N/Pass Pass Pass Pass Pass

TABLE 5 | General starting-point formulas for NeoRez R-4000. Formulations

Matt Clearcoat E-1070

Matt Black E-1080

Metallic Silver E-1075

NeoRez ® R-4000 Pigment preparation Cosolvents Wetting aid Leveling agent Demineralized water Thickener Waxes/Matting aid Defoamer Total

74.6 12.8 0.6 0.6 4.7 5.2 0.7 100

70 3.2 18 0.5 3.4 0.8 100

70 2.9 10 0.3 3 4.3 100

TABLE 6 | Isocyanate additions required for 2K performance. 2K Formulations

2K Clearcoat E-1070

2K Matt Black E-1080

2K Metallic Silver E-1075

Finished formulation 1:1 isocyanate blends Total

87 13 100

87 13 100

87 13 100

The standards established by General Motors and Volkswagen are amongst the most difficult to meet. But considering the plethora of chemicals, food items and reagents that may be residing on a coated plastic surface during mid afternoon sun in Phoenix it stands to reason that the polymers used to protect and beautify these substrates need to be top performers. NeoRez R-4000 is a new and effective polymer to help the formulator meet this challenge. 䡲

Acknowledgements The authors convey thanks to Ilse Koks- van den Nouweland, Sandy Wheeler and Delia Kriticos for experimental application work, and Herman Ryborz and Stefan Geboers for contributing the numerous synthesis and not giving up.

For more information and our complete product portfolio visit:

www.BrilliantAdditions.com ® MINEX is a registered trademark. All rights reserved. © 2010

SPECIALTY AND PERFORMANCE MINERALS

Visit ads.pcimag.com 34

䡲䡲䡲

028 DSM FT.indd 34

References 1. Dietrich, D. Prog. Org. Coatings 1981, 9, 281. 2. SatGuru, R.; McMahon, J.; Padget, J.C.; Coogan, R.G. J. Coatings Techn. 1994, 66, (830), 47. 3. Wilkinson, T.S. PhD thesis (1997), Lancaster University Lancaster, UK. 4. Lucas, H.R.; Mealmaker, W.E.; Giannopous, N. Prog. Org. Coatings 1996, 27, 133. 5. vd Waals, A.; Satguru, R.; Swaans, R.; Dekkers, C. PPCJ 2009, 1, 20-21.

This paper was presented at the Coatings for Plastics Symposium sponsored by PCI Magazine, Chicago, 2009.

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 9:04:22 AM

Milling-Media Review: Bead Milling Operating Parameters – Part Two

I

n the last Milling-Media Review (PCI, March 2009), we introduced some of the parameters and considerations necessary for operating agitator bead mills. For this issue, we continue with the same theme, focusing essentially on the nature and significance of the feed materials and their effects on the overall milling process.

Operating Parameters As a first step, it is important to review the scope of activity for agitator bead mills and detail, to some degree, the physical nature of the materials processed. Figure 1 gives

an overview of the general field of comminution. It can be seen that agitator bead mills tend to operate in the range from approximately a few hundred microns down to nanometer sizings. The feed materials vary considerably from industry to industry, however some of the basic concepts are common to all. Material hardness, size and density are all critical considerations, but equally important is the nature of the particles themselves – whether they are primary particles, aggregates or agglomerates (Figure 2). All of these factors have significant bearing on the required milling process.

Process Requirements The requirement to reduce particle size or disperse materials is necessary in many industries to enhance and improve the final properties of particular products. The actual targets can vary significantly from industry to industry. In the paint and ink industry for example, it can be optical characteristics, gloss/transparency, etc. In

FIGURE 1 | Classification of comminution processes. FINE COMMINUTION CRUSHING GRINDING COARSE FINE ULTRAFINE NANO 10-6

COLLOIDAL Coll. disperse Coarse disperse

10-5

10-4

10-3

10-2

AGITATOR BEAD MILLS

10-1

1

102

103

10 PARTICLE SIZE (MM)

FIGURE 2 | Illustration of primary, aggregate or agglomerate particles.

FIGURE 3 | Relation between intensity of color and median size. Intensity of Colour (%)

COARSE FINE

100 80 60 40 20 0

0.5

1

2

5

10

Particle Size (μm) FIGURE 4 | Micrograph of pigment particle size and corresponding color produced.

Primary Particles

1 μm

Aggregates

Agglomerates By Dr. Paul Hassall, Saint-Gobain, ZirPro | SEPR, Le Pontet, France 36

䡲䡲䡲

036 SEPR FT.indd 36

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 10:04:14 AM

Part 4 TABLE 1 | Mineral hardness figures and densities. Mineral

FIGURE 5 | Illustration of comminution and deagglomeration. Density

1

Clay

2

Gypsum

CaSO4

2.3

2.5

3

Calcite

CaCO3

2.6

4

Zincite

ZnO

5.4

5

Hematite

Fe2O3

5.0

6

Rutile

TiO2

4.2

7

Quartz

SiO2

2.6

8

Zircon

Zr2SiO4

4.5

9

Corundum

Al2O3

4.0

10

Diamond

Comminution

3.5

other industries, it may be a purely physical consideration, such as the development of active surface area for ceramic processing. A good example to review is the development of color intensity; this is usually determined by the median particle size of the product. The graph in Figure 3 details the intensity development of a particular color with the median particle size D50. The actual effects can be seen on Figure 4 where a micrograph of the pigment particles size is shown next to the pigment color produced. The level of achieved grind obviously greatly affects the final quality of the product. The nature of the feed material and the target condition are important considerations for the milling process.

FIGURE 6 | Bead wear and feed hardness.

Feed Hardness

Comminution and Deagglomeration Comminution – True comminution is the grinding of primary particles into smaller sizes. This process requires sufficient energy to break the structural bond of the material itself. Deagglomeration – Deagglomeration is the breaking of agglomerates or aggregates into primary particles in order to disperse the particles in the medium. This requires only sufficient energy to break the binding forces (surface forces) of the particles. Figure 5 illustrates these principles.

Feed Material Size, Hardness and Density Size The size of the largest feed particles will particularly determine the size of the grinding media used. There is a ‘Stress Energy’, SE, required to break feed particles; in general a larger SE is required to break larger particles and therefore larger milling media will be necessary. The media will normally be in the region of 20-40 times larger than the feed particles. Practically, the feed particles need to fit easily between the voids of the milling media.

Deagglomeration

Bead Wear

Hardness Mohs

Hardness The hardness of the feed particles will also impact on the required energy levels. If the particles are hard and difficult to break, then more energy will be required to break them down. This may require larger and/or denser milling media or may result in higher mill energy requirements and/or longer process times. Some typical mineral hardness figures and densities are shown in Table 1. The hardness of the feed particles will also have an effect on the wear rates of the milling media and the machine parts. Generally harder feed materials will result in higher mill and bead wear (see Figure 6 for bead wear). For milling media, the comparative hardness of the feed to the media is a critical factor. The media ideally should have a surface hardness higher than that of the feed. If the reverse situation occurs, there can be excessive wear on the media resulting in rapid loss of milling efficiency. It is also important to consider that the selection of mill lining materials, their hardness and elasticity etc., will significantly affect the rate of overall wear. PA I N T & C O A T I N G S I N D U S T R Y

036 SEPR FT.indd 37

䡲䡲䡲

37

2/19/10 10:04:19 AM

Milling-Media Review: Part 4

TABLE 2 | Waterborne architectural paint formula example. Pigment Dispersion

Formulation wt%

Water Clay Defoamer Preservative Dispersing agents TiO2 rutile 0.25-0.3 μm Aluminium silicate 0.035 μm PPC 0.3 μm GCC 0.5 μm Calcite 2.7 μm Calcite 7 μm Mica 27 μm Coalescent agent Silicone resin emulsion TOTAL

25.5 1.0 0.3 0.2 7.0 12.5 5.0 5.0 5.0 12.5 15.0 5.5 1.0 4.5 100%

Density Feed material density will also have an effect, although this is often overshadowed by considerations of concentration and viscosity of the feed. Nonetheless, it is prefer-

able to use milling media of higher density than all of the target product particles present in the formulation. It is important to consider that many products contain a large number of raw materials; various fillers and pigment types for example. All these materials have different characteristics, yet they all need processing at the same time, through the same milling operation. A paint formulation can contain five to 10 different solid components as shown, for example, in Table 2.

Conclusion The requirements of the milling process, (comminution/ deagglomeration) and the nature of the feed material, are important factors when selecting milling media. The first consideration should be process demand, to ensure that the bead is capable of transferring sufficient energy to achieve the grind action required. This, however, needs to be considered against the overall cost effectiveness of the process. The bead properties, size, etc., need to be matched to process; if this is not achieved, costs can escalate, particularly in terms of energy consumption and machine/bead wear. 䡲 For further information e-mail [email protected].

Elcometer 456 Coating Thickness Gauge. One gauge–A world full of applications. The key to the superiority of the 456 is its measurement system featuring a range of interchangeable probes 씰 씰 씰 씰 씰 씰 씰 씰

All Ferrous models will accept ANY Ferrous 456 probe All Non-Ferrous models will accept ANY Non-Ferrous 456 probe All Dual FNF models will accept ANY 456 probe High speed accurate readings Three memory options –Basic, Standard, Top Easy to use menu driven display-available in 22 languages Standard and pre-defined calibration options Integral and separate probe options US & Canada 800.521.0635 • www.elcometer.com

England Tel: +44 (0) 161 371 6000 • France Tel: +33 (0)2 38 86 33 44 Asia +65 6462 2822 • Germany Tel +49 (0) 7366 91 92 83 • Belgium Tel +32 (0)4 379 96 10

Visit ads.pcimag.com 38

䡲䡲䡲

036 SEPR FT.indd 38

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 10:04:26 AM

Binder Transfer Mouvex C-Series sealless eccentric disc pump provides low shear, C

A

coatings plant that produces both cationic paste with pigment and cationic binders without pigment for truck shipment to automotive OEMs was experiencing difficulties when transferring the compounds from mobile tanks to trucks. In particular, the types of pumps that were being used were incapable of totally draining the pipes, hoses and mobile tanks used in the process, leading to wasted time and materials, as well as an increase in the probability of leakage. The trucks are loaded with cationic binder from mobile tanks, meaning frequent human involvement; therefore, the plant operators were looking to upgrade to a style of pump that would make the overall operation cleaner and more efficient. Because of the unique types of binders that are handled, as well as the operators’ requirements for clean, time-sensitive performance, a versatile pump needed to be incorporated, one that is sealless, provides low shear, clean-inplace capabilities and high volumetric efficiencies.

Four years after installation, the pump is still working perfectly. At the end of the loading process the pump totally drains the inlet hose, mobile tank and outlet pipe, which is key to its operation, and, since the C18i does not have a mechanical seal, there is no risk of product leakage. An eccentric disc pump was ideal for this application because of the following important design benefits.

• •

•

•

The Solution The new pump selected for this type of application was one that featured eccentric disc technology (Figure 1). With that in mind, a Mouvex C-Series sealless eccentric disc pump – Model C18i, specifically – was installed at the plant.

FIGURE 1 | C-series disc pump. O-rings Bearings

Disc Disc Nut

•

• Sealless design in which there are no mechanical seals, magnets, rubber or PTFE diaphragms. Low shear handling of products with low slip, lower internal velocities and ultra-low agitation. Clean-in-place capability allows the pump to be completely drained, flushed and cleaned without disassembly. High volumetric efficiency that is able to maintain a constant flow rate at a given viscosity throughout its pressure range. Good compression performance and the ability to run dry (up to 10 seconds) enable excellent self-priming capabilities and complete line stripping of suction and discharge lines. Self-adjusting operation maintains delivery/pressure performance over time through the use of a self-adjusting disc/cylinder.

Because of the latter characteristic, eccentric disc pumps can be used as dosing pumps. Since the pump is automatically self-adjusting, it maintains greater efficiency and repeatability over time than traditional lobe or gear pumps.

Pump Characteristics Drive Shaft

Cylinder Bellows

All Mouvex C-Series pumps have a shear rate of sec -1 = 0.9 rpm, which is lower than other types of pumps used in coatings applications. This is due in part to the gentle, low velocity action of the disc and cylinder, and the extremely low slip rate of the pump. Unlike other technologies, eccentric disc pumps do not have required clearances that can cause slip, which is the portion of the pumped product that is forced back to the suction side of the pump due to pressure through the clearances. In C-Series pumps, the discharge pressure exerts itself against the eccentric disc in a way that assists in maintaining axial contact with the cylinder, thus mitigating the usual effect that dis-

By Chistophe Jovani, Marketing Manager | Mouvex, Auxerre, France 40

䡲䡲䡲

040 Blackmer FT.indd 40

MARCH 2010 | W W W . P C I M A G . C O M

2/16/10 8:29:48 PM

in Coatings , CIP and high volumetric efficiency for binder transfer applications charge pressure has on slip in pumps. It is this low slip between the disc and cylinder that gives the C-Series the ability to self-prime and line strip. Mouvex C-Series pumps are capable of handling viscosities of up to 10,000 Cp, working pressures up to 130 psi (9 bar), capacities of 4 to 158 gallons per minute, operating temperatures up to 176 °F and a particle-size range of 1 to 3 millimeters. Regarding Mouvex’s clean-in-place technology, the C-Series holds 3A Approval Certification and is designed per European Hygienic Equipment Design Group (EHEDG) specifications to be flushed and cleaned in place. When installed for clean-in-place (CIP) operation, unlike rotary lobe pumps, it experiences no loss of performance due to vertical drain porting (Figure 2). When cleaning, pressure is introduced to the back of the eccentric disc through the pump chamber. When the flush pressure overcomes the spring, the disc moves away from the cylinder, allowing the

FIGURE 2 | Clean-in-place operation. Cylinder

Disc

Hub Shaft

Axial spring loading CIP internal Disc movement due Cleaning solutions pass through action to flush pressure the pumping chamber cleaning solution to pass through the pumping chamber. This feature allows a relatively large volume of cleaning fluid to sweep through the pump, providing a thorough

AMAZING FINISHES DON’T JUST HAPPEN We’ve had years of practice to perfect ours. Few specialty chemical manufacturers can offer the same level of performance or experience in the coatings industry. That has given us plenty of practice at perfecting an extensive line of additives – from pigment dispersions and colorants to defoamers – to achieve that perfect finish. So don’t settle for anything less than a proven performer.

t Black Shield carbon black pigment dispersions t FOAM BLAST® defoamers/antifoams t MASIL® reactive silicones/silanes t Hilton Davis® color dispersions for paints/stains t CVC specialty epoxies t Kalama K-FLEX® dibenzoate plasticizers TM

TM

For more information on these products, visit www.emeraldmaterials.com

® Registered trademarks of Emerald Performance Materials, LLC ™ Trademarks of Emerald Performance Materials, LLC © 2009 Emerald Performance Materials, LLC

Visit ads.pcimag.com PA I N T & C O A T I N G S I N D U S T R Y

040 Blackmer FT.indd 41

䡲䡲䡲

41

2/16/10 8:29:59 PM

Binder Transfer in Coatings

cleaning and often eliminating the need for bypass piping for the CIP mode. Where maintenance is concerned, Mouvex C-Series eccentric disc pumps consist of very few parts. The cylinder-disc assembly can be replaced without disturbing the suction piping or drive components.

Eccentric Disc Technology vs. Others Because of all of these characteristics, Mouvex eccentric disc pumps are able to supply important benefits that pumps traditionally utilized in the coatings market sector cannot supply.

think your product can only be processed on a horizontal mill? Cosmetics • Inks • Pesticides • Paints • Finishes • Coatings • Chemicals

think again… think… immersion milling technology

• Air-Operated Diaphragm (AOD) Pumps. AODs have traditionally been the pump of choice in the coatings market because of their low initial purchase cost. However, there are certain types of AOD pump brands that can be less energy efficient than others that use leadingedge air-distribution systems. • Gear Pumps. The second most popular pump choice behind AODs due to their capability of handling higher viscosity ranges are gear pumps. The weaknesses of gear pumps include excessive seal leakage; inability to self prime; a flow rate that is jeopardized when wear begins; high internal velocities that affect fluid dynamics, resulting in shear; and clearances that result in slip as pressures increase and viscosities decrease. • Centrifugal Pumps. The primary drawback of centrifugal pumps is their high rate of slippage. Centrifugal pumps typically have lower efficiencies than eccentric disc pumps. • Lobe Pumps. Lobe-type pumps perform like gear pumps, meaning they have many of the same drawbacks that gear pumps have. Also, the need to seal two shafts doubles the expense of seals and the potential for leakage.

Conclusion

N Quick color changes N 30 - 50% faster production times

N Superior Product Quality N Reduced Media Usage

N Low Maintenance

N Increased Solids

If you’re interested in seeing our mill in action just call 252-338-4705 and make arrangements for a test in our lab. We’re so confident that our mill will meet your requirements that we’ll reimburse you for travel expenses if we are unable to meet or exceed your current standard.

A final benefit of the Mouvex Eccentric Disc Pump is that it is a multi-use piece of equipment, meaning that it can be used in many applications. In the coatings industry, that could include the pumping of pigments, resins, solvents and additives. These capabilities help make eccentricdisc technology the perfect solution when faced with the challenges of addressing pump seal, suction, product shear and volumetric efficiency concerns. Through the incorporation of such unique benefits as leak-free operation and line-stripping capabilities, the eccentric-disc principle makes the pump extremely flexible, allowing the pumping of low-viscosity, high-viscosity and highly abrasive materials within a single process – all with the same pump. This makes the pump not only a longer-lasting, more efficient piece of equipment, but a multi-tasking one, as well – and possibly the answer for many difficult pumping applications in the coatings industry. 䡲 For more information on Mouvex, visit www.mouvex.com, and PSG at www.pumpsg.com or Jovani@ mouvex.com.

Visit ads.pcimag.com 42

䡲䡲䡲

040 Blackmer FT.indd 42

MARCH 2010 | W W W . P C I M A G . C O M

2/17/10 9:22:59 AM

Fluorosilicone Hybrid Technology Bridging the Gap Between Performance and Sustainability

G

rowth ro wth t h th thro through roug ugh h in innovati innovation tion m must ustt be us guided by the commitment to do so in an environmentally sustainable manner. Because sustainability is fundamental to long-term economic success, continuous efforts to reduce the environmental impact while simultaneously improving health and safety aspects of current and future products are necessary. Sustainability means good business. Companies are routinely increasing the priority of sustainability and eco-innovation in many decision-making arenas. This is not just from the products they make or sell to ensure compliance with current legislation, but from supporting the principles of sustainability through business strategies, processes, products and solutions. Acting responsibly creates economic growth and value and improves the quality of life, creating balance among the three main pillars of sustainability: economic prosperity, environmental quality and social equity. Recent developments in the field of fluorosilicone hybrid coatings and additives have successfully bridged the gap between providing unique performance and satisfying demanding environmental requirements. Fluorosilane anti-fingerprint coatings, hydrosilylation-cure tetrafluoroethylene easy-to-clean coatings, silicone-modified fluoroacrylate textile treatments and fluorosilicone UV-cure resin coatings are some examples of these new sustainable technologies. The synergistic effect of combining fluorine and silicone chemistry results in protective coatings that provide excellent chemical resistance, weatherability, abrasion resistance and thermal sta-

FIGURE 1 | Reaction mechanism of a hydrosilylation-cure tetrafluoroethylene copolymer. Alkenyl Functional TFEC F *

F

F

F

F

F *

F

F

R

F

F

R

F

F

R

Si Si-H Functional Crosslinker Catalyst (ex. Pt)

F *

F

F

F

F

F

bi bili lity ty. Eliminating Elim El imiinatin ting g oz ozon onee-de deplleti ting chemicals, c em ch mical icals, reducing reducing bility. ozone-depleting energy consumption, transforming to water-based systems and resolving PFOA/PFOS regulatory constraints are possible with fluorosilicone hybrid chemistry. chemistry

Sustainability Means Good Business Chemistry brings great value to society. Exciting new materials and technologies, comfort, convenience and economic opportunity are all outcomes of innovation in chemistry. Chemicals are essential to modern life. But how can we balance the need for technological innovation and economic growth with the need to protect human health and the responsibility to provide for future generations? Concern about the impact our lifestyles have on the environment and nonrenewable resources is growing. This concern comes not only from government agencies, but also from industrial users and consumers. Increasing sensitivity to the impact materials have on people and nature is causing proactive responses from industry to ensure the sustainable nature of innovation. The challenge then becomes the balance of innovation to benefit society and the responsibility to protect our environment. While this may seem like a daunting hurdle, it is, in fact, a very realistic goal. Ensuring our companies have a financially viable future is a natural outcome of maintaining this balance. This was confirmed in a recent international research study conducted for Dow Corning Corporation by the independent market research company Harris Interactive, where attitudes toward sustainability among companies around the world were revealed. One of the key findings was that environmental and sustainability factors have a strong influence on the selection of suppliers in all geographies.1 This response highlights the need to provide this balance. The result is both sustainable business and a better environment.

* F

F

R

F

F

R

F

F

Energy Conservation

R

S R *

F F

F F

R

F F

F

R *

F

Among the most obvious, and measurable, benefits to the balance of business and the environment are ways to reduce energy usage. Most coating technologies need energy to cure. Heat cure is a common curing method for urethanes, acrylic, fluorine and silicones. Finding ways

By Steven Block | Dow Corning Corporation, Midland, MI 44

䡲䡲䡲

044 Dow Corning.indd 44

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 10:04:52 AM

Fluorosilicone Hybrid Technology: Bridging the Gap Between Performance and Sustainability

to reduce the curing temperature or the time to cure will save energy. When doing a coil coating operation, for example, heat is required to cure these coatings; however, the coil itself heats up, absorbing more energy and costing more to operate the coating line. One of the new fluorosilicone technologies that has recently been developed requires both a lower cure temperature and a shorter cure cycle. The technology uses a hydrosilylation-cure tetrafluoroethylene copolymer (TFEC) in the reaction mechanism described in Figure 1. This hydrosilylation cure is a common silicone addition cure with the added benefit of having no cure byproduct, which means there is essentially no shrinkage of the cured coating membrane. This cure method requires less energy than traditional melamine or urethane systems and it does not require the engineering systems necessary to capture, scrub, condense or incinerate byproducts. With the Si-H functional crosslinker used in the TFEC hydrosilylation system, the cure mechanism combines breaking the carbon-carbon double bond in the pendant vinyl group on the polymer backbone followed by the crosslink with the Si-H compound. The curing can take place at a temperature as low as 150 ºC. At this temperature this coating takes around 100 seconds to cure (with cure being defined as how long it takes to withstand 100 double rubs with MEK). The

MEK Resistance (double rubs) 100

FIGURE 2 | Fluorosilicone coating cure/time relationship.

Si cure TFEC 230 ºC Melamine cure 150 ºC Si cure TFEC 150 ºC

Si cure TFEC 180 ºC

Isocyanate cure 150 ºC 0

20

40 60 80 Cure Time (seconds)

100

TABLE 1 | Properties of the UV-cure fluorosilicone-hybrid hardcoat technology. PET Film Test Contact angles, degrees Taber abraser* Abrasion (steel wool)* Pencil hardness Adhesion

Condition

Hybrid Hardcoat

Acryclic

Control

H20 n-Hexadecane 1kg, 100 cycle

107 65 5

66 -24

72 -53

#0000, 500gf, 30 times

0

3

27

JIS K-5600

4H

3H

3H

JIS K-5600

100/100

100/100

100/100

*Abrasion result is the difference in haze before and after testing ΔH. A larger value means lower abrasion stability. 46

䡲䡲䡲

044 Dow Corning.indd 46

cure rate, as a function of time and temperature, needs to be balanced with the rest of the process line. For highvolume processes, this developing fluorosilicone coating can completely cure in 10 seconds at 230 ºC. The cure time relationship is shown in Figure 2. Typical melamine and isocyanate cure coating systems are shown for reference and as a point of relative comparison. To understand the effect on the overall heat requirement, a simple example will highlight the impact of this lower cure temperature and cure time of the hydrosilylation-cure TFEC coating technology versus polyvinylidene fluoride (PVDF). In 2006 approximately 6.7 million metric tonnes of steel was coated globally in coil coating processes.2 The cure temperature of the new TFEC coating is 90 ºC lower than PVDF (150 ºC compared to 240 ºC). Using the standard heat capacity of steel as 0.45 J/g/ºK3 and assuming that 8% of the total coil coating used PVDF coating in 20062, the resultant energy savings is 7.9 x 1015 Joules annually. Using a natural gas price of $8.20/ MCF4 yields a net savings of nearly $150M per year. The U.S. Department of Energy (U.S. DOE) surveyed residential houses in 2005 and found that the average annual energy consumption per house is 1 x 1011 Joules.5 Therefore the potential energy savings with the new TFEC coating is enough to supply approximately 80,000 residential houses in the United States each year. When energy savings can be described in a manner that has a concrete foundation the impact is clear even to the most casual observer. The impact on the environment from this decreased energy use is a reduction of 975,000 metric tonnes of CO2 emitted to the atmosphere annually. It has been reported that 1 MCF of natural gas requires 0.18 tree to offset the CO2 produced in the decomposition of this 1 MCF.6 This new TFEC coating technology, using the assumptions above, converts to a savings of 7.3 million MCF of natural gas. To offset the CO2 produced from this amount of natural gas would take 1.3 million trees to convert the CO2 to oxygen. An even more efficient cure method is using UV energy from bulbs with a specified wavelength, instead of fossil fuel-produced heat energy. These new UV-curing systems require much less heat energy and also cure significantly faster. Improvements in both energy usage and productivity are achieved with UV cure coatings. The new UV-cure fluorosilicone-hybrid hardcoat technology gives the benefits of cost savings from lower energy demands as well as improved hydrophobic, oleophobic and easy-to-clean properties as shown in Table 1. This new UV-cure hybrid technology can reduce the energy demand for the same quantity of coil coated by 1.76 x 1016 Joules/year, or 16.2 million MCF of natural gas. If, hypothetically, all the PVDF coating used for coil applications were replaced with the new UV-cure coating technology the reduction in natural gas combustion could yield a reduction of 2.2 million metric tonnes of CO2. This savings would result in 2.9 million fewer trees needed to convert this amount of CO2 to oxygen. The energy savings from using the UV cure coating technology would heat approximately 180,000 houses in the United States each year.

Improving Air Quality The Earth’s ozone layer protects all life from the sun’s harmful

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 10:05:01 AM

Fluorosilicone Hybrid Technology: Bridging the Gap Between Performance and Sustainability

TABLE 2 | Product performance of the C6-based textile treatment compared to current C8 and C4 fluorocarbon treatment chemicals. Test Method

Substrate O.W.B. Nylon

Water repellency AATCC 22 (spray test)

Polyester Cotton Nylon

Oil repellency AATCC 118

Polyester Cotton Nylon

Water repellency IPA dropper test (internal method)

Polyester Cotton

Hand

Polyester

0.4 0.8 0.4 0.8 3.2 4.8 3.2 4.8 3.2 4.8 3.2 4.8 3.2 4.8 3.2 4.8 3.2 4.8

Current Fluorosilicone Current C8 Coating C6 Hybrid C4 Coating 100 100 80 100 100 100 6 6 5 6 3 6 8 8 4 4 4 5 Good

90 100 90 100 100 100 6 6 5 5 5 5 9 9 5 5 5 5 Good

80 100 80 80 90 90 2 2 5 5 3 4 2 2 3 3 2 4 Poor

radiation, but human activities have damaged this protective layer. Less protection from ultraviolet light will likely, over time, lead to higher skin cancer and cataract rates as well as crop damage. In response to the prospect of increasing ozone depletion, the governments of the world created the 1987 United Nations Montreal Protocol as a global means to address this global issue. As a result of the broad compliance with this Protocol and industry’s development of ozonefriendly substitutes, the total global accumulation of ozonedepleting gases has slowed and has now begun to decrease.7 This has reduced the risk of further ozone depletion. Now, with continued compliance, recovery of the ozone layer is expected by late in the 21st century. There are currently 191 countries phasing out the production of ozone-depleting substances in an effort to safeguard the ozone layer. For more than 50 years, chlorofluorocarbons (CFCs) were thought of as miracle substances. They are stable, nonflammable, low in toxicity and inexpensive to produce. Over time, CFCs found uses as refrigerants, solvents, foam blowing agents and in other, smaller applications. CFCs are now being regulated out globally specifically to reduce their negative effect on depleting atmospheric ozone. However, not all chemicals containing fluorine are considered ozone-depleting substances. Fluorochemicals that do not contain chlorine are excluded from the definition of materials that have been found to add ozone

Eversorb® Product Types • Benzophenone

• Benzotriazole

• HALS

• Performance Products

Eversorb® Applications • Automotive Coatings • Refinish Coatings • Wood Coatings • Coil Coatings • Powder Coatings • New Unique Water Based UV for Coatings

Visit us at the

American Coatings Show Booth #1113

• ISO 9001 Certified in 1994 • ISO 14001 Certified in 1996 • OHSAS 18001 Certified in 2001 EVERLIGHT USA, INC. 10507 Southern Loop Boulevard, Pineville, NC 28134 (704) 588-1004 (800) 252-3247 Fax: (704) 588-0051 E-mail: [email protected] http://www.ecic.com Visit ads.pcimag.com pci03104Ever.indd 1

48

䡲䡲䡲

044 Dow Corning.indd 48

2/2/10 9:16:07 AM

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 10:05:07 AM

Fluorosilicone Hybrid Technology: Bridging the Gap Between Performance and Sustainability

depletion. Specifically, new families of fluorosilicone hybrid technologies have been developed with improvements to their impact on the environment from the choices of solvents that are used. One of the newest of these coating innovations is a water-based penetrating stain repellent that completely eliminates solvent

by using water as the diluent. This waterbased fluorosilane material gives water and oil repellency to porous construction materials. Applied as a post treatment it provides both hydrophobic and oleophobic characteristics to substrates such as pavers, mortar, grout and natural stone. These new fluorosilane anti-stain treatments can

replace existing solvent-based penetrants to give the desired surface functional performance while at the same time eliminating the VOCs that are used in traditional treating agents. Performance and durability have been optimized to ensure the application requirements are being met. Treated substrates retain their original appearance with reduced dirt pickup and subsequently easier cleaning. In other recently developed fluorosilicone hybrid coating systems that still use solvents care has been taken to deliberately select solvents that are low in VOCs and do not contain hazardous air pollutants (HAPs). For example, the hydrosilylationcure TFEC coating technology uses n-butyl acetate (n-BuOAc) as the solvent at a high solids content of 55-60%. Research has also shown that the use of t-butyl acetate (t-BuOAc) can be used in this system, further improving the environmental footprint of this coating. In 2004 t-BuOAc was designated as VOC-exempt by the U.S. Environmental Protection Agency (U.S. EPA).8 This revision modifies the definition of VOC to say that t-BuOAc will not be a VOC for the purposes of VOC emissions limitations or VOC content requirements. There has also been an intentional effort to select the most eco-friendly solvent at the lowest solvent concentration in the UVcure hybrid hardcoat technology. Implementing propylene glycol monomethyl ether (PGME) as the carrier fluid for this system, at a solids concentration of nearly 40%, achieves the objectives of both creating a high-performing coating and in an environmentally conscientious manner. Higher solids content formulations, and those containing no VOCs, can be accomplished using UV-cure technologies. There are two primary benefits to air quality. The first one is by developing high solids coating formulations, where the absolute value of VOCs emitted per unit of coating is reduced. Consider that more than 2500 metric tonnes of coating are projected to be sold in the U.S. protective coatings market by 2011.2 The potential impact of increasing the solids content from the typical solvent-based heat cure system of around 30% to a high solids UV cure coating at 55% solids results in a theoretical reduction of nearly 600 metric tonnes of solvent annually. The second advantage to air quality with UV-cure materials is the reduction in energy needed to cure the coating, and the corresponding reduction in emissions from generating the energy required to cure

Visit ads.pcimag.com 50

䡲䡲䡲

PCI04094Qlab-panel.indd 1

044 Dow Corning.indd 50

MARCH 2010 | W W W . P C I M A G . C O M

3/19/09 10:53:46 AM

2/19/10 10:05:13 AM

Fluorosilicone Hybrid Technology: Bridging the Gap Between Performance and Sustainability

the coating. A recently completed study by the U.S. DOE has quantified energy savings from converting a heat cure coating to a UV-cure coating on aluminum cans.9 Ultimately, this report concludes that an industry-wide potential annual energy savings of 2.3 x1012 Joules by the year 2010 is possible if UV cure coatings

completely replace heat-cure coatings on aluminum cans.

Fluorine-Based Polymer Regulations In recent years studies conducted by government agencies have recognized concerns regarding the bioaccumulation of

perfluoroocanoic acid (PFOA) in humans. PFOA is an unintended industrial byproduct from the production of “C8” fluoropolymers. A C8 telomer is a chemical compound that contains the perfluoroalkyl group C8F17. The chemical formula for PFOA is C8F15O2H. In practice the terms PFOA and C8 (so called because of the carbon chain length) are often used interchangeably and include the principal salts of the acid (e.g., ammonium salt, alkali metal salt). Many water and oil repellents that contain C8 telomer compounds are used for long-term protection of textiles and carpets. PFOA is very stable in the environment, so it does not readily degrade. Once it enters the body it is eliminated very slowly so PFOA may remain in the body for relatively long periods of time. The half life in humans is about 4.5 years. Although current research does not establish that the levels of PFOA found in the environment cause adverse human health effects, studies do indicate that PFOA causes adverse effects in laboratory animals that have been given high doses over a long period of time.10 In 2000, the U.S. EPA became concerned about data that indicated PFOA is found in human blood in the general population. Since then, the U.S. EPA and the fluorochemical industry have cooperated in studies, and collected and shared information regarding PFOA. In January 2005 the EPA published a draft risk assessment on PFOA based on the available studies and data at that point.11 It was at this time the EPA announced the creation of the “2010/15 PFOA Stewardship Program” and asked fluorochemical manufacturers to participate in the program. To participate in this program the fluorochemical manufacturers committed to the following goals. • Reduce product content and facility releases of PFOA, precursors of PFOA and higher homologue perfluorinated substances (e.g., C9, C10, C12) by 95% by 2010 (from a year 2000 baseline). • Work toward the elimination of such chemicals from environmental releases and products by 2015. • Publish annual reports on progress toward these goals. Response to the concern over PFOA has resulted in a new developing family of fluorosilicone water-based hybrid emulsion textile treatment chemicals based on C6 chemistry. The U.S. EPA has characterized the data for C6 fluorochemicals as showing “different and less toxic” than PFOA. This is the same statement that is also used to compare C4 fluorochemicals to C8 fluorochemi-

Visit ads.pcimag.com

䡲䡲䡲

PCI05084Schold.indd 1 52

044 Dow Corning.indd 52

MARCH 2010 | W W W . P C I M A G . C O M

4/1/08 4:00:30 PM

2/19/10 10:36:23 AM

cals10. The EPA has also concluded it considers C6 and C4 compounds comparable in toxicity based on current toxicity studies. The result of a joint development project between Dow Corning and Daikin Industries is a new fluorosilicone hybrid treatment chemical that is PFOA-free. The problem with existing fluorine and silicone chemistry initially presented a significant technical challenge. Typically the use of a copolymer with dimethylsilicone side chain causes a reduction in oil repellency. Silicones are oleophilic by nature so a simple blend of silicones with fluorochemicals impedes the oil repellency of the fluorochemical component. Organofunctional silanes are commonly used to add softness to textiles. However, when these compounds are added as a blend to the fluorochemical treatment, the oil repellency is negatively affected. In addition, the stability of the emulsion can be an issue. This led to the concept, and eventual successful development, of a hybrid graft copolymer. The silicone backbone of this new copolymer gives the softness to the textile while the fluorine component imparts the oil repellency and durability. Ultimately the synergy of this novel chemistry solution is achieved in this hybrid system. Table 2 demonstrates the product performance of this new C6-based textile treatment as compared to current C8 and C4 fluorocarbon treatment chemicals.

Keeping Surfaces Clean Body oils contain lipids, salts, peptides, water and maybe even bacteria, and these components are often inadvertently trans-

FIGURE 3 | Comparative surface cleanliness before and after wiping. Fingerprint Before Wiping

Fingerprint After Wiping

PFPE Silane

C8F17 Silane

Untreated

ferred to surfaces that are touched. An increasing number of electronic devices now offer touch screen displays to enhance the user-device interface, where fingerprints can deposit unwanted contamination to the surface. Because of the prevalence of touch screens being used more in public places the implication for potential transfer of fingerprints, and the compounds in the fingerprint, is growing, too. Applications for public use touch screens include ATMs, check-in kiosks in airports, directional displays in shopping malls, and on public transportation. In every one of these applications undesirable contaminants may be unknowingly deposited on the surface of these displays, awaiting the next user who can be easily contaminated with these unwanted spe-

Visit ads.pcimag.com PCI07094EWK.indd 1

6/15/09 3:21:09 PM

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

044 Dow Corning.indd 53

䡲䡲䡲

53

2/19/10 10:05:26 AM

Fluorosilicone Hybrid Technology: Bridging the Gap Between Performance and Sustainability

cies. The need for cleaning these surfaces for hygienic reasons is obvious, but the practicality of cleaning them is very timeconsuming and expensive. In industrial settings the use of shared safety glasses presents another challenge. The U.S. Occupational Safety and Health Association (OSHA) has prescribed that

decontamination of shared personal protective equipment (PPE) between uses is mandatory to disinfect the surfaces.12 Decontamination methods must (1) physically remove contaminants; (2) inactivate contaminants by chemical detoxification or disinfection/sterilization; or (3) remove contaminants by a combination of both

Global Expert in Waterborne Paint and Coating Additives

@

TH

RHODAFAC®, RHODASURF®, SOPROPHOR®, ABEX®, GEROPON®, SIPOMER® PAM & WAM Guarantee Emulsion Stability and greatly Enhance Adhesion.

t Rh o

dia

Visi

BOO

Rhodia develops paint additives that meet the ever-changing requirements of the paint industry today, tomorrow and beyond. We offer innovative performance solutions and custom-made products for a variety of applications.

#1943

RHODOLINE® WA, RHODAFAC® NS AND GEROPON® Enhance Surface Wetting, Color Development, improve Gloss and Dispersion Stability. RHODOLINE® DF Performance Additive to Avoid/Reduce Foam during Processing and Application of Waterborne Formulations. RHODOLINE® FT Freeze-Thaw Stability for Low/Zero VOC Paint Formulations. RHODOLINE® OTE A Novel Additive to Extend Open Time for Low/Zero VOC Paint Formulations. RHODIASOLV® Low Odor Coalescing agents for Low/Zero VOC Paint Formulations

AN EXTENSIVE RANGE OF ADDITIVES FOR PAINT INNOVATORS Wetting & dispersing agents Coalescing agents

www.rhodia.com [email protected] Defoamers Special additives Additives for latexes synthesis

North America Phone: +1-609-860-4000 Fax: +1-609-860-0463 Europe Phone: +33 (0) 1 53 56 50 00 Fax: +33 (0) 1 53 56 53 90 Asia Pacific Phone: +65 - 6291 1921 Fax: +65 - 6394 3376 Latin America Phone: + 55 11 3741-7637 Fax: +55 11 3741-8378

physical and chemical means. This process is a non-value-added cost to industry where improvements to surface chemistry may positively affect the health of the user. Rather than trying to find a suitable decontamination method, a new fluorosilicone surface coating has been developed that actually repels fingerprints and the associated contaminants that may be contained in skin oils. This patented oleophobic and hydrophobic alkoxysilane functional perfluoro-polyether (PFPE) compound could help in keeping these surfaces cleaner. This material is especially useful on display screens and hygienic ware to reduce the accumulation of fingerprints and any natural skin oils. The comparative effect on the surface cleanliness is shown in Figure 3. This new hybrid polymer exhibits the oleophobicity of fluorine and hydrophobicity and durability of silicone. Improved durability over current chemical treatments is obtained by the use of a monofunctional terminal alkoxy silane modification to the linear PFPE polymer. The alkoxy silane reactive end will covalently bond to the surface via hydrolysis and condensation reactions to either hydroxyl- or silanol-containing compounds. This covalent bond gives the needed durability in touch screen display applications and eyewear. The resistance to wear by rubbing makes the surface cleaner for a longer period of time, which is a major improvement of this new technology. When the surface needs to be cleaned all that is needed to remove surface dirt and oil is to simply wipe it off. The easy-to-clean surface comes from the very low surface energy of the alkoxy silane functional PFPE polymer. That means the need for cleaning chemicals to remove oil, water and dirt is minimized, and the aesthetics are improved. Solar panels can also benefit from having the surface of the top glass sheet chemically treated. By using a fluorosilicone coating to lower the surface energy of the glass, water and dirt do not bond as easily, which means more of the sun’s energy is converted into electricity. The more physical barriers there are between the sun and the photovoltaic cell, the lower the operating efficiency. In the world of solar panels the drive now is to maximize the solar panel performance to optimize energy output. Increasing energy production in a solar panel reduces the overall cost of energy, so every incremental improvement becomes an important factor. Solar panels are expected to last up to 30 years in most applications, so a small gain in performance is magnified because of the expected service life.

Visit ads.pcimag.com 54

䡲䡲䡲

044 Dow Corning.indd 54

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 10:05:31 AM

Fluorosilicone Hybrid Technology: Bridging the Gap Between Performance and Sustainability

The overall trend of solar energy costs, as measured by price per watt peak, continues to decline with the Solar Module Retail Price Index most recently at $4.61/watt in the United States and €4.48/watt in Europe.13 Technologies that can continue to positively affect this trend will likely be adapted in the photovoltaic industry.

References 1 2 3 4 5 6 7

Conclusion Innovative fluorosilicone technologies offer many improvements to the environment. Positive impacts from this new range of coating chemistry include reduced VOCs and HAPs, elimination of PFOA-containing C8 chemicals, and energy savings from coatings with reduced energy needed for curing. Less energy for curing means a reduction in fossil fuel needed to produce this energy and a resultant reduction in CO2 production. The hybrid approach combining fluorine and silicone chemistry actually results in materials that exhibit the best characteristics of each technology. Silicones, with their natural polymer flexibility and UV resistance, and fluorine, with durable and oleophobic surfaces, are synthesized in many different polymers and resins in coating applications. Keeping surfaces clean and making them easy to clean are not solely for aesthetic purposes. These cleaner surfaces may also reduce person-to-person contamination. Innovative fluorosilicone materials are a foundation for sustainable business and offer concrete solutions to positively affect the environmental footprint of coatings. 䡲

8 9 10 11 12 13

http://www.dowcorning.com/content/about/aboutmedia/AltEnergy_Survey_ Results_2008.pdf U.S. Paint & Coatings Industry Market Study: 2006-2011; Kusumgar Nerlfi & Growney, Inc. http://www.physics.uci.edu/~silverma/units.html http://www.eia.doe.gov/oil_gas/natural_gas/info_glance/natural_gas.html http://www.eia.doe.gov/emeu/recs/recs2005/c&e/detailed_tables2005c&e.html http://www.americanforests.org/resources/ccc http://web.worldbank.org/WBSITE/EXTERNAL/NEWS/0,,contentMDK:20128036~ menuPK:34463~pagePK:64003015~piPK:64003012~theSitePK:4607,00.html http://www.epa.gov/EPA-AIR/2004/November/Day-29/a26069.htm http://www.osti.gov/bridge/servlets/purl/751067-9Vs9f7/webviewable/751067.pdf EPA, PFOA Homepage: http://www.epa.gov/opptintr/pfoa/pfoastewardship.htm Draft Risk Assessment Of The Potential Human Effects Associated With Exposure To Perfluorooctanoic Acid and Its Salts U.S. Department of Labor, Occupational Safety and Health Administration, OSHA 3151-12R, 2003 http://www.solarbuzz.com/ModulePrices.htm

Acknowledgements Mr. Mike Hales, Corporate Eco-Innovation Manager, Dow Corning Corporation; Mr. Masayuki Hayashi, Development Chemist, Dow Corning Toray Ltd.; Dr. Peter Hupfield, Technology Leader, Dow Corning Ltd.; Dr. Yasou Itami, Chief Researcher, Daikin Industries Ltd.; Mr. Eiji Kitaura, Development Chemist, Dow Corning Toray Ltd.; Dr. Don Kleyer, Senior Development Chemist, Dow Corning Corporation; Dr. Tetsuya Masutani, Business Development Manager, Daikin Industries Ltd.; Dr. Yasuhiro Nakai, Research Chemist, Daikin Industries Ltd.; Dr. Bill Schulz, Application Engineering Manager, Dow Corning Corporation; Ms. Janet Smith, Development Technologist, Dow Corning Corporation; Mr. Yoshinori Taniguchi, Process Engineer, Dow Corning Toray Ltd. For more information, visit www.dowcorning.com/ContactUs or e-mail steve.block@ dowcorning.com.

THE SOURCE FOR CUSTOMIZED TECHNOLOGY for 30 Years ▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪

CHEMICAL GRAFTING

▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪▪

“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 Visit ads.pcimag.com pci12094AdvP.indd 1

56

䡲䡲䡲

044 Dow Corning.indd 56

11/10/09 2:25:51 PM

MARCH 2010 | W W W . P C I M A G . C O M

2/19/10 10:05:37 AM

Zero-Voc, Water-Based Performance equivalent to solvent-based and high-VOC w

I

t is clear that laws governing the use of VOCcontaining coatings are becoming increasingly more stringent. For example, the maximum permissible level of VOC for Essential Public Service Coatings in California has been 100 g/L since July 1, 2006. It is reasonable to expect that other states will eventually enact similar legislation. For coatings manufacturers, future success depends upon the availability of products that have low levels of VOC; these products will provide a safer workplace for applicators and result in a cleaner environment. Since 1982, when the first bisphenol A-based solid epoxy dispersion and modified amine system came to market as an adduct suitable for metal protection, waterbased epoxy systems have been used for high-performance industrial primers and topcoats over metal due to their fast dry time, corrosion resistance, good pot life and low odor. Although water-based epoxies have successfully replaced traditional solvent-based epoxy/polyamide coatings in many high-performance industrial applications, the VOC content of these water-based epoxies is typically 200-350 g/L. So now, even though water-based, the usage of these coatings is increasingly limited by VOC regulations. The technical challenge of developing low- to zero-VOC water-based epoxies is a difficult and complex task that involves attention to the total formulation and all of its compositional materials including resins, pigments and additives. Unfortunately, most water-based epoxies containing very low levels of solvent do not exhibit the same performance as do the heavy-duty solvent-based epoxies and high-VOC water-based epoxies. Major differences are evident in film formation and application properties.

TABLE 1 | Comparison of various water-based epoxy systems. Liquid Epoxy Self-Emulsifying System

Previous Solid Epoxy Dispersion System

New Innovative Solid Epoxy Dispersion System

175-240

500-800

500

VOC (g/L)

0-120

200-350

0

Pot life @77 ºF/50% R.H.

1-2 h

4h

5.5 h

Dry tack free @77 ºF/50% R.H.

>6 h

2h

2h

Crosslink density

High

Low

Medium

Epoxy Equivalent Weight (EEW)

A zero-VOC water-based epoxy topcoat has been formulated without aid of solvent, acid, diluent or plasticizer. It is based on a new innovative bisphenol-A “1”-type solid epoxy resin dispersion cured with modified amine. The new development offers high gloss, fast cure, long pot life and excellent resistance to water, humidity, chemical and corrosion on metal and concrete substrates. The performance properties of the new zero-VOC water-based epoxy topcoat are comparable to solvent-based epoxy/polyamide and high-VOC water-based epoxies.

Experiment and Discussion Binder System Water-based epoxies used in conventional protective coating formulations are based on two principal technologies, i.e., liquid epoxy self-emulsifying systems and solid epoxy dispersion systems (Table 1). With epoxy equivalent weight ranging from 175 to 240, liquid epoxy self-emulsifying systems are very rich in epoxide groups. The combination of concentrated epoxides and amine hydrogens in the same emulsion particle provides coatings with high crosslink density and good chemical and abrasion resistance, but very short usable pot life, low flexibility and low impact resistance. These films are often too brittle for use on metal substrates. Since the film formation of liquid epoxy emulsion is dependent upon chemical reaction to increase viscosity, the dry time is very slow, often taking more than six hours to reach a tack-free state.¹ These liquid epoxy coatings do exhibit good handling, flow and coalescence without the aid of co-solvents, and can often be formulated to very low or zero VOC. Systems based on solid epoxy dispersion technology offer much faster dry times due to coalescence of the epoxy particles through water and co-solvent evaporation. Solid epoxy resins, with equivalent weights ranging from 500 to 800, provide coatings with lower crosslink density films that are more flexible, adhere better and have better impact resistance than liquid epoxy systems. Pot life is much longer due to the lower concentration of epoxides and amine hydrogens. Solid epoxy dispersion systems are closer in performance, especially on metal substrates, to traditional solvent-based epoxy polyamide systems. The major weakness of the epoxy dispersion type of system is its tendency to form heterogeneous films with epoxy-rich and amine-rich domains due to incomplete coalescence. To aid in processing and to overcome the poor flow and coalescence of the solid epoxy, co-solvents have to be added to the dispersion thereby eliminating any possibility of a zero-VOC formulation.¹

By Wendy Zhao, Scientist | The Sherwin Williams Company, Chicago, IL 58

䡲䡲䡲

MARCH 2010 | W W W . P C I M A G . C O M

058 SherwinWill_Showcase.indd 58

2/19/10 10:38:53 AM

Epoxy Topcoat C water-based epoxies A new and innovative solid epoxy dispersion topcoat, cured with a modified water-soluble amine binder system, incorporates the best characteristics of liquid epoxy emulsion and solid epoxy dispersion technologies and can be formulated to zero VOC. It is based on a bisphenol-A “1”type solid epoxy (EEW 500) using an internal surfactant built into the epoxy resin. When reacted, the internal surfactant becomes epoxy functional and is non-leachable, resulting in cured films with very good water resistance. A unique and patented high-speed dispersion process used for production of the epoxy dispersion yields a very small particle size (0.4 microns) without adding solvents or reactive diluents, providing good film formation, good storage stability properties and low to zero VOC formulation capability. The new zero-VOC water-based epoxy topcoat formulated with this binder system exhibits long pot-life (5.5 h @ 77 ºF/50% R. H.), short dry time (2 h tack free @ 77 ºF/50% R. H.), very good corrosion resistance (4,000 h salt fog) and good chemical resistance.

Pot Life and Film Formation Unlike solvent-based systems, termination of pot life in many water-based epoxy coatings is not always indicated by a gradual increase in viscosity. Early water-based epoxy systems suffered from overly rapid cure rates and poor gloss and color stability during pot life. The catalyzed paint would exhibit a time related, slow degradation in gloss as in-pot cure advanced during application. This degradation gave variability and patchiness of the coated

product, especially in cut-in perimeter areas on large architectural applications. These areas sometimes showed up as patches with non-uniform gloss and color after being filled in by roller application or otherwise touched up at different intervals after mixing. The pot life of waterbased epoxy coatings is influenced by a number of factors, such as emulsion particle size, the chemical nature of the epoxy resin and curing agent and the equivalent weight of both the epoxy resin and the curing agent. In general, preemulsified, small-particle-size, high-epoxy-equivalentweight resins give the longest pot life. In some systems, attempts to improve curing agent dispersion and extend pot life by the addition of volatile acid such as acetic acid have been successful. However, unless the amount of acid is carefully controlled, both water and corrosion resistance can suffer. The curing agent is blocked by acids that subsequently evaporate from the applied film to release the amine for reaction with the epoxy. Because the curing agent is blocked, this approach reduces cure rates. Pot life was evaluated on the new zero-VOC waterbased epoxy topcoat versus a commercialized water-based epoxy topcoat using a solid epoxy dispersion system by measuring viscosity, gloss and color change periodically after initial mixing of the epoxy and curing agent components. End of pot life was deemed the point where the catalyzed coating rose above 120 KU or exhibited a sharp gloss reduction and/or significant color change. Test results, shown in Figure 1 and Table 2, indicate that due to the ultra-fine particle size and the internal surfactant

TABLE 2 | Pot life evaluation on new zero-VOC W/B epoxy vs. commercial W/B epoxy @ 77 °F and 50% R.H. Time (min)

Viscosity (KU)

Gloss @ 60°/20°

Delta E

Zero-VOC W/B Epoxy

Commercial W/B Epoxy

Zero-VOC W/B Epoxy

Commercial W/B Epoxy

Zero-VOC W/B Epoxy

Commercial W/B Epoxy

Initial

98.6

96.7

93.9/82.0

92.9/64.0

Standard

Standard 2.98

30

100.8

103.9

95.1/83.1

94.2/76.0

0.49

60

101.1

109.8

96.9/84.5

96.8/70.9

0.60

3.24

90

102.8

118.0

95.7/81.2

94.0/63.0

0.98

3.60

120

106 3

Î132.4

96.9/83.6

Î 86.4/58.4

1.17

Î 5.10

150

107.6

146.6

97.0/79.9

80.2/54.0

1.32

12.9

180

109.6

94.5/69.8

1.64

210

112.8

94.9/64.7

1.83

240

114.3

93.3/60.7

2.05

270

118.1

91.8/58.7

2.36

300

119.3

90.3/58.2

2.57

330

Î 121.7

Î 89.7/57.6

Î 3.14

Î: End of Pot Life PA I N T & C O A T I N G S I N D U S T R Y

058 SherwinWill_Showcase.indd 59

䡲䡲䡲

59

2/19/10 10:39:00 AM

Zero-Voc, Water-Based Epoxy Topcoat

FIGURE 1 | Pot life evaluation on new zero-VOC W/B epoxy vs. commercial W/B

Viscosity (KU)

epoxy @ 77 °F and 50% R.H. 150 140 130 120 110 100 90 80

Thixotropes and Pigmentation

30

60

90 120 150 180 210 240 270 300 330 360 Time (min)

Gloss Degree

Zero-VOC W/B Epoxy

Commercial W/B Epoxy

100 90 80 70 60 50 40 0

30

60

90 120 150 180 210 240 270 300 330 Time (min)

Color Change (Delta E)

Zero-VOC W/B Epoxy @ 60 degree Commercial W/B Epoxy@ 60 degree

Zero-VOC W/B Epoxy @ 20 degree Commercial W/B Epoxy @ 20 degree

14 12 10 8 6 4 2 0 0

30 60

90 120 150 180 210 240 270 300 330 Time (min) Zero-VOC W/B Epoxy

Commercial W/B Epoxy

TABLE 3 | Comparison of thixotrope efficiency in various pigmented systems. Water-Soluble Amine Main Items of Part A

Main Items of Part B

Water and additives Pigment Thixotropes

75

85

110

Previous Solid Epoxy Dispersion

Water-Soluble Amine

Water-Soluble Amine

Water and additives

Water and additives

Water and additives

85

75

75

1:1

4:1

4:1

3

5

12

76

80

98

Part B viscosity (KU) Mixing ratio (A: B) Sag (wet mils) Mixed viscosity (KU)

䡲䡲䡲

Previous Solid New Innovative Solid Epoxy Dispersion Epoxy Dispersion

Water and additives Pigment Thixotropes

Part A viscosity (KU)

60

built onto the epoxy resin, the new zero-VOC water-based epoxy topcoat exhibits a long pot life and very good gloss and color stability throughout the pot life. These properties make it an ideal product for large area applications.

Water and additives Pigment Thixotropes

Dry film thickness requirements for water-based industrial maintenance topcoat applications are typically in the range of 2 to 5 mils requiring wet film capability of 5 to 12 mils. For the new zero-VOC water-based epoxy formulation, achieving optimum flow and sag control without the benefits of large organic solvent amounts is a difficult task requiring the formulator to rely more on coating additives. Although conventional types of thixotropes used in other water-based coatings, such as bentonite clays, cellulosics (HEC, HMHEC), alkali-swellable polymers (ASE, HASE) and hydrophobically modified urethane associative (HEUR) thickeners can be used, the selection of thixotropes as well as the balance between thixotropy and flow control for the new zero-VOC water-based epoxy system is extremely critical. Thixotropes that introduce any degree of real viscosity are counterproductive. Certain types of surfactants and emulsifiers added to the epoxy and amine resins during the dispersion or emulsion process significantly reduce the thixotropic efficiencies of associative thickeners. Conventional powder thixotropes, such as the bentonite clays, silicas and the high-molecularweight cellulosics, are often problematic in water-based epoxy formulations, especially when a high-gloss finish is required, so the selection of these materials is limited. The zero-VOC water-based formulation relies on a carefully balanced blend of flow control agents, thixotropes and formula pigmentation to achieve the desired film properties and required sag resistance. Pigments used in the formulation of the zero-VOC water-based epoxy, including color and hiding pigments, anti-corrosive pigments and extenders used for specific functional purposes, can also cause increased paint viscosity. This makes optimization of formula pigmentation, together with all other formula ingredients, a very complex task. With water-based epoxy formulations, sometimes the epoxy dispersion is pigmented and sometimes the amine curing agent is pigmented. However, in any two-component system, the choice of which component to pigment is normally governed by desired mix ratio. Pigmenting the larger component is always preferred. This makes it much easier for the mixed paint to maintain a full body viscosity and achieve optimal hiding power. The innovative solid epoxy dispersion used in the new zero-VOC water-based epoxy topcoat has an internal epoxyfunctional surfactant built onto the polymer backbone that has proven to have less tendency to reduce the efficiencies of thickeners compared to water-soluble amine or older, solid epoxy dispersion technologies (Table 3). A combination of organic and inorganic thickeners package is used to optimize sag resistance of the paint film. Pigmenting in the epoxy dispersion, the larger component in the 4:1 mix ratio of the new zero-VOC water-based epoxy topcoat, results in full body viscosity and optimized hiding power of the mixed paint. A flow/leveling agent is used along with the high-efficiency thickeners to balance thixotropy and flow control. With all

MARCH 2010 | W W W . P C I M A G . C O M

058 SherwinWill_Showcase.indd 60

2/19/10 10:39:07 AM

the above successful strategies adopted in the formulation, the new zero-VOC water-based epoxy topcoat achieved the desired film properties with good sag resistance (12 mils wet) and flow properties.

Coating Performance Mechanical Properties The zero-VOC W/B epoxy topcoat described in this paper has excellent mechanical properties as shown in Tables 4, 5 and Figure 2.

Early Moisture Resistance The new zero-VOC water-based epoxy topcoat has very good early moisture resistance as tested in a mist box. This test determines the effect of water misting on an applied coating film during various stages of the coating cure cycle. The mist box cabinet is equipped with six fog nozzles utilizing tap water and has a panel rack for supporting test specimens at an angle of 30º from vertical. After the coating is applied at recommended film thickness, samples cured for 2, 4 and 6 h and longer intervals if necessary, are exposed to the mist cabinet for 24 h. The panels are removed from the mist box and compared to control panels cured at 77 ºF and 50% R.H. Degree of blistering is checked immediately and after recovery using ASTM D 714. Gloss readings are taken according to ASTM D 523 and compared to the con-

TABLE 4 | Mechanical properties. Gloss ASTM D 523 Flexibility ASTM D 522 Direct impact ASTM D 2794 Abrasion resistance ASTM D 4060; 1000 cycles, 1 kg load Pencil hardness; 7-day cure Tape adhesion ASTM D 3359; 7-day cure; 1 coat over steel Patti adhesion ASTM D 4541; 7-day cure; 1 coat over concrete

>90 @ 60° Pass 1/8” in. mandrel 100 in. lbs. 150 mg loss H 5B 550 psi

TABLE 5 | Drying schedule. Properties

Zero-VOC W/B Epoxy Topcoat

Drying time @ 4.0 mils wet, 50% RH To touch: To handle: To recoat: minimum maximum To cure Pot life Sweat-in-time

50 °F

77 °F

120 ºF

1h 5h 8h 30 days 7 days 8h 30 min

45 min 4h 6h 30 days 7 days 5.5 h None

25 min 2h 3h 30 days 3 days 3.5 h None

We’re going further with Calfax® DPOS. Our proprietary Calfax® sulfonation technology continues to expand as we secure our position as the world's leading supplier of DPOS for the full range of Emulsion Polymerization applications. When you work with Pilot, you can be sure that you will go further in your product development efforts.

Contact us to learn more about our broad product offerings or to request samples.

Calfax®

World’s #1 Brand of Disulfonate Visit ads.pcimag.com PA I N T & C O A T I N G S I N D U S T R Y

058 SherwinWill_Showcase.indd 61

䡲䡲䡲

61

2/19/10 10:39:12 AM

Zero-Voc, Water-Based Epoxy Topcoat

TABLE 6 | Early moisture resistance.

FIGURE 4 | QUV – A (ASTM D 4587) – Delta E.

Dry Time

Blistering (ASTM D 714)

Gloss @ 60° (ASTM D 523)

Adhesion (ASTM D 3359)

2h 4h 6h Control

10 10 10 10

85 86 93 93

10 10 10 10

TABLE 7 | QUV – A (ASTM D 4587) – gloss retention.

12 10 8 6 4 2 0 250 hours

250 h

500 h

96% retention

71% retention

83% retention

57% retention

500 hours

Zero-VOC W/B Epoxy Gloss Topcoat

Zero-VOC W/B epoxy gloss Commercial W/B epoxy gloss

Zero-VOC W/B epoxy topcoat/ commercial W/B epoxy primer Commercial W/B epoxy topcoat/ commercial W/B epoxy primer Commercial S/B epoxy topcoat/ commercial S/B epoxy primer

FIGURE 5 | Cyclic weathering (ASTM D 5894) – 10 cycles. 10

TABLE 11 | 2000 hours salt fog resistance – ASTM B 117. Topcoat/Primer

Commercial W/B Epoxy Gloss Topcoat

Blistering

Rusting

Creepage

10

10

8

10

10

7

10

9

7

8 6 4 2 0 Blistering

Rusting

Creepage

Zero-VOC W/B Epoxy Topcoat/Commercial W/B Epoxy Primer Commercial W/B Epoxy Topcoat/Commercial W/B Epoxy Primer

TABLE 12 | 4000 hours salt fog resistance – ASTM B 117. Topcoat Zero-VOC W/B epoxy topcoat Commercial W/B epoxy topcoat

Commercial S/B Epoxy Topcoat/Commercial S/B Epoxy Primer

Blistering

Rusting

Creepage

10 3

10 2

8 8

FIGURE 6 | Cyclic weathering (ASTM D 5894) – 10 cycles.

Hours

FIGURE 2 | Drying curves – zero-VOC W/B epoxy gloss topcoat. 9 8 7 6 5 4 3 2 1 0

Zero-VOC W/B Epoxy Topcoat/ Commercial W/B Epoxy Primer

40

50

60

70

80

90

100

110

120

Temperature, ºF To Touch

To Handle

To Recoat

Pot Life

Commercial W/B Epoxy Topcoat/ Commercial W/B Epoxy Primer

Commercial S/B Epoxy Topcoat/ Commercial S/B Epoxy Primer

trol panels. Adhesion checks per ASTM D 3359 are made at 1 and 24 h recovery periods. The zero-VOC water-based epoxy topcoat showed excellent early moisture resistance after only 2 h cure (Table 6).

QUV Resistance FIGURE 3 | QUV – A (ASTM D 4587) gloss retention. 100 80 60 40 20 0 250 hours

500 hours

Zero-VOC W/B Epoxy Gloss Topcoat Commercial W/B Epoxy Gloss Topcoat

62

䡲䡲䡲

The QUV (ASTM D 4587) chamber utilizes a 4-h light cycle of intense light, using UVA 340 lamps at 60 ºC followed by 4 h condensation on the coating surface at 50 ºC. Under these conditions, the zero-VOC W/B epoxy gloss topcoat showed excellent gloss retention of greater than 70% after 500 h exposure (Table 7 and Figure 3) and color change of less than 5.0 delta-E (Table 8 and Figure 4). This is significantly better performance than seen with the commercial W/B epoxy topcoat.

Corrosion Weathering Resistance ASTM D 5894 describes a cyclic weathering test that includes wet/dry and light/dark cycles to mimic natural

MARCH 2010 | W W W . P C I M A G . C O M

058 SherwinWill_Showcase.indd 62

2/19/10 10:39:18 AM

Zero-Voc, Water-Based Epoxy Topcoat

exposures. Test panels are exposed to alternating periods of one week in a QUV chamber and one week in a cyclic fog/dry chamber. The QUV/condensation cycle is 4 h UV

TABLE 8 | QUV – A (ASTM D 4587) - Delta E. Zero-VOC W/B epoxy gloss topcoat Commercial W/B epoxy gloss topcoat

250 h

500 h

3.2 Delta E

5.4 Delta E

8.2 Delta E

12.0 Delta E

TABLE 9 | Cyclic weathering (ASTM D 5894) – 10 cycles. Topcoat/Primer Zero-VOC W/B epoxy topcoat/ commercial W/B epoxy primer Commercial W/B epoxy topcoat/ commercial W/B epoxy primer Commercial S/B epoxy topcoat/ commercial S/B epoxy primer

Blistering

Rusting

Creepage

10

10

9

10

10

9

10

10

8

Salt Fog Resistance

TABLE 10 | Cyclic weathering (ASTM D 5894) – 15 cycles. Topcoat Zero-VOC W/B epoxy topcoat Commercial W/B epoxy topcoat

at 60 ºC and 4 h condensation at 50 ºC, using UVA-340 lamp. The fog/dry chamber runs a cycle of 1-h fog at 35 ºC and 1-h dry-off at 35 ºC. The fogging electrolyte is a relatively dilute solution consisting of 0.05% sodium chloride and 0.35% ammonium sulfate. The new zeroVOC water-based epoxy topcoat applied over the commercial water-based epoxy primer was rated as 10 with no blistering and no rusting, and scribe performance was rated as 9 with 1/64th inch scribe creep after 10 cycles (Table 9, Figure 5). This performance is comparable to the commercial water-based epoxy topcoat/primer system and commercial solvent-based epoxy topcoat/ primer system (Figure 6). The zero-VOC water-based epoxy topcoat applied with two coats over sand blasted steel was rated as 10 with no blistering and no rusting after 15 cycles. The scribe performance was rated as 8 with 1/32th inch scribe creep (Table 10, Figure 7). In this test, the performance was significantly better than the commercial water-based epoxy topcoat (Figure 8).

Blistering

Rusting

Creepage

10 5

10 3

8 8

The salt fog test run is according to ASTM B 117; the test panels are continuously exposed in the cabinet with a wet and dark salt fog environment. The fogging electrolyte solution consists of 5% sodium chloride sprayed at 95 °F (35 °C). The zero-VOC water-based epoxy topcoat applied over

z Recover Lost Product z Eliminate Residual Product Contamination & Off-Spec Batches z Eliminate/Reduce Flush Waste & Disposal z Reduce Downtime Between Batches z Safe & Easy For Operators To Use z Rapid Return On Investment Call today for further information and a copy of our video “CALL TOLL FREE:

888-973-0079”

Inline Services Inc. 27731 Commercial Park Dr. Tomball TX 77375 Tel: 281.401.8142 Fax: 281.401.8147 E-mail: [email protected] web: www.inlineservices.com

Visit ads.pcimag.com 64

䡲䡲䡲

MARCH 2010 | W W W . P C I M A G . C O M

058 SherwinWill_Showcase.indd 64

2/19/10 1:39:12 PM

Zero-Voc, Water-Based Epoxy Topcoat

FIGURE 7 | Cyclic weathering (ASTM D 5894) – 15 cycles.

FIGURE 10 | 2000 hours salt fog resistance – ASTM B 117.

10 8 6 4 2 0 Blistering

Rusting

Creepage

Zero-VOC W/B Epoxy Gloss Topcoat Commercial W/B Epoxy Gloss Topcoat

FIGURE 8 | Cyclic weathering (ASTM D 5894) – 15 cycles.

Zero-VOC W/B Epoxy Topcoat/ Commercial W/B Epoxy Primer

Commercial W/B Epoxy Topcoat/ Commercial W/B Epoxy Primer

Commercial S/B Epoxy Topcoat/ Commercial S/B Epoxy Primer

FIGURE 11 | 4000 hours salt fog resistance – ASTM B 117. 10 8 6 4 2 0 Blistering

Zero-VOC W/B Epoxy Topcoat / Sandblasted steel

Commercial W/B Epoxy Topcoat/ Sandblasted steel

FIGURE 9 | 2000 hours salt fog resistance – ASTM B 117.

Rusting

Creepage

Zero-VOC W/B Epoxy Gloss Topcoat Commercial W/B Epoxy Gloss Topcoat

FIGURE 12 | 4000 hours salt fog resistance – ASTM B 117.

10 8 6 4 2 0 Blistering

Rusting

Creepage

Zero-VOC W/B Epoxy Topcoat/Commercial W/B Epoxy Primer Commercial W/B Epoxy Topcoat/Commercial W/B Epoxy primer Commercial S/B Epoxy Topcoat/Commercial S/B Epoxy Primer

TABLE 13 | Chemical resistance (ASTM D 1308). Reagent

Zero-VOC W/B Epoxy Topcoat

10% Hydrochloric acid Good 10% Nitric acid Good 10% Phosphoric acid Good 10% Sulfuric acid Good 25% Acetic acid Good 15% Sodium hydroxide Excellent 28% Ammonia Excellent 50% Ethanol Good Xylene Excellent MIBK Excellent MEK Excellent Mineral spirits Excellent Ethylene glycol Excellent Toluene Excellent Gasoline Excellent Water Excellent Brake fluid Good Bleach Excellent Motor oil Excellent Per ASTM D 1308: Fair = Pass 6 h; Good = Pass 24 h; Excellent = Pass 7 days 66

䡲䡲䡲

Zero-VOC W/B Epoxy Topcoat / Sandblasted steel

Commercial W/B Epoxy Topcoat/ Sandblasted steel

the commercial water-based epoxy primer was rated as 10 with no blistering and no rusting, and scribe performance was rated as 8 with 1/32th inch scribe creep after 2000 h (Table 11, Figure 9). This performance is comparable to the commercial water-based epoxy topcoat/primer system and commercial solvent-based epoxy topcoat/primer system (Figure 10). The new zero-VOC water-based epoxy topcoat applied with two coats over sandblasted steel was rated as 10 with no blistering and no rusting after 4000 h. The scribe performance was rated as 8 with 1/32th inch scribe creep (Table 12, Figure 11). In this test, the performance was significantly better than the commercial water-based epoxy topcoat (Figure 12).

Chemical Resistance The new zero-VOC water-based epoxy topcoat has excellent resistance to a wide variety of industrial and household chemicals. Results of chemical resistance spot tests run in accordance with ASTM D 1308 (Table 13) shows the zero-VOC epoxy topcoat resists acids, bases, industrial solvents such as ketones, alcohols, glycol ethers, and aliphatic and aromatic hydrocarbons and various other chemicals such as bleach, motor oil and brake fluid.

MARCH 2010 | W W W . P C I M A G . C O M

058 SherwinWill_Showcase.indd 66

2/19/10 10:39:32 AM

Recommended Systems

TABLE 14 | Recommended systems.

The new zero-VOC water-based epoxy topcoat can be applied directly to concrete, metal and primed substrates. The coating is compatible with a wide variety of primers including water-based acrylics, water-based epoxies and solvent-based epoxies. These systems offer comparable exterior durability and corrosion resistance to high-VOC water-based epoxy topcoat/primer systems and solvent-based epoxy topcoat/primer systems. Table 14 shows examples of recommended systems.

Conclusion A zero-VOC water-based epoxy topcoat has been formulated based on a new innovative solid epoxy resin dispersion cured with modified water-soluble amine without adding solvent, acid, diluent and plasticizer. The new development offers high gloss, fast cure, long pot life and excellent resistance to water, humidity, chemical and corrosion on metal and concrete substrates, making it suitable for many industrial maintenance applications. The performance properties of the new zero-VOC waterbased epoxy topcoat are comparable to solvent-based and high-VOC water-based epoxies. The new zero-VOC water-based epoxy offers an excellent alternative to replace conventional epoxy coatings when VOC regulation compliance is critical. 䡲

New Ownership / A World of Possibilities

䡲 “Green” PUD’s – Zero nMP & Zero VOC 䡲 Nano-Engineered PUD’s - for Improved Performance 䡲 Anti-Graffiti Coatings – Zero nMP 䡲 Fire Retardant PU Dispersions – Halogen Free 䡲 Functional PU Films for Thermoforming Applications Contact Ernie Gulla at 1-888-205-8126 or via email at: [email protected] Dudley, MA • Phone: 508-943-9052 • www.maceco.com AC Show Booth #823

Concrete

2 cts zero-VOC W/B epoxy topcoat

2 cts zero-VOC W/B epoxy topcoat

1 ct acrylic primer

1 ct acrylic primer

1-2 cts zero-VOC W/B epoxy topcoat

1-2 cts zero-VOC W/B epoxy topcoat

1 ct W/B epoxy primer

1 ct W/B epoxy primer/sealer

1-2 cts zero-VOC W/B epoxy topcoat

1-2 cts zero-VOC W/B epoxy topcoat

1 ct S/B epoxy primer

1 ct S/B epoxy primer/sealer

1-2 cts zero-VOC W/B epoxy topcoat

1-2 cts zero-VOC W/B epoxy topcoat

References 1

2 3 4 5 6

Dubowik, D.A.; Ross, G.C. A Novel Waterborne Epoxy Resin for Zero VOC Two Component Coatings. Paint and Coatings Industry 2000, 9. McAndrew, T. P. Low-VOC Non-toxic Primer for Coatings. Paint and Coatings Industry 2002, 10. Hare, C. Protective Coatings. SSPC 94-17. Chapter 15, P. 205 and Chapter 28, 400. Roy II, G.A.; Weinmann, D. Can Waterborne Epoxies Answer the Market’s Challenge? Paint and Coatings Industry 2000, 6. Oldring, P. “Waterborne & Solvent Based Epoxies and Their End User Applications”, Chapter 10, P. 486-490. Fox, C.J.K. A New Rheology Modifier for Waterborne Industrial Coatings Formulation and Performance. Paint and Coatings Industry 2000, 9.

EIGER

MACHINERY INC.

SUPPLIER SHOWCAS ES

MACE Polymers & Additives, Inc. The Polyurethane Specialists

Steel

GR AYSL AKE, ILLINOIS

The laboratory “M series Mills” are ideal for producing realistic dispersion samples for research, and quality control applications. These self pumping & self contained mills can wet mill samples as little as 25 ml’s, providing results that will answer dispersion questions. Investigating Nano dispersions? The “M” series mills can use media sizes less than 0.3 mm diameter and are capable of producing sub-micron particles. Ideal for paints, inks, colorants and chemicals. Pilot scale and production mills are also available.

Contact EMI - Eiger Machinery, Inc. for more information or to arrange a demonstration. AC Show Booth #1836

Tel: 847-548-0044

www.EIGERUS.COM

Visit www.pcimag.com/ac_show TODAY to get easy access to AC Show updates! • C Conference f Schedules • Exhibitor Information • Dining Guide for Charlotte

And, much more! PA I N T & C O A T I N G S I N D U S T R Y

058 SherwinWill_Showcase.indd 67

䡲䡲䡲

67

2/19/10 10:39:36 AM

0HHWXVDWWKH$PHULFDQ&RDWLQJV6KRZERRWK1R



70 2[\OLQN  )RUEHWWHU ZDWHUERUQH FRDWLQJV

P RODUCTS 䡲 Mixer

CHARLES ROSS AND SON CO.: A new design of the PowerMix (planetary disperser) combines two slow-speed planetary stirrers with two conventional high-

$QHZSHUIRUPDQFHDGGLWLYHIRU  Ŷ 6KRUWHU  Ŷ %HWWHU  Ŷ ,PSURYHG Ŷ +LJKHU  Ŷ ,QFUHDVHG

GU\LQJWLPH EORFNLQJUHVLVWDQFH VROYHQWUHVLVWDQFH KXPLGLW\UHVLVWDQFH FURVVOLQNLQJ

&DOOXVIRUDIUHHVDPSOH 2[\OLQN#EXKOHUJURXSFRP 86$&DQDGD (XURSH$VLD  ZZZEXKOHUJURXSFRP

Visit ads.pcimag.com

Purity through innovation Global Sieving and Filtration Specialists

speed dispersers. Independently driven agitators revolve on their own axis, while at the same time on a common axis. Highspeed blades provide an intensive shearing action, while the planetary stirrers continually move material into the blades. Call 800/243.ROSS.

䡲 Defoamer

COGNIS: Dehydran 2293 offers superior defoaming performance and excellent long-term efficiency. It is a high-performing product for high-gloss, highly pigmented systems and clear coatings, and is completely free of VOCs and solvents. Visit www.cognis.com.

䡲 Dispersion

WACKER: VINNAPAS® EF718 was devel-

Filtration without the Mess or Stress

The Self-Cleaning Russell Eco Filter®... • Improves the quality of your liquids • Offers you tool free & easy dis-assembly • Reduces your time & labor costs Call us at: USA: 704 588 9808

See us at Booth 2124 Visit ads.pcimag.com

68

䡲䡲䡲

068 Products.indd 68

oped as a low-VOC, APEO-free binder for environmentally friendly and low-odor paints. Offering scrub resistance, early water resistance and low odor, it can be used as a replacement for vinyl acrylics and styrene acrylics. It requires no coalescent to form a film because of the selfcoalescence of VAE copolymers and offers improved thickener response over other VAE and vinyl acrylic commercial products. Visit www.wacker.com.

䡲 Carbon Nanotube

SOUTHWEST NANOTECHNOLOGIES: SWeNT® SMW 100 was developed for polymer composites that require better electrical and mechanical performance than is possible from conventional multi-wall carbon nanotubes. Target applications include conductive polymers, reinforced elastomers and buckypaper materials for structural composite manufacturing. Visit www.swentnano.com.

MARCH 2010 | W W W . P C I M A G . C O M

2/17/10 3:57:12 PM

P RODUCTS

Type ZY Premium Type ZY Type ZS

䡲 Dewpoint Meter

Type Z

ELCOMETER: Elcometer 319 with Blu-

Type GZ

®

SiLibeads

King„ of all Beads” strong powerfull

etooth® is durable, rugged, dustproof and waterproof to IP66. It has sensors that range from -40 º F to 1760 º F, and it records all key climatic values with up to five parameters displayed together. High and low limits can be set against each parameter, triggering visual and audible alarms when a limit is exceeded. Features include inbuilt memory and statistics, remote data logging, and magnets for secure attachment to any steel structure. E-mail [email protected].

䡲 Solar Sensor

ATLAS: The XenoCal Solar sensor provides user-friendly, precise measurement and calibration exclusively for UV preconditioning of PV modules. It measures irradiance or radiant exposure. Values in two wavelength bands are displayed depending on the IEC standard selected from the menu. The sensor is capable of operating in harsh environments such as ambient temperatures up to 70 °C; it is watertight. Visit www.atlas-mts.com.

䡲 Coating Thickness Instruments FISCHER TECHNOLOGY: DEL-

than just grinding media

TASCOPE ® FMP30, ISOSCOPE ® FMP30 and DUALSCOPE® FMP40 coating thickness gauges feature more memory and extensive graphical and statistical evaluation capabilities. Available with an integrated Bluetooth interface, FMP Series handheld gauges have a large selection of interchangeable probes that have a wide measurement range. Visit www.fischer-technology.com.

nd ess a proc nalysis a cost ead gh b u o r s th aving ycling s t s co rec rs mina e s g illin ops wet m worksh and

e Pleas s at visit u oating C rican Ame o Sh w 36 6 no.: 1 Stand ril p 5A 13 -1

䡲 Surfactant

CHEMGUARD: S-764P is a VOC-free, short-chain, phosphateester-based product. The surface activity rivals competitive longer-chain perfluoro products now on the market, with no need to increase concentrations to obtain similar results. It is chloride free and available as an easy-to-use liquid. Applications include paint, adhesives, graphic arts, waxes and polishes, and metal plating. E-mail [email protected].

䡲 Spectrophotometer

X-RITE: VS450™ measures a wide range of wet and dry samples SIGMUND LINDNER GmbH Oberwarmensteinacher Str. 38 D-95485 Warmensteinach / Germany Phone (++49) 92 77 - 99 40 Fax (++49) 92 77 - 9 94 99 E-Mail: [email protected] www.sili.eu

Your innovative and reliable partner for 155 years

Visit ads.pcimag.com 70

䡲䡲䡲

068 Products.indd 70

without touching test surfaces. Features include: the ability to measure samples at a distance without contact, Line of Sight™ visibility to easily position the sample, Active Visual Targeting™ that projects a prominent illuminated target ring onto the sample, two aperture sizes of 6 mm and 12 mm, integrated gloss sensor for gloss measurements on wet and dry samples, improved measurement capabilities on two- and three-dimensional objects, and best-inclass color accuracy and repeatability. Visit www.xrite.com. 䡲

MARCH 2010 | W W W . P C I M A G . C O M

2/17/10 9:19:23 AM