Paint & Coating Industry November 2011

November 2011 VOLUME 27, NUMBER 11

INSIDE Smart Coating for Corrosion Protection

Paint

Coatings Industry

A New Era in Superwetters Nanotechnological Barbwire

Globally Serving Liquid and Powder Formulators and Manufacturers

Emerging Technologies

www.pcimag.com

Es

s ão g u ê ç Se r tu : tro Po43) n m D e a l e ágina c i (P e p

Cinilex Cin nillex x Yellow Yel ello lo ow SY1H SY S Y1H H (PY110) (PY11 PY11 PY 10))

Cinilex Cin inilex Yellow Yello ow SY2T SY2T SY 2T (PY110) (PY1 (P Y110 10))

Cinilex Cin inil inil ille ex DPP ex DPP PP Orange Orang ra n ra ng ge SJ1C SJ1C SJ 1C (PO73) (PO O7 73 3)

Cinilex Cin inil ilex e DPP ex DPP P Rubine Rub ubin i e SR6T SR S R6T 6T (PR264) (P PR R R26 264) 26 64) 4)

Cinilex Cinillex DPP DPP Red Red ed SR1C SR1C (PR254) SR (PR25 PR R2 25 54 4))

Cinilex Cinil ilex e DPP DPP P Rubine Ru ub bin i e SR5H SR R5H 5H (PR264) (PR PR26 26 264) 64))

Cinilex Ciin nil i ex Red Red SR4C SR4 R C (PR177) ( R177 (P 77 7)

Cinilex Cinilex x DPP DPP Red Red ed SR2P SR2P (PR254) (PR PR25 PR 2 4))

Cinilex Cin inil ilex ex Red Red e SR3C SR3C SR C (PR177) (PR17 177) 7)

Cinilex Cin inilex ilex x DPP DPP P Red Red ed ST ST S T (PR254) (PR R25 54))

www.cinic.com HEADQUARTERS

CINIC CHEMICALS(SHANGHAI) CO., LTD. 1730 Huilian Road, Qingpu Industrial Park Shanghai 201707, P.R. China Tel:+86 21 5240 0178 Fax:+86 21 5240 0136 E-mail: [email protected]

EUROPE

AMERICA

9, Croisee des Lys 68300 Saint-Louis, France Tel: +33(0)3 8989 4476 Fax:+33(0)3 8989 4493 E-mail: [email protected]

651 Holiday Drive, Foster Plaza 5, Suite 300 Pittsburgh, PA 15220, USA Tel:+1 412 928 3228 Fax:+1 412 202 0839 E-mail: [email protected]

CINIC CHEMICALS EUROPE Sarl

CINIC CHEMICALS AMERICA,LLC

CREATING TOMORROW’S SOLUTIONS

MAKE THE MOVE TO VINNAPAS ® EF8300 – THE NEW VAE BINDER FOR HIGH PERFORMANCE PAINTS

VINNAPAS® EF8300 is a new VAE copolymer dispersion that is produced without the use of APEO and ideal for flat to semi-gloss paints. This allows the formulation of paints with low VOC (< 5 g/l), very low residual VAM (< 200 ppm) and overall high performance, e.g. excellent scrub resistance, good block resistance as well as good wet adhesion and water resistance. Make the move to the technology of the future today. Visit us at www.wacker.com/interior-paints

Water-based microbial control from ISP Capture the Value of Aqueous Dispersions

The leader in microbial control additives and the first to commercialize water-based IPBC based biocides, ISP brings innovative, eco-friendly solutions to the world.

Cost control

World-class microbial control

Excellence in responsible care

Solvent-free, highly concentrated aqueous dispersions with reduced volume requirements

High performing, water-based dry film and in-can protection additives available in 20% to 40% concentrations

pH neutral, APE-surfactant free products for safer handling and better compatibility with today’s formulations

Find out what it means to capture the value of water-based microbial control. Visit ispcoatings.com/water

20

38

CONTENTS PAINT & COATINGS INDUSTRY, VOLUME 27, NUMBER 11

November 2011

FEATURES 20 Advances in the Chemistry of Melamine Acrylate Oligomers, 26 32 38 41 42 62 68 78

Bomar Specialties Integrated Tinting Systems for a Low-VOC Future, CPS Color Surfactant Evaluation in Preparing Acrylic Ultrafine Latexes, Cytec Industries Inc. Formulation Optimization Utilizing DOE Mixture Statistics, OMGroup Paint and Coatings Additives A New Way to Produce Antimicrobial Coatings, AM Coatings Innovation and Sustainability Highlighted at ABRAFATI 2011 A New Era in Superwetters for Waterborne and UV-Curable Coatings and Inks, Dow Corning Corp. A Multifunctional Coating for Autonomous Corrosion Control, NASA Innovation Drives Compact Paint Process for Waterborne Automotive OEM Coatings, PPG Industries

Seção Especial em Português 44 Ponto de Vista 46 Desempenho Superior de Películas Secas de Revestimentos por meio 50 56 60

do Controle da Liberação de IPBC, Ashland Specialty Ingredients Tecnologia de Poliuretanos Bicomponentes à Base de Água para Vernizes Automotivos Aplicações, Perstorp Novo aditivo umectante de substratos para Produtos adesivos à base de água com baixo teor de VOC, Troy Corporation Produtos

62

ONLINE FEATURES

w w w. pcimag.com Lubricious Medical Coatings Resist Particle Shedding During Use, Bayer MaterialScience LLC Custom Oven Solution Divides to Conquer Aerospace Manufacturer’s Increased Capacity Challenge, Carbolite Technical Breakthrough on Ceramic Coating, GMM Development Limited Green Manufacturing Practices in America Can Help Profits, Will Help Planet, Fabricators & Manufacturers Association Pigment Discovery Expanding Into New Colors – Including Orange, Oregon State University Peroxide-Resistant Coating for Cleanroom Renovation, European Industrial Paint Centre

DEPARTMENTS 6 8 12 14 18 86 88 90

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

ON THE COVER: Cover photo courtesy of www.photos.com.

BUSINESS TOOLS 82 Emerging Technologies 86 Supplier Showcases PCI - PAINT & COATINGS INDUSTRY (ISSN 0884-3848) is published 12 times annually, monthly, by BNP Media, 2401 W. Big Beaver Rd., Suite 700, Troy, MI 48084-3333. Telephone: (248) 362-3700, Fax: (248) 362-0317. No charge for subscriptions to qualified individuals. Annual rate for subscriptions to nonqualified individuals in the U.S.A.: $115.00 USD. Annual rate for subscriptions to nonqualified individuals in Canada: $149.00 USD (includes GST & postage); all other countries: $165.00 (int’l mail) payable in U.S. funds. Printed in the U.S.A. Copyright 2011, by BNP Media. All rights reserved. The contents of this publication may not be reproduced in whole or in part without the consent of the publisher. The publisher is not responsible for product claims and representations. Periodicals Postage Paid at Troy, MI and at additional mailing offices. POSTMASTER: Send address changes to: PCI - PAINT & COATINGS INDUSTRY, P.O. Box 2145, Skokie, IL 60076. Canada Post: Publications Mail Agreement #40612608. GST account: 131263923. Send returns (Canada) to Pitney Bowes, P.O. Box 25542, London, ON, N6C 6B2. Change of address: Send old address label along with new address to PCI - PAINT & COATINGS INDUSTRY, P.O. Box 2145, Skokie, IL 60076. For single copies or back issues: contact Ann Kalb at (248) 244-6499 or [email protected].

Audited by BPA Worldwide

Printed in the U.S.A.

V I EWPOINT

Brazil Set for Growth I recently had a very interesting telephone conversation with David P. Nick, President and CEO of DPNA International, Inc. In the course of talking about this month’s ABRAFATI event in Sao Paulo, Brazil, Dave educated me on the BRICS alliance. I often read about the fast-growing economies and coatings growth in Brazil, Russia, India, China and South Africa (the BRICS countries), but I did not realize that these countries have formed a trade alliance unlike anything else. BRICS is not a formal trading bloc, but rather a loose economic alliance not based on currency, politics or traditional trading guidelines. Each of these countries has something the others want. To name a few, Brazil has land, oil and agriculture products; Russia, oil and gas; China, an enormous work force and the need for oil and gas; India has extensive IT knowledge and resources; and South Africa has precious metals and diamonds, and is the gateway to Africa. Rather than establishing trade agreements based in dollars

Selecting the best Additives is Child’s Play Serving the Paint and Coatings Industry with innovative silicone additives for better flow, leveling, slip, mar resistance, and foam control. Innovative Silicones for your Technology

Manufacturer of organo modified & reactive silicones. SILTECH CORPORATION 225 Wicksteed Avenue, Toronto, Ontario, Canada, M4H 1G5 Tel: (416) 424-4567 Fax: (416) 424-3158 www.siltechcorp.com

Visit ads.pcimag.com 6



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

or euros, these countries have created barter agreements. For example, China might agree to build a highway system in South Africa, complete with funding, a labor force and equipment, in exchange for a multi-year contract to develop the country’s coal or metal resources. Such an alliance has the potential to make these countries’ continued growth something real and sustainable. It isn’t dependent on what happens in Europe or the United States. According to Nick, “BRICS represents a collective shift in economic power from the G-7 developed countries to the developing world, and many other countries are eager to join the club.” I look forward to reading more about BRICS and watching its development in the coming years. Despite a recent press release from ABRAFATI (Brazilian Coatings Manufacturers Association) that indicates that coatings growth in Brazil diminished this year compared to the 10% growth in 2010, the future looks bright. The overall growth of the coatings industry in Brazil this year should be 1.3% (due to the questionable international economic climate and a hesitation to remodel or build), reaching 1.377 billion liters, whereas a 4% expansion of sales is expected in 2012. In an effort to foster economic and social development, the Brazilian government has launched a housing program, Minha Casa Minha Vida 2, and has extended the IPI tax reduction. According to Dilson Ferreira, Executive President of ABRAFATI, “It is important to stress that, in addition to the great events that we will have until 2022 (including the 2014 FIFA World Cup and the 2016 Summer Olympics), which will ensure a sustainable growth, the structural reasons that stimulate sales will still be present for many years to come. Among these factors, the most noteworthy are investments in housing and infrastructure, the amplification of segments related to oil exploration and distribution, the strengthening of the internal market and the growth of the middle class.” In an effort to reach this growing market and the attendees at the upcoming ABRAFATI event, PCI introduces our first Portuguese supplement in this issue, which will be distributed at the show. We hope our Portuguese readers will find this information helpful and informative, and that we will be able to provide further supplements like this in the future.

By Kristin Johansson, Editor | PCI

Markets:

Architectural Coatings

Industrial Coatings

Container Automotive

Civil Aerospace Engineering

Coatings Technologies:

SolventBorne Coatings

WaterBorne Coatings

Powder Coatings

Surface/Substrate:

Wood

Brick

Concrete

Marine & Maintenance

UV Coatings

Metal

Stucco

High Solids Coatings

Vinyl

Plastic

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

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

The Glocal® Chemical Distributor.

I NDUSTRY NEWS

Research Firm Predicts Market for Green Chemistry to Reach $98.5 Billion BOULDER, CO – According to a new report from Pike Research, the market for green chemistry represents an opportunity that will grow from $2.8 billion in 2011 to $98.5 billion by 2020. “Green chemistry markets are currently nascent, with many technologies still at laboratory or pilot scale,” said Pike Research President Clint Wheelock. “And many production-scale green chemical plants are not expected to be running at capacity for several more years. However, most green chemical companies are targeting large, existing chemical markets, so adoption of these products is limited less by market development issues than by the ability to feed

extant markets at required levels of cost and performance.” Pike Research forecasts that green alternatives in the polymer sector will

School of Polymers Honors Industry Leader HATTIESBURG, MS – The University of Southern Mississippi School of Polymers and High Performance Materials, Hattiesburg, MS, honored and memorialized the late Sidney Lauren, a leader in the coatings industry, on September 23 with the dedication of the Sidney Lauren Memorial Learning Center. The center is made possible by a donation from the Coatings Industry Education Foundation (CIEF). The CIEF has been a generous contributor of scholarships to polymer science students for more than a quarter of a century, including many who graduated from Southern Miss. The event included an opening ceremony, a brief history of the long-standing relationship between the CIEF and Southern Miss, an overview of Sidney Lauren’s life and work by the Lauren children, presentation of the donation, acknowledgement of individual CIEF Sidney Lauren Memorial Scholarship recipients, a demonstration of the new Sidney Lauren Online Learning Center, and an announcement of the first annual “Sidney Lauren Memorial Lecture” to be held at the Annual Waterborne Symposium in February 2012.

Use of Gold in Inks and Pastes on the Rise GLEN ALLEN, VA – Industry analyst firm NanoMarkets has released a new report, Printed Gold: Gold Inks and Pastes Market, 2011. The report examines the market for gold inks and pastes in the electronics and solar industries. It discusses both the gold pastes used in traditional applications, such as wire bonding and brazing, and a new breed of ink-based gold nanoparticles. These next-generation inks are expected to find uses in MEMS, data storage and computer memory, “green” electronics, photovoltaics (PV), and sensors. NanoMarkets estimates that the total volume of gold consumed by gold inks and pastes for electronics and PV applications will reach 13.7 metric tons by 2016. Although the gold pastes market is mature, NanoMarkets sees an opportunity for nanopastes, which would serve traditional thick-film markets but could provide significantly lower processing 8



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

represent the highest penetration level (5.7 percent) within the total chemical market, as it is somewhat more developed than the other key sectors. The special, fine and commodity chemical sectors are more nascent and will enjoy somewhat lower penetration rates during the forecast period. The three major themes driving the green chemistry movement forward are: waste minimization in the chemical production process, replacement of existing products with less-toxic alternatives and a shift to renewable (non-petroleum) feedstocks. For additional information about the report, Green Chemistry, visit, www.pikeresearch.com.

costs. According to the report, the main new business opportunities will come mainly from novel applications using nano-inks. One of these opportunities may come from printing a thin layer of gold nanoparticles on optical disks, such as CDs and DVDs, which could greatly increase the amount of information being stored. Gold nanorods, in particular, have been noted as a material that can help provide new technology strategies for optical information storage. A printed layer of gold nanoparticles may also help to boost the efficiency of solar panels. In this context, NanoMarkets notes, printing has taken on a growing role in PV in recent years. The report also notes that the market for gold inks and pastes will be driven not just by the rise of alternative energy sources but also by environmental regulation. For more information about this report, visit www.nanomarkets.net.

ASTM Releases New Standards W. CONSHOHOCKEN, PA – A new ASTM guide standardizes a useful, fast and easy technique for collecting infrared spectra of nonaqueous liquid paints right out of the can. The new standard, ASTM D 7588, Guide for FT-IR Fingerprinting of a Non-Aqueous Liquid Paint as Supplied in the Manufacturer’s Container, is under the jurisdiction of Subcommittee D01.21 on Chemical Analysis of Paints and Paint Materials, which is part of ASTM International Committee D01 on Paint and Related Coatings, Materials and Applications. The new guide will be useful for quality, formula and process control, failure analysis, chemical identification, and compositional and raw material comparisons. A new standard, ASTM G 207, Test Method for Indoor Transfer of Calibration from Reference to Field Pyranometers, was developed by Subcommittee G03.09 on Radiometry, part of ASTM International Committee G03 on Weathering and Durability. ASTM G 207 facilitates calibration of solar sensors used in accelerated testing under simulated sunlight and outdoor weathering

AEROSOL® Surfactant – APE Free Sulfosuccinate Technologies and Customized Low VOC Wetting Agents Cytec offers a range of APE free sulfosuccinate surfactants for use in emulsion polymerisation. For acrylic, vinyl acrylic and styrene acrylic latex systems these water soluble highly effective surfactants offer: s0RIMARYORSOLEEMULSIlCATION s%XCELLENTPRE EMULSIONSTABILITY s#LEANROBUSTREACTIONKINETICSWITHHIGHCONVERSION s%XCELLENTMECHANICALSTABILITY s-INIMALGRITANDCOAGULUMINTHElNALLATEXnIMPROVING OPERATIONALEFlCIENCIES s4HEABILITYTOOPTIMIZELATEXFORMULATIONSFORDESIREDSOLIDS PARTICLESIZEANDVISCOSITY These latexes can subsequently be formulated into architectural coatings imparting: s%NHANCEDGLOSS s%XCELLENTHIDINGPOWER s'OODBLOCKRESISTANCE s'OODSCRUBRESISTANCE s2EQUIREDRHEOLOGY In addition Cytec offers a range of wetting agents for the formulation chemist offering: s&AST DYNAMIC DEEPWETTING s,OWFOAMINGVERSIONS s,OW6/#VERSIONS s#USTOMIZEDPRODUCTS 0LEASECONTACT#YTECFORTECHNICALSERVICEADVICEIFYOUHAVEANY unsolved issues with architectural coatings.

Email: [email protected] I Worldwide Contact Info: www.cytec.com ©2010 Cytec Industries Inc. All rights Reserved .

I NDUSTRY NEWS tests as well as performance monitoring of solar energy conversion systems.

AAMA Releases New Standard SCHAUMBURG, IL – The American Architectural Manufacturers Association (AAMA) has published a new standard,

AAMA 633-11, Voluntary Specification, Performance Requirements and Test Procedures for Exterior Stain Finishes on Wood, Cellulosic Composites and Fiber-Reinforced Thermoset Window and Door Components. The standard covers factory-applied coatings intended for service in exterior environ-

T

®

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

ments, and describes test procedures and performance requirements for exterior stain finishes for windows, doors and similar building products. For additional information, visit www.aamanet.org.

Hydraulic Institute Releases New Test Standard PARSIPPANY, NJ – The Hydraulic Institute (HI) announced that both the Centrifugal Pump Test Standard (ANSI/HI 1.6 − 2000) and the Vertical Pump Test Standard (ANSI/HI 2.6 − 2000) have been superseded by the newly released Standard for Rotodynamic Pumps for Hydraulic Performance Acceptance Tests, (ANSI/HI 14.6 − 2011). The new test standard contains significant updates and is considered the new global reference for testing centrifugal and vertical pumps.

Directory of Paint Manufacturers in Central and Eastern Europe Now Available

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.

*

Call for Papers Issued for SSCT Annual Meeting

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. 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

Visit ads.pcimag.com 10



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

WIENER NEUDORF, Austria – The Directory of Paint Manufacturers Central and Eastern Europe (CEE) 2011 has been released and is now available for purchase. The report, authored by Dr. Josef H. Jilek, contains country information, paint and coatings statistics, production capacity, export and import data, production ranges, and major coatings producers. Visit www.chem4cee.com/index. php?publications for more information.

r

TM

ST. AUGUSTINE, FL – The 2012 SSCT Annual Meeting will take place March 11-14, 2012, at the Renaissance Resort at World Golf Village, St. Augustine, FL. The theme of the meeting is “Blast Off Into the Ever-Evolving, Ever-Challenging World of Coatings.” The Southern Society for Coatings Technology is currently seeking technical speakers for this event. Any interested parties should e-mail Ursula Thomas at [email protected].

ECOAT 2012 to Take Place in Orlando ORLANDO, FL – ELECTROCOAT 2012 will take place April 11-12, 2012, at the Rosen Centre Hotel in Orlando, FL. The event is an educational conference for everyone involved in the electrocoat business and for people interested in learning about electrocoating. Visit www.electrocoat.org/conference for additional information. 

We are thinking about the same thing you are… How to make your products greener and their performance pure gold. Our customers come to us to help them stay ahead of competitive pressures by helping to re-formulate existing products and innovate new ones – meeting “green” goals while preserving and even enhancing performance. We call it Greenability. You’ll call it genius.  Another fine result of the Innovation Principle – . Let us help you work through the formula for Greenability.

L

www.byk.com

C ALENDAR Meetings, Shows and Educational Programs NOV. 21-23 ABRAFATI São Paulo, Brazil www.abrafati2011.com.br

DEC. 7 3rd Vietnam International Coatings Exhibition Ho Chi Minh City, Vietnam

13-17 Waterborne Symposium New Orleans www.psrc.usm.edu/waterborne

22 Paint & Coatings Basics Hampton, UK www.pra-world.com

7-8 ASTM International Committee G02 on Wear and Erosion New Orleans www.astm.org

22-24 Smart Coatings Orlando, FL www.smartcoatings.org

22-23 Adhesives for Wind and Solar Technology Berlin www.european-coatings.com 23-25 ChinaCoat 2011 Shanghai www.chinacoat.net 24-25 Automotive Coatings Berlin www.european-coatings.com 29-DEC. 1 Radiation Curing Technology Hampton, UK www.pra-world.com

28-31 11th International Paint, Resin, Coatings & Composites Fair Tehran, Iran www.ipcc.ir/

MARCH 11-14 SSCT 2012 Annual Technical Meeting St. Augustine, FL www.ssct.org 11-15 Pittcon 2012 Orlando, FL www.pittcon.org

2012 JAN. 30-FEB. 2 SSPC 2012 Tampa, FL www.sspc.org

FEB. 6-10 Polymers and Coatings Introductory Short Course San Luis Obispo, CA www.polymerscoatings.calpoly. edu

13-14 Professional Paint Formulation Hampton, UK www.pra-world.com 27-29 WESTEC 2012 Los Angeles www.westeconline.com

APRIL 3 PSCT Technical Symposium Horsham, PA www.psct.org 11-12 ELECTROCOAT 2012 Orlando, FL www.electrocoat.org 15-17 ASC Spring Convention Denver, CO www.ascouncil.org 17-20 PaintExpo Karlsruhe, Germany www.paintexpo.com 18-20 The Chemistry, Physics & Mechanics of Adhesion Science Stewart-Newburgh, NY www.mstconf.com

K?Xl^\]\Xkli\jXe\nZfcfiC:;gXe\ck_Xk_\cgj Gfn[\i>Xl^\]\Xk dXb\ d\Xjli\d\ dXb\d\Xjli\d\ekj\Xj`\iXe[dfi\XZZliXk\% K_\E\n>Xl^\1 z Gi\[`ZkjZli\ Gi\[`ZkjZli\[k_`Zbe\jjf]ZfXk`e^Y\]fi\`kZli\j% z

D\Xjli\j]c D\Xjli\j]cXkXe[Zlim\[jlYjkiXk\j`eZcl[`e^ jk\\c#Xcld` jk\\c#Xcld`eld#gcXjk`Z#nff[#Xe[D;=% z

8ccfnjd 8ccfnjd\Xjli\d\ekj`ed\ki`ZXe[LJ:J n`k_Xi\ n`k_Xi\jfclk`fef](d`Zife% z Jkfi\j Jkfi\j)''d\Xjli\d\ekj`ed\dfip% z

COLOR LCD PANEL

=\Xkl =\Xkli\j\e_XeZ\[\c\Zkife`Zjk_Xkjg\\[ZXcZlcXk`fej Xe[ Xe[`dgifm\XZZliXZp%

US and Canada 800.521.0635 | www.elcometer.com England +44 (0) 161 371 6000 | France +33 (0)2 38 86 33 44 Asia +65 6462 6 2822 | Germany +49 (0) 7366 91 92 83 | Belgium +32 (0)4 379 96 10

Visit ads.pcimag.com 12



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

t abou ree, s u k F As hyde ow e d l a L Form Free and s C ide VO Bioc C O V

REICHL UND PARTNER

WELL

PROTECTED

Water is synonymous with well-being, but it also promotes the growth of bacteria, fungi and algae. Protecting aqueous formulations such as paints, coatings, adhesives and sealants from microorganisms requires customized solutions. Our experts choose from a wide range of biocides and preservatives to develop the best protection system to meet your special needs. Our PREVENTOL® products provide in-can preservation, dry-film mold protection, and surface protection. LANXESS Material Protection — Industrial preservatives and antimicrobials you can always trust

LANXESS Corporation • Material Protection Products • 111 RIDC Park West Drive, Pittsburgh PA 15275, USA Phone: 1-800-LANXESS or 412-809-1000 • Fax: 412-809-1068 • Email: [email protected] www.mpp.us.lanxess.com

C O M PA N Y NEWS

Arkema Coating Resins Introduces New Trademark CARY, NC – Arkema Coating Resins has announced a new trademark that will be applied to the company’s waterborne emulsion polymer products sold worldwide. The new name, ENCOR™ Polymers, will be used for both current and new products sold for use in architectural and industrial coatings, traffic paints, specialty coatings, pressure-sensitive adhesives, sealants, construction products, graphics arts, and floor maintenance products.

JNS Smithchem to Represent German Companies PATERSON, NJ – JNS Smithchem LLC has been appointed the sales representative covering northern New Jersey, New York and the New England states for Keim Additec Surface GmbH and Silcona GmbH. Keim Additec Surface GmbH, Kirchberg, Germany, is a manufacturer of specialty wax additives and surface conditioners featuring zero-VOC and APEO-free products. Its sister company, Silcona GmbH, is a supplier of high-performance additives for

ENCOR Polymers will principally replace the UCAR trademark now applied to many of the company’s waterborne emulsion products, as well as the Craymul® and Esi-Cryl® trademarks acquired with the purchase of the coating resins businesses of Cook Composites and Polymers and Cray Valley. Other Arkema Coating Resins trademarks, including SNAP™ Structured Nano-Acrylic Polymers and EnVia™, will continue to be used in all geographies. wetting and surface modifications in environmentally friendly coating systems. The U.S. subsidiary company, KEIM-ADDITEC Surface USA LLC, has offices in Wilmette, IL.

Evonik Lays Foundation for Two Innovation Centers ESSEN, Germany – Klaus Engel, Chairman of the Executive Board of Evonik Industries, has laid the foundation stones for two research and development centers at the company’s Essen, Germany, site.

C O M PA N Y N E W S

One center is for new, environmentally friendly additives and special binders for the coatings industry. The other center is for products for the cosmetics industry. In total, the group is set to invest some €31 million in the two building complexes. The innovation center for the coatings industry is to be completed at the end of 2012.

Archway Sales to Distribute for AkzoNobel ST. LOUIS, MO – AkzoNobel Performance Additives has appointed Archway Sales Inc., St. Louis, MO, as its distributor for the Louisiana, Texas, Oklahoma and New Mexico markets.

Color-Logic Appoints Upper Midwest Representative PPG to Supply Coatings Used in New Caterpillar Plant PITTSBURGH – Caterpillar Inc. has selected PPG Industries’ industrial coatings business as the sole heavy-duty equipment coatings supplier for a new motor grader assembly plant in North Little Rock, AK. In addition to serving as a single-source coatings supplier, PPG is providing on-site technical and product approval support, and in-plant training of paint-line operators through its Knowledge College service in coating application technologies.

Perstorp Doubles Caprolactone Capacity PERSTORP, Sweden – Perstorp has doubled production capacity of its Capa™ caprolactone plant in Warrington, England. The company’s second Capa stream is based on the same proprietary technology as its first stream.

WEST CHESTER, OH – Color-Logic has named MSM Color as its manufacturers’ representative for Minnesota, western Wisconsin, Iowa, North Dakota, South Dakota, Nebraska, Kansas and the Kansas City, MO, area.

AP Plastics to Distribute for Sulzer Mixpac USA PEABODY, MA – AP Plastics LLC, now an affiliate of Adhesives Packaging Specialties, is a recognized distributor for Sulzer of Salem, NH. Under this agreement, AP Plastics will develop and promote the sale of Sulzer’s product line throughout North America for its static mixers, cartridges, dispensing guns, dual syringes and accessories.

Croda Expands Esters Plant in North America EDISON, NJ – Croda Inc. announced the official opening of its new facility for the production of lubricant esters at its Atlas Point manufacturing site in New Castle, DE. The Atlas Point manufacturing site will now be able to manufacture lubricantquality esters, targeting growth in high-end lubricant applications. Food-grade esters for lubricant base fluids and additives

Arkema Coating Resins delivers innovative products and targeted support that allow you to capitalize on amazing new opportunities. For example, our SNAP™ 720 Structured Nano-Acrylic Polymer uses advanced particle morphology design to offer formulators excellent gloss and adhesion plus outstanding block resistance and film hardness in a no or low VOC architectural coating. If you haven’t already tried this 100% acrylic binder, it’s definitely worth looking into.

technology that’s really deep.

Visit www.arkemacoatingresins.com/SNAP for more information about SNAP™ Structured Nano-Acrylic Polymers. At Arkema Coating Resins, we’re focused on your future.

SNAP™ is a trademark of Arkema Inc. ©2011 Arkema Inc.

arkemacoatingresins.com

Milling

C O M PA N Y NEWS

Grinding Dispersing

will be supplied in addition to water-soluble lubricity additives for stamping and drawing lubricants.

Dow Announces Capacity Expansions MIDLAND, MI – The Performance Monomers business of The Dow Chemical Co. (Dow) announced a 15-percent increase in capacity for the production of 2-ethylhexyl acrylate at its Hahnville, LA, facility. Dow has increased its propylene glycol capacity by an additional 10 kilotons per annum (KTA) at its Stade, Germany, plant. Dow’s Performance Monomers business announced that capacity for the production of crude acrylic acid (CAA) at its Böhlen, Germany, facility has expanded by 25 percent. The additional CAA at Böhlen will be used to increase butyl acrylate and glacial acrylic acid production at the site. The Performance Monomers business also announced a 10-percent increase in capacity for the production of glycidyl methacrylate at its Freeport, TX, facility.

Alkyd Emulsion Receives Innovation Prize

y t i l a u q 4 o t i r 85 spi since 1

rman e G e h T f

®

SiLibeads

... better grinding

Beads were not our invention, but we make them to perfection.

COLOMBES, France – Cray Valley Resins, a business that is now part of Arkema Coating Resins, was awarded the Ringier Technology Innovation prize for its Synaqua® 4804 alkyd emulsion. This waterborne paint binder is an innovative alkyd emulsion that helps produce top-quality gloss paint with application characteristics very close to those of solvent paint.

Clariant Receives Paint & Pintura Awards SÃO PAULO, Brazil – Technology innovation, differentiated services and strong customer relationships have secured Clariant a hat trick of awards in the Brazilian paint and varnish industry’s Paint & Pintura awards for 2011. In addition to achieving Best Supplier in the categories Emulsions, Pigment Dispersions and Organic Pigments, Clariant was also elected the Master Top 10 Company for the third year in a row.

Ecology Coatings Nominated for U.S. Green Chemistry Challenge WARREN, MI – Ecology Coatings Inc. has been nominated for the U.S. Green Chemistry Challenge 2012. This program recognizes chemical technologies that incorporate the principles of green chemistry into their design, manufacture and use. Ecology Coatings was nominated based on its GRAS (generally regarded as safe) coatings, which reduce toxic chemicals contained in food packaging products.

BASF Receives Design Award for Automotive Color Innovation

More than 155 years: SIGMUND LINDNER GmbH Oberwarmensteinacher Str. 38 · 95485 Warmensteinach / Germany Phone (+49) 92 77 - 99 40 · Fax (+49) 92 77 - 9 94 99 E-Mail: [email protected]

www.sili.eu Visit ads.pcimag.com 16



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

SOUTHFIELD, MI – BASF Coatings has been honored with a design award for XFine®, its unique automotive color innovation. The German Design Council selected the paint manufacturer as a winner of the 2011 Automotive Brand Contest, the first international brand and design competition for the automotive industry. XFine has also been nominated for the 2012 German Design Award.

Univar Acquires Brazilian Distributor REDMOND, WA/SÃO PAULO, Brazil – Chemical distributor Univar Inc. has acquired Arinos Química Ltda. (Arinos). Arinos is a leading chemical distributor in Brazil, providing both specialty and commodity chemicals as well as highvalue services. 

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

oth r bo at u o t Visi treet A 11 n o S FATI 20 A ABR

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

N AMES IN THE NEWS  Watson Standard

 BYK-Gardner has named Rae Roby Regional

has appointed Cynthia Blomquist EH&S Manager. Wesley E. Horton was appointed Assistant Director of Manufacturing, and Richard Newman was appointed Process & Maintenance Engineer.

 Nubiola has hired Jeff Cayce as Technical Sales Manager, Coatings.  Dow Coating Materials has appointed Michael

Cauchi

Lewis West Coast Sales Manager.

 Plasticolors Inc. has appointed Andrew Locy Chemist within the Coatings Technical Group. Margaret Dvorak has been appointed Product Development Specialist.

 BASF Automotive Refinish has named Vitor

Roby

Margaronis Marketing Director for BASF Coatings, North America.

 Tim Miller has been appointed President of Flame Control Coatings. Ryan Najmulski was hired as the new Marketing Manager.

 Bruce Rose has been appointed Product Manager for UCT’s silanes, silicones and platinum catalysts.

Sales Manager for the Michigan and Northern Ohio Region. Sam Cauchi, Sales Manager for Canada, is now responsible for covering all of Canada. Sheila White has been named the company’s new Customer Care Center Manager for North America. Mary Llewellyn, of the company’s Customer Care Center, will be Margaronis responsible for all of Canada and will be working with Cauchi. Scott Richeson, also a team member in the Customer Care Center, will work with Andy Stummer covering the Mid-Atlantic USA territory. Sandrine Letendre, one of the newest members of the Customer Care Center, will handle the West Coast USA area and work with Ed Smyth. Patrick Weaver, another new member of the Customer Care Center, will handle the White Southwest USA area and work with Joe Daniels. Corey Cohen joins BYK-Gardner USA as Applications Specialist to the company’s applications staff, and Josh Egbert joins BYK-Gardner USA as the Service Administrator.

 JNS Smithchem LLC has appointed John P. Sari Regional Sales Manager. Sari will be responsible for growing the company’s customer and supplier base in southern New Jersey, Pennsylvania, Delaware, Maryland and Virginia. 

ew N

COATING THICKNESS GAGES

Now smarter, faster and more powerful than ever before and stilll... ■

Rugged, weatherproof, ergonomic design

■

All models include memory, statistics, HiLo alarm and a USB port

■

Simplified paperless QA – no software required

Simple. Durable. Accurate. For a demo visit

www.PosiTector.net A f re e w e b - b a s e d a p p l i c a t i o n o f f e r i n g s e c u re c e n t ra l i z e d ur gage m a n a g e m e n t o f t h i ck n e s s re a d i n g s where yothe cloud meets

TM

1-800-448-3835 www.defelsko.com ko . c o m 45 Years of Quality

18



Advanced model

Made in U.S.A.

+ 1 ( 31 DeFelsko Corporation • Ogdensburg, New w YYork o r k • +1 3315 15 ) 3393-4450 9 3 - 4 4 5 0 • [email protected] [email protected] Visit ads.pcimag.com

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

4KIOGPV(KURGTUKQPU

=QW T' Q NQT7G N G EVK Q P

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¸X *5& 2JYMTITW&QP^Q5MJSTQ*YMT]^QFYJX

-JZHTYJHM1YI 5MTSJ-*:'&(+F] *2FNQXFQJX%MJZGFHMHTQTWHTR .SYJWSJY\\\MJZGFHMHTQTWHTR

Advances in the Chemistry of

Melamine Acrylate Oligomers

M

elamine formaldehyde (MF) resins are widely used in industry. They belong to a class of amino resins that are used as crosslinkers for thermoset coatings. MF resins co-react with polyester, alkyd, epoxy, polyurethane and acrylic resins to impart hardness, durability, chemical resistance and heat resistance to many industrial coatings.1,2 Such mixtures of resins are cured at high temperatures. MF resins are prepared by the reaction of melamine and formaldehyde under basic conditions, followed by acidic etherification with an alcohol. The triazine ring has six

reactive groups that can be used to prepare oligomers with unsaturated reactive groups. Melamine acrylates (MAs) have both acrylic and either hydroxyl or alkoxy groups. These acrylates undergo photopolymerization (UV cure) by a free radical mechanism due to the presence of the acrylate group. The hydroxyl or alkoxy groups can be cured by condensation. In this article, we report on new UV-curable MA oligomers, present their properties as viscous liquids and their outstanding properties as cured MAs (thin films). The melamine acrylates are designated as BMA or XMA.

Structures of the Prepared MAs FIGURE 1 | Generic structures of prepared O

MAs.4

O N

O N

N

N

O

N

O

N O

O

O

O

O

N O

XMA-220

BMA-222

O

O

N

O

N O

O N O O

O

O

N O

O

O

XMA-224 S

O

N

O

O

O N

O

O

N

OH

O

N O

O

O

O

O S

O

O

S

XMS-224

LS XMA-222

TABLE 1 | Residual formaldehyde in BMA-2223 after acid neutralization and prepared with a standard and a proprietary catalyst.

Free formaldehyde, wt.%a a

Standard Catalyst

Proprietary Catalyst

1.0 %

0.025%

Determination error is 15%

The generic structures of monoacrylate XMA-220, triacrylate BMA-222,3 pentaacrylate XMA-224, MA with a grafted photoinitiator (PI) LS® XMA-222, and a sulfide group containing XMS-224 are presented in Figure 1. Unfortunately, almost all melamine resins have the unpleasant odor of formaldehyde.2 Much effort is devoted to reducing the formaldehyde content in MF resins.2 Mineral or organic acid is used in a standard dark cure (condensation) of MF resins, which is accompanied by demethylolation and by an additional release of formaldehyde. An acid-catalyzed reaction of MF resins with the formation of MA also leads to the evolution of formaldehyde. The addition of a proprietary base terminates equilibrium reactions in acidic solutions containing melamine and, therefore, brings to a halt any further evolution of formaldehyde. The remaining free formaldehyde is stripped. Moreover, we selected a catalytic system that results in a clear (not a turbid) resin. For this discussion, BMA-222 (Figure 1) is selected as an example. One can see a dramatic difference in the level of formaldehyde before and after neutralization (Table 1). According to many users, BMA-222 does not have a formaldehyde odor. In addition to reducing free formaldehyde in the final liquid resin, the neutralizing agent leads to an increase in the shelf stability of BMA. It is known that acid induces further condensation of MF resins, which leads to an increase in viscosity (d) and eventually

By Ahmet Nebioglu, Ph.D., Director of Applied Technology | Bomar Specialties, Torrington, CT; and Igor V. Khudyakov, Ph.D., D.Sc. IVK contributed to this paper prior to joining Solutia Inc., Fieldale, VA, as a Senior Chemist. 20



NOV EMBER 2011 | W W W . P C I M A G . C O M

MA oligomers can be used as additives to strengthen films of urethane acrylates. We prepared a number of formulations in order to observe the effect of MA addition on the mechanical properties of a flexible (“soft”) cured oligomer BR-304.3 These formulations are listed in Table 4. Formulations MA0, B10, B20, X10 and X20 contain 30 wt.% of IBOA and 2.0% of Irgacure 184. L0 and L10 were prepared to estimate the effect of LS XMA-222 addition on the UV cure of urethane acrylate.

to gelation. This condensation is prohibited in BMA/ XMA due to lack of free acid. LS XMA-222 (Figure 1) utilizes grafted PI LS oligomers, and formulations with them do not require an addition of PI, as they are self-initiated.5,6

Physical Properties of the Liquid and Cured MAs

7000 6000 5000 4000 3000 2000 1000 0

4

XMA-220 BMA-222 XMA-224

Elongation-at-Break (%)

FIGURE 2 | Tensile strength and elongation-at-break of MA formulations. All individual MAs were diluted with 50 wt.% of a common diluent, isobornyl acrylate IBOA. Irgacure 184 (2.0%) was added to the formulations. Determination error of the values can be seen in the figure. Tensile Strength (psi)

Synthesized BMA/XMA oligomers have relatively low Mw (< 2,000 g/mol) and a relatively low d. We observed that BMA cures faster than urethane acrylates of the same functionality under similar conditions, and BMA requires a much lower amount of PI for it to cure. In particular, we cured trifunctional urethane acrylate BR-1443 and trifunctional BMA with PI Irgacure 184. The oligomers were of comparable Mw, and each oligomer was diluted twice with a common diluent tripropyleneglycol diacrylate TRPGDA (Table 2). The striking difference between BMA-222 and BR-144 in this example is the concentration of PI: BMA222 can be cured with an extremely low concentration of a common PI (Irgacure 184). It is an order of magnitude lower than the concentration of PI required for the urethane acrylate cured under our experimental conditions (Table 2). The mechanical properties of the MA oligomeric films are presented in Figure 2. Pentaacrylate XMA-224 (Figures 1 and 2) has the highest tensile strength, probably due to a high crosslink density expected for the cured multifunctional monomers/oligomers. Also, as expected, monoacrylate XMA-220 (Figure 1) has the lowest tensile strength and the largest elongation-at-break among the studied XMA/ BMA (Figure 2). MA oligomers are widely used in UV-curable wood coatings. Emission of volatile and extractable byproducts during UV curing is a problem for furniture, ink and food applications. Much effort is devoted by both academia and industry to develop non-migrating PIs.5,8,9 MAs can be a good choice to get films with low extractables due to their efficient cure response at low PI concentrations. It was mentioned previously that BMA-222 can be cured into tack-free films with even 0.1% of PI, and Irgacure 2959 in particular. The latter PI is approved by the Food and Drug Administration. MA with a grafted Irgacure 2959 (LS XMA-222, Figure 1) demonstrates negligible leaching of the PI. We prepared two formulations with the goal of comparing PI extractability: one with LS XMA-222 (named F1) and the other with a dissolved Irgacure 2959, named F2 (Table 3). F1 and F2 have approximately the same concentration of free/grafted PI, namely 2%. Cured pieces of films F1 and F2 of the same shape and mass were each kept in the same volume of THF for 72 h. We measured only the leached PI and byproducts of PI photolysis by GC-MS analysis of the two supernatants. It follows from the data in Table 3 that the extractable concentration from the F1 film is essentially lower than that from the F2 film. There are reasons to expect much lower extractable concentrations considering that MA oligomers can be cured with a very low concentration of PI, namely [PI] 300 ºC). To the best of our knowledge, the highest reported refractive index organic polymer is n D20 =1.757.12 The polymer was not UV cured but was cast from a solvent, which is accompanied by VOCs. There is commercial interest in coatings with high n D20, which can be obtained at mild conditions at ambient temperatures and with low or zero VOCs. Therefore, UV-cured, high-n D20 coatings attract much attention of researchers.13 Besides all the known advantages of UVcurable formulations, UV cure leads to increased n D20 due to an increase in molecular polarizability through molecular orientation and volume shrinkage. Polymers containing aromatic groups and highly polarizable atoms such as nitrogen, sulfur, phosphorus, bromine and iodine show relatively high nD20.14,15 Among these heavy atoms, sulfur-containing polymers are of particular interest due to their low color, raw material availability and variety of mechanical properties of the formed films. MA oligomers have relatively high nD20 of 1.5 by themselves due to a high concentration of (hetero)aromatic groups and nitrogen atoms (Table 5). The Michael addition reaction of thiols, RS-H to electron-deficient vinyl groups in maleimides16 and acrylates,17 is well documented. The nucleophilic character of thiols, RS-H, allows the synthesis of C-S bond-containing products with a high yield. In order to increase nD20 of MA oligomers, we synthesized the thiol adducts of XMA-224 (Figure 1) by a reaction of aromatic thiols with acrylate groups. As expected, the new thiolmodified MAs have higher nD20 (Table 5). We also prepared a number of adducts of XMA-224, gradually increasing initial relative concentration of thiophenol. As anticipated, an increase in thiol concentration led to an increased nD20 of the adduct. However, a thiol addition to acrylates consumes the acrylate groups available for UV cure, and hence decreases the tensile strength and toughness of the cured coatings. Therefore, there is a tradeoff between the strength/toughness of the films and nD20. All of the thiol-modified MAs (Table 5) yield transparent, colorless films after UV cure. The cure of oligomers leads to a 1-5% increase of nD20 (Table 5). Thiol structure essentially affects nD20 of the adducts (Table 5). We were able to get the n D20 of modified melamine acrylate oligo-

Fan-tastic! COLORTREND® 808 No-VOC High Performance Colorants Introducing COLORTREND® 808HP No-VOC colorants and Vivid Expressions™, the newest color collection offering 480 of the brightest, cleanest colors in the coatings industry. Vivid Expressions™ provides the flexibility to expand an existing COLORTREND® system or be used as a stand alone point-of-sale color system. Now you will experience broader color space for brighter colors, plus high performance solutions for better durability, superior fade resistance and improved opacity. By utilizing this latest No-VOC colorant technology you will also meet growing market demands and exceed environmental regulations. As the largest independent colorant manufacturer and a global leader in specialty chemicals, Evonik continues to deliver eco-friendly, innovative, color system solutions. Just one more step to making our world safer, brighter, better – inside and out! colored by colortrend™

s Contact u E for a FRE fandeck

For more information, please contact your local Account Manager. Colortrend USA LLC 2 Turner Place P. O. Box 677 Piscataway, NJ 08854 USA phone +1 732 981 5347 www.evonik.com/colortrend

Advances in the Chemistry of Melamine Acrylate Oligomers

mers up to 1.62 (X-4 in Table 5). As projected, n D20 of the oligomer and of the cured film increases as the number of aromatic groups in the thiol increases (X-2 vs. X-5 in Table 5). Furthermore, alkyl groups usually lead to lower n D20 of polymers due to a decrease in polarizability.13,14 In fact, X-5, which has a similar structure to X-1 except for the presence of the methyl substituent in thiol, has a lower n D20 (Table 5). X-1 oligomer is particularly interesting for industrial application due to its relatively low cost of raw materials, low color and low (for oligomers) viscosity of ~5,000 cP at room temperature. Table 6 presents compositions of four UV-curable formulations denoted as F1 – F4. Fi are based on X-1. Mechanical properties of the cured films Fi are also presented in Table 6. MAs with high n D20 can be used in protective coatings for plastics and in antireflective coatings for a wide variety of substrates.

Thermostability of MAs Resistance to high temperatures is a valuable property of protective coatings in a number of applications. We ran TGA experiments on two MA oligomers and on one urethane acrylate BR-344. Table 7 presents the results. It follows from the data in Table 7 that the studied MA oligomers are rather resistant toward high temperatures and obviously are more resistant than urethane acrylates. (The carbamate fragment is the known weakest link in all of the polyurethanes.) It is not surprising that MAs are used as additives to impart high temperature resistance to many industrial coatings.

TABLE 6 | Formulations Fi containing XMS-224 and mechanical properties of the corresponding films at 25 º C. F1

F2

F3

99

69

49

-

-

-

-

49

IBOA,wt.%

-

30

-

-

TRPGDA, wt.%

-

-

50

50

X-1, wt.% XMA-224, wt.%

Darocur 1173, wt.%

1

1

1

1

5400

400

150

100

Tensile strengtha, psi

87

270

399

6700

Elongation at breaka ,%

8

30

5

3.3

Tensile modulusa, psi

1.2

2.9

51

320

Durometer hardnessa

74A

73A

54A

85A

d a, cP

a

F4

Determination error is 10%.

TABLE 7 | Results of TGA study on three cured oligomers.a XMA-224b

BMA-222b

BR-3443

ºCc

290

239

209

Temperature of 5.0% of the mass loss, ºCc

295

290

251

Temperature of 2.0% of the mass loss,

a Each of the three oligomers was diluted with 30 wt.% of IBOA. 2.0% of Irgacure 184 was added to formulations. Conditions of cure are presented in Table 2. b Reference Figure 1 for the structure. c Determination error is ± 1 ºC.

24



NOV EMBER 2011 | W W W . P C I M A G . C O M

Summary Melamine resins are well known in the coatings industry. Many melamine acrylates are used as protective coatings, as release coatings for reusable plywood,18 etc. In particular, BMA-222 is used in the furniture industry. We prepared a series of UV-curable MAs with different acrylate functionalities, which undergo fast photoplymerization with a low concentration of PI. Although the MF has been functionalized, the resin MA still possesses much of the melamine properties. One can purposefully alter the melamine acrylate mechanical properties by varying functionalities of MA or using mixtures of MAs with other oligomers. In our opinion, X-1 (Table 5) is the most interesting among the entire synthesized melamine acrylates. It has low viscosity, can be synthesized from readily available commercial raw materials, and its formulations produce colorless films. PI-grafted MA demonstrates negligible leaching from the cured coating in THF. We synthesized five oligomers by addition of thiols to acrylate groups of MA. The most valuable property of the new sulfur-containing oligomers is their high n D20. These oligomers will find applications in antireflective coatings. 

References 1

Webster, G. Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints: Prepolymers and Reactive Diluents for UV and EB Curable Formulations; Wiley: New York, 1997. 2 Wicks, Z.W.; Jones, F.N.; Pappas, S.P.; Wicks, D.A. Organic Coatings Science and Technology; Wiley: New York, 2007, ch.7. 3 http://www.bomarspecialties.com 4 Nebioglu, A., Leon, J.A., Khudyakov, I.V. RadTech USA, Chicago, 2008. 5 Khudyakov, I.V., Turro, N.J. Photochemistry and UV Curing: New Trends, Fouassier, J.P., Ed., Research Singpost: India, 2006, ch. 21. 6 Allen, N.S., Marin, M.C., et al. J. Photochem. Photobiol. A. 1999, 126, 135. 7 Pa (pascal) is an SI unit of pressure, of tensile strength, of tensile modulus. However, such non-SI units as psi and ksi are often used in the coatings industry. 145 psi = 1 MPa. 1 ksi stands for 1000 psi or 1 kPa = 145 ksi. In this work we use all three units. 8 Carlini, C., Angiolini L. Adv. Polym. Sci. 1995, 123, 127. 9 Schwalm, R. UV Coatings Basics, Recent Developments and New Applications; Elsevier: Amsterdam, 2007, ch. 5. 10 Nebioglu, A., Soucek, M.D. J. Polym. Sci. Pol. Chem. 2006, 44, 6544. 11 Dušek, K., Galina, H., Mikes, J. Polym. Bull. 1980, 3, 19. 12 Sadayori, N., Hotta. Y. U.S. Patent Application Publication 20040158021A1, 2004. 13 Morford, R.; Shih, W.; Dachsteiner, J. Proceedings of SPIE 2006, 6123. 14 Groh, W., Zimmermann, A. Macromolecules 1991, 24, 6660. 15 Olshavsky, M., Allcock, H. R. Macromolecules 1997. 30, 4179. 16 Houseman, B.T., Gawalt, E.S., Mrksich, M. Langmuir 2003, 19, 1522. 17 Ludolf, N.P., Tirelli, N., Cerritalli, S., Cavlli, L; Hubbell, J.A. Bioconjugate Chem. 2001, 12, 6536. 18 Hall, R.P. US Patent 3,899,611, 1975.

Experimental Product

Cut your Milling Costs without sacrificing © 2011, 3M. All Rights Reserved. 3M is a trademark of 3M.

performance.

Introducing 3M™ Micro Milling Media ZGC* For years Yttria-Stabilized Zirconia beads have been the standard for high-energy micro milling. Now there’s a product with all the performance of Yttria-Stabilized Zirconia, but at a fraction of the price—3M™ Micro Milling Media ZGC. What does this mean for your milling operations? Now, not only can you cut your milling costs, but you can also afford to use higher performing media to make smaller particle sizes in less time. For more information and to purchase 3M micro milling media, go to www.3M.com/ZGC. *Notice: This experimental product has not been introduced or commercialized for general sale, and is subject to change or withdrawal without notice.

ITS)SERIES

Integrated Tinting

Systems

for a Low-VOC Future

P

This article is Part 1 of a four-part series on converting to an integrated tinting system.

aint manufacturers face many conflicting demands. Their clients have come to expect instant availability of high-quality, highperforming, reliable paints in every imaginable color. At the same time, ever-tightening VOC regulations need to be observed in a very competitive market environment. What appears like an impossible proposition is actually an excellent time to think about tinting systems more generally and to put one’s business on a stronger footing. As paint manufacturers are urged by regulatory bodies to convert their tinting systems to lowVOC colorant technology, they are also given an opportunity to rethink their set-up and make significant changes. Conversions are best managed in a comprehensive way, applying the principles of integrated tinting system design. For best results, paint producers need to understand both the benefits of integrated tinting and their own business needs. Working in partnership with a complete tinting

Gloss Level 60º

FIGURE 1 | Gloss level of a silk alkyd paint with various colorant types and levels. 50 45 40 35 30 25 20 15 10 5 0

systems solutions provider, they will be able to convert to a customized system that mitigates the above challenges while keeping total cost of ownership low. There has been a concern with volatile organic compounds (VOCs) for many years, as some are known to cause potential harm to human health and/or the environment. VOC levels in paint are therefore carefully regulated but, so far in the United States, the contribution made by VOC-containing colorants has not been taken into account. With new legislation announced by the South Coast Air Quality Management District (SCAQMD) this is set to change. From January 1, 2014, VOC levels in colorants must not exceed 50 g/L for all architectural and water-based industrial coatings.1 Paint manufacturers now have less than two years to prepare for the changes. Many currently underestimate what the conversion to low-VOC colorants might mean to their business. Research published by the SCAQMD2 has shown that very few paint manufacturers have given any thought at all to the changes, and of those who did, only a quarter are really aware of its implications. The majority of the respondents, particularly small- and medium-sized companies, admitted to not knowing what to expect in terms of time needed for the conversion, overall cost and training involved, or whether their existing dispensing equipment would be compatible with low-VOC colorants.

Traditional Tinting Systems

0 v% Colorant Load (reference)

7 v% Universal Colorant Load

7 v% Alkyd Colorant Load

15 v% Alkyd Colorant Load

TEST PROCEDURE: SFS-EN ISO 2813 (1999)

The first step is to understand exactly what a tinting system does and the different types of tinting systems. Tinting systems for paints, designed to deliver the exact shade of color to customers, are based on standardized components, including colorants, dispensing and mixing equipment, control software and a color formula database designed to match the selected color marketing tools. Most paint manufacturers aim to offer the broadest possible range of coating formulations and products to

By Martijn Kunnen, Head of Sales, Colorants EMEA and Total Solutions CE; and Sven Heutz, Sales & Service Manager | CPS Color, Sittard, The Netherlands 26



NOV EMBER 2011 | W W W . P C I M A G . C O M

The Conversion Question Conversion to a low- or zero-VOC colorant system is the only option due to legislation. However, the key is to select a new tinting system that will deliver the best possible long-term results for the individual business needs; in other words, to convert to an integrated tinting system. Such a system is more than the sum of its parts. It is a comprehensive approach to tinting system design that is customized to meet the business objectives of the individual paint manufacturer. Design of such systems requires thorough analysis of the manufacturer’s current business

model and future objectives. It also demands intimate technical knowledge of all tinting system components to optimize and fine tune the performance of each element: colorants, dispensing and mixing equipment, control software and a color formula database design.

The Best of Both Worlds For one business we examined alkyd coatings technologies, an important business segment for this paint producer. Therefore, a customized colorant set was selected to combine the advantages of a single universal system with those of a dual system. Water-based colorants are paired with a selection of UV-resistant, high-performance colorants plus economical colorants for the universal and solvent-based ranges. Such a system may, for example, consist of 24 colorants in total: 10 water-based, six universal and eight solvent-based ones. Colorants that are only needed in small quantities are set up as universal colorants. They can be used with both water-based and solvent-based systems, increasing their consumption. Since color formulas contain only minor amounts of

FIGURE 2 | Dry time variability for a high-gloss alkyd tinted with different colorants and levels. 600 500 Drying Time (min.)

serve the diverse needs of their customers. In an effort to become more efficient, they adopted a universal colorant system for tinting a broad variety of products: from water-based latex architectural coatings to solventborne industrial maintenance coatings. Such systems typically consist of 12 universal colorants. While this works well in terms of offering a broad range of products at the point of sale, the paints’ quality may not always be entirely satisfactory due to the contribution of water from the universal colorants. Users of alkyd paints, for example, have a high demand for deep colors that can require a large colorant load. Introducing too much water into an alkyd product, however, can impair workability and application characteristics of the paint. Here, a solvent-based colorant would achieve a better result (Figures 1 and 2). For example, 15% of a solvent-based colorant in a silk alkyd paint can be handled without a problem, while the addition of only 7% universal colorant will significantly reduce the gloss level of the coating (Figure 1). However a high-gloss alkyd paint with 7% universal colorant may require a longer drying time (Figure 2). One way around this problem is to operate a dual system, which is one that consists of two sets of colorants, one water-based, one solvent-based. This ensures maximum compatibility with the base paint – but it can lead to problems with the colorants themselves. Doubling the number of colorants means that the consumed quantity of colorant declines by half on average. Some colorants, such as violet-red or magenta, are only used in very small amounts to less than one liter per year. This means they remain in their canisters for too long and may start to thicken or deteriorate, causing problems within the dispenser (Figure 3). The picture becomes clear: whether single or dual, users of traditional, water-based, universal colorant systems either face limitations in terms of paint quality and characteristics, or experience adverse effects on colorant and equipment quality. If they replace their current lines with corresponding ones stripped of VOCcontaining additives, they may well conform to incoming regulation, but the other difficulties will remain. What’s more, a simple “pour-over” is set to introduce further issues, as companies already experimenting with such a solution reported in the AQMD colorant survey. Half of them reported problems with clogged and dried-up nozzle tips, and some experienced variable viscosity and lack of compatibility in terms of gloss, water sensitivity and other features. Generally, low-VOC colorants are known to pose challenges with storage, mold growth and surface drying.

400 300 200 100 0

7 v% 0 v% Universal Colorant Load Colorant Load (reference)

15 v% Alkyd Colorant Load

Test Procedure: ASTM 5895 – 01e1

FIGURE 3 | Variable rates of consumption for different colorants in an average tinting system. 16% 14% 12% 10% 8% 6% 4% 2% 0%

t n LC C r a e e e e H HC id LC it HC id g be nt HC LC LC le e w Ox low Wh ed Ox ran Um age ack lack Red Vio Gre lue lue o l w el B R l O l d B B M B Ye llo Y Re Ye

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



27

Integrated Tinting Systems for a Low-VOC Future

magenta or violet, their impact on the performance characteristics of the final product is minimal. It is important to integrate rules into the color formula database to ensure that only compatible colorants can be chosen with a selected product. Silicate and silicone-based paints, for instance, can only be tinted with water-based and universal colorants. While unlimited amounts of solvent-based colorants can be added to alkyd-based products, universal colorants may only be added in small amounts. This helps define the perfect balance between cost/performance and consumption of each individual colorant (Figure 4).

stics, including abrasiveness and speed of sedimentation or drying, could have a negative effect on the lifetime of pumps, valves or other mechanical parts. The right dispensing technology or even a combination of different technologies should be carefully considered. Further, it is important to select the optimal canister sizes and determine suitable stirring and recirculation needs for each individual colorant (see sidebar). This will help ensure that the colorant remains fresh in the canister, which will help minimize maintenance interventions.

The Formula of Color An Integrated Concept The challenge of a comprehensive, advanced tinting system extends beyond combining the colorants and color formulas. Proper configuration of the entire tinting system, including dispensing equipment, must be considered. Customization of a dispenser begins with an analysis of the retailer’s business model and average tinted sales volume. This will determine the speed requirements to properly serve the end-user customer. Once that is determined, the dispenser type must be carefully matched to properly support the colorant technology and established set of colorants. The behavior of the colorants over time within the dispenser must be also considered. Their various characteri-

Creating an accurate formula database is a critical part of integrated tinting system performance. The correct color formula rules ensure that the appropriate colorants are selected to achieve desired performance characteristics; for instance, UV-resistant colorants are used with exterior products. They minimize the overall formulation cost and optimize colorant consumption between all single colorants, meaning each single colorant should achieve a reasonable turnover to overcome technical problems. Through this process, a small selection of the color formulas may turn out to be more expensive than they previously were. However, the overall improved performance of the system will balance this out in the end. Maintenance costs and down times will be minimized as throughput of slow-moving colorants is improved. Lower total cost of ownership and superior tinting system performance are the ultimate objective of integrated tinting solutions.

Responsible Service Service is another key part of the tinting process that should not be overlooked. As integrated tinting systems are designed to fine tune all tinting components, it is important that the service provider be well versed in both the mechanics of the equipment and the characteristics of the colorant set. True tinting system support is best provided by a global network of trained specialists in colorants and system technology, who are able to modify existing systems and provide consultative assistance in case of problems. Choosing a partner who is responsible for the performance of all components of an integrated tinting system is a true competitive advantage. Consistent monitoring of color shade, strength and rheology during the production process results in assured color accuracy and reproducibility.

FIGURE 4 | Dual system vs. combined system.

n te ico ica Sil Sil

tex La

lic

ry Ac

d lky d ne lky il A A O ha il et m O r u i d lyu ng Lo Me Po

Water

Solvent

Consultative Services When setting up a truly integrated tinting system, it is important to make the right strategic business decisions throughout the design phase that create a sustainable, competitive advantage for the paint manufacturer. By working with a partner, capable of understanding all aspects of tinting system design, paint manufacturers can be assured that their business priorities will be achieved. Once implemented, only a supplier with comprehensive capabilities will be responsible for the long-term functionality of the complete integrated tinting system.

BINDER TECHNOLOGIES Water-based Water-based

28



Solvent-based Universal

Solvent-based

NOV EMBER 2011 | W W W . P C I M A G . C O M

Environmental Regulations – Not Just for Southern California As with many environmental legislative trends, what starts in Southern California quickly makes its way across the country. Is your company ready to implement upcoming

Painting is a cinch ...

With a paint that works with you! Introducing Eastman Optifilm™ additive OT1200 Extends open time, for improved wet edge and workability in paint Today’s paint has less workability time making it difficult to easily fix or paint over a mistake. Eastman Optifilm™ additive OT1200 — the newest addition to Eastman’s Optifilm portfolio — enables formulators to create low-VOC paints with improved open time and wet edge without negatively affecting other properties. OT1200 performs under a wide range of application conditions. The result is compliant paints with significantly improved workability and easier cleanup. For more information on Eastman Optifilm™ additive OT1200, visit us at www.eastman.com/optifilmOT1200 or call 1.800.EASTMAN for a free sample.

From the Eastman Optifilm™ family of products. Enabling performance, aesthetics, and compliance in architectural paints.

Eastman and Optifilm are trademarks of Eastman Chemical Company. © Eastman Chemical Company, 2011.

Integrated Tinting Systems for a Low-VOC Future

Come to King for Rheology Modifiers K-STAY Attributes: ®

K-STAY

x

Liquid Thixotropes

x x x x

For use in pigmented solventborne systems Highly efficient - low use levels Excellent sag control and pigment suspension Easy handling - pourable Alternative to discontinued Ircogel® products1 NEW K-STAY® 511 For Pigmented Solventborne Systems

K-STAY 511 0.2% K-STAY 511

0.4% K-STAY 511

Panel: Sag control with 0.2% and 0.4% dosage of K-STAY 511 - Polyester Can/Coil Coating

NEW K-STAY® 555 For Pigmented Solventborne Systems 3% Ircogel® 955

3% K-STAY 555

K-STAY 555

Comparison: 3% K-STAY 555 to 3% Ircogel 955 Polyester Bake Enamel

K-STAY® 501 For Pigmented Solventborne Systems K-STAY 501

Fumed Silica

Organo-Clay

changes to environmental legislation? The questions below will help to determine your own business readiness. If you are like many paint producers, you will find several questions difficult to answer. That is when a comprehensive tinting solutions provider can consult with you to design a system that will serve your company for years to come. • Are you currently conducting research and development on near zero-VOC colorants? • What is the timeframe to complete development and testing of a new near zero-VOC colorant system? • Do you have the technical resources in terms of lab personnel and equipment to complete a colorant technology conversion? • What are the steps involved in a colorant technology conversion to near zero-VOC colorants? • Will you need to adapt your color formula database or color formulation parameters to optimize performance of a new colorant system? • What is the expected timeframe to implement a change-over from glycol-containing to near zero-VOC colorant technology? • Will a near zero-VOC colorant system be compatible with your current, installed base of dispensing equipment? • What issues do you expect to experience in your point-of-sale operations as a result of a conversion to near zero-VOC technology? • What is the cost associated with retrofitting existing tinting equipment to meet the requirements of a near zero-VOC colorant system? • Is it preferable to invest in new dispensing equipment to avoid problems in the field, such as frequent mistints and maintenance downtime? • What is the one-time cost associated with a colorant technology conversion? The second article will delve deeper into the area of colorant technology to find new ways to deliver a sustainable advantage for your business. We will explore the colorant options beyond the traditional, commoditized, 12 colorant set, including highstrength colorants and colorants for specialized applications such as façade coatings. 

For additional information, contact Bart Wilbanks, Technical Account Manager, Colorants, CPS Color, at 800-728-8408 or 704-588-8408 ext. 240.

K-STAY 501

References 1

Comparison: K-STAY 501 to fumed silica and organo-clay Thixotropes at recommended use levels - Polyester/HMMM Coating

1

Ircogel® is a registered trademark of Lubrizol Advanced Materials, Inc. 2

New VOC Content Requirements for Colorants – passed June 3, 2011. PAR 1113 would establish VOC content limits for colorants effective Jan 1, 2014. The VOC content limit for colorants used to tint architectural coatings, excluding maintenance coatings would be 50 g/L. The VOC content limit for colorants used to tint waterborne industrial maintenance would also be 50 g/L. The VOC content limit for colorants used to tint solventborne industrial maintenance coatings would be 600 g/L. AQMD Colorant Survey 2010, Re: Proposed amended rule 1113.

Visit Us At

www.kingindustries.com Email: [email protected] Phone: 203-866-5551

Visit ads.pcimag.com 30



NOV EMBER 2011 | W W W . P C I M A G . C O M

Follow PCI on Facebook at www.facebook.com/PCIfan on Twitter at http://twitter.com/PCIMag and on Linkedin at www.linkedin.com

Surfactant Evaluation in Preparing Acrylic Ultrafine Latexes Influence on Paint Properties

W

aterborne acrylic latexes can be prepared via batch, seeded, in situ seeded and continuous polymerization. In this investigation, the seeded process was used for the preparation of nano-size seeds with a target average particle size of Dn ≤ 50 nm. These nano-size seeds were then used for the preparation of ultrafine full latexes via a semi-batch process with a target average particle size of Dn ≤ 100 nm. Surfactant concentrations were optimized to ensure minimal grit and coagulum and clean reactions with the final surfactant concentration of 0.45 parts per hundred of monomer (phm) in the final latex. Additionally, these ultrafine dispersions were evaluated for latex film appearance, gloss, adhesion and water pick-up performance. Finally, the dispersions were utilized to prepare semigloss paints to illustrate the effect of particle size on select paint properties (i.e., appearance, gloss, block and adhesion).

Introduction Waterborne coatings are applied on wood, metal, plastics, flooring and paper substrates to improve their aesthetics and provide protection from light, salt, heat and moisture. The key ingredients in a coating formulation are the pigment and binder. Pigments impart opacity, durability, anticorrosion and rust inhibition to the coating; the latex binder forms a film and holds pigment, filler and other components together, and additionally protects the substrate. The binder also contributes to the gloss, blocking and adhesion of the film. Surfactants play a critical role in binder preparation and are used to control particle size, reaction kinetics and latex stability.1,2 However, surfactants can negatively impact the block, scrub, adhesion and gloss properties of the coating, so it is generally desired to utilize minimal levels of surfactant and nano-size particles to circumvent these issues. Our investigations focused on screening various surfactants for making ultrafine latexes and determining the impact of these surfactants and latexes on paint properties.

Surfactant Selection A surfactant is a key ingredient in latex preparation. Four types of surfactants were selected for the acrylic seed and ultrafine full blown (FB) latex preparations. The benchmark surfactant utilized in the experiment was DowFax 2A1™ (DPOS). DPOS was selected as a control, as it is claimed in the literature to generate ultrafine particles at low surfactant use levels and offer excellent colloidal stability. Three types of AEROSOL® surfactants from Cytec Industries (i.e. sulfosuccinamates, monoester sulfosuccinates and diester sulfosuccinates) were also evaluated. The products included AEROSOL 22 (tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, 22), AEROSOL 18P (disodium Noctadecyl sulfosuccinamate, 18P), AEROSOL A-102 (disodium ethoxylated alcohol [C10-C12] half ester of sulfosuccinic acid, A-102), AEROSOL EF-800 (proprietary sulfosuccinate surfactant mixture, EF-800), AEROSOL MA-80 (sodium dihexyl sulfosuccinate, MA-80) and AEROSOL OT-75 (sodium bis (2-ethylhexyl) sulfosuccinate, AEROSOL OT-75). Table 1 gives an overview of the various surfactants, select properties and features.

Experimental Results and Discussion Seed Preparation and Characterization Acrylic seed batches of 20% solids were prepared via a batch process (Table 2). This seed recipe was elected with goals of achieving a Tg ~14 °C binder, and seed particle size target was 40 to 50 nm at 5 phm surfactant use. The deionized water and surfactant solution were heated to 82 °C and mixed with an A310 impeller. At 50 °C bath temperature, the monomer solution was charged to the reactor. At a 75 ºC bath temperature, the initiator was charged and the agitation speed was increased from 200 rpm to 320 rpm. Following 1.5 h of reaction, the batch temperature was dropped to 40 °C. The seed was drummed out and filtered through a finer mesh filter for grit. All seed latexes achieved the desired conversion to 20% solids and evidenced nil to very minimal grit.

By Azhar Awan, Senior TS&D Scientist, and Dave Vanzin, TS&D Manager Americas, Cytec Industries Inc., Stamford, CT 32



NOV EMBER 2011 | W W W . P C I M A G . C O M

TABLE 1 | Surfactant properties and characteristics. Type

Critical Micelle Concentration (% weight)

Surface Tension (dynes/cm)

Alkyl diphenyl oxide disulfonate

0.03

34

Sulfosuccinamate

0.04

36

AEROSOL 18P AEROSOL A-102

Sulfosuccinamate Monoester sulfosuccinate

0.06 0.1

40 29

AEROSOL EF-800

Monoester sulfosuccinate

0.03

31

AEROSOL MA-80

Diester sulfosuccinate

1.5

28

AEROSOL OT-75

Diester sulfosuccinate

0.12

26

Surfactant DPOS AEROSOL 22

Seed particle sizes are detailed in Figure 1. AEROSOL 18P produced seed particles of 37 nm and exhibited no obvious negative process artifacts (i.e., minimal aggregates, grit and coagulation). The fine seed particles, narrow size distribution and clean process attributable to AEROSOL 18P could possibly be explained as follows: (a) the use level of 5 phm is sufficient for the seed particle full coverage; (b) the AEROSOL 18P diffusion rate fits quite well with the seed particle formation and its growth; and/or (c) the molecule anchored well and was not easily displaced when the seeds were mixed and sheared during polymerization. The AEROSOL 22 also yielded a small seed particle of 47 nm. Additionally, no coagulum and grit were observed. It is speculated that AEROSOL 22 has less affinity for the monomer droplets and poor pre-emulsion stability but possesses a higher affinity for the particle and its stability. AEROSOL A-102 yielded a seed particle size of 49 nm. AEROSOL A-102 offers a stable pre-emulsion, and this is highly desirable for various EP process schemes where reaction ingredients are charged from a single line and tank. This better emulsion stability means that AEROSOL A-102 has a stronger affinity for the acrylic monomers. Therefore, at any given time during polymerization, it is less available for particle protection and stability. Seed particles prepared with DPOS were 50 nm, and there was no reactor build-up or grit observed. The AEROSOL EF-800 surfactant produced seed particles of 55 nm, which was greater than the desired size. The pre-emulsion stability was poor compared to DPOS but better than AEROSOL 18P and AEROSOL 22. The larger size particles and build-up on the reactor blades are probably attributable to the lower affinity of this surfactant for the acrylic seed particles. The AEROSOL OT-75 surfactant yielded a final seed particle size of 55 nm. It is hypothesized that the larger size seed attributed to AEROSOL OT-75 limits its availability to support the stability and growth of the primary particle. This higher emulsion stability and more solubility within polymer particle core could mean that AEROSOL OT-75 possesses limited ability to support particle nucleation and its growth. The AEROSOL MA-80 was selected to facilitate the preparation of larger size particles, yielding a seed particle size of 72 nm. One could expect that due to its high

Features Ultrafine particle size, water resistance and colloidal stability Small particle size, excellent salt tolerance, mechanical stability Emulsifier and dispersant Sole emulsifier, excellent stability Sole emulsifier, imparts excellent stability, high tolerance for water-sensitive polymers Dynamic surface properties, costabilizer/ emulsifier Excellent co-emulsifier, outstanding wetting and dispersing properties

CMC, AEROSOL MA-80 would be expected to produce bigger size particles.

Ultrafine Full Blown Latex Preparation and Characterization The amount of the seed for the FB latex for AEROSOL 18P and other seed batches was calculated using Table 3, and for AEROSOL 18P it was 66.5 grams. The FB latex theoretical average particle size was 85 nm. The surfactant

TABLE 2 | Pure acrylic latex seed recipe. Reaction Ingredients

Amount (g)

Butyl acrylate (BA) Methyl methacrylate (MMA) Acrylic acid (AA) Deionized water (DI Water) Surfactant (phm) Ammonium persulfate (APS) DI water for catalyst Total Seed solids (%)

23.6 15.0 0.7 144.0 5.0 0.4 15.0 203.7 ~20

FIGURE 1 | Seed batches particle size and particle size distributions from various surfactants. 72.6 Seed Particle Size (nm) Seed Particle Std (nm) 55.1 50.4

49

47.3 37

12.6

11.9

D

PO

S

AE

RO

SO

L

22 R AE

O

SO

L

18

P

A

O ER

SO

L

A-

10

2

AE

RO

SO

15.7

15.1

12.7

9.8

L

EF

-8

00

AE

RO

SO

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

L

M

A-

80



33

Surfactant Evaluation in Preparing Acrylic Ultrafine Latexes

TABLE 3 | Seed calculation methodology for the preparation of FB latexes. 18P seed average Dn particle size (nm) FB latex target particle size (nm) Total solids (%) Seed amount (g) Surfactant level for FB latex (PHM) Theor. volume growth factor (about) Total polymer (g) Total polymer volume (ml) Seed polymer volume (ml) Seed polymer (g) Seed solids (%) SAA from seed (g) Monomer added for Fb latex (g) Monomer added for Fb latex (ml)

37 83 45.0 66.5 0.44 11.3 142.6 101.9 9.0 12.6 19.0 0.63 130.0 92.9

TABLE 4 | Recipe used for FB latex preparations. Reaction Ingredients

Amount (g)

Seed (19-20%) solids BA MMA AA DI water Sodium bicarbonate APS DI water for APS Total ingredients Solids (%)

~ 60.00 55.00 70.00 2.70 110.00 0.35 0.90 10.00 249.30 45

TABLE 5 | Latex characterizations. Surfactants Used

DPOS

AEROSOL AEROSOL AEROSOL AEROSOL AEROSOL 22 18P A-102 EF-800 MA-80

Surfactant level 0.45 (phm) Measured solids (%) 45.0 Conversions (%) 100.0 pH 4.75 Mean particle size 110 (nm) std± 16 Latex film thickness T - 2.5 mil wet Adhesion 8 Viscosity (cP) 25 Freeze/thaw F stability (cycles)

0.45

0.45

0.45

0.45

0.45

44.7 99.9 4.5

45.0 100.0 4.2

45.0 100.0 5

48.0 100.0 4.5

46.0 100.0 3.9

87

88

125

93

bimodal

23

23

15

25

B/T

T

T

T

T

10 12

10 30

10 33

10 22

10 40

F

3

1

F

F

T: Transparent, B/T: Bluish/Transparent; and F: Failed

TABLE 6 | Water intake properties. Surfactant Used for the Seed

Films Immersed for 30 min in Water

Films Immersed for 1 h in Water

Films Immersed for 4 h in Water

DPOS AEROSOL 22 AEROSOL 18P AEROSOL A-102 AEROSOL EF-800 AEROSOL MA-80

Nil Nil Nil Nil Nil Nil

Nil Nil Nil At the edges At the edges Hazy

Hazy Hazy Hazy Hazy Hazy Hazy

34



NOV EMBER 2011 | W W W . P C I M A G . C O M

from seed was 0.6 g, and this overall amount was used in each batch and was 0.45 phm. The FB latex recipe is given in Table 4. Initially, DI water was added to the seed and the seed gently mixed. After DI water addition, the seed was then mixed for 2 more min and charged to the reactor. After the seed solution charge, the process conditions for the FB latex were similar to the seed preparation with the exception that the monomers were charged over 2.5 h. Latex characterizations are given in Table 5. The theoretical and experimental solids are in good agreement. Batches were rated Pass/Fail, with Pass designating minimal coagulum, grit and residual monomers, and Fail designating that coagulum, grit or residual monomers exceeded polymerization process norms. The AEROSOL OT 75 batch was the only failure, as it coagulated during polymerization. The control latex prepared from DPOS yielded a particle size of 110 nm. Latexes prepared from the AEROSOL 22 and AEROSOL 18P sulfosuccinimate surfactants evidenced particle sizes of 87 and 88 nm respectively, and grit, coagulum and reactor build-up were low (AEROSOL 22 was 0 and AEROSOL 18P was 0.4 g). The particle sizes of latexes prepared from the sulfosuccinate surfactants AEROSOL A-102 and AEROSOL EF-800 were 125 and 93 nm, respectively, and additionally, these products evidenced 0 and 2 g coagulum. The AEROSOL MA-80 surfactant-based latex produced a particle size of 180 nm with some fine particles. The viscosity of all the final latexes was below ~50 cps, which is desired by latex and paint producers as this facilitates easy transfer, addition and mixing. To assess surfactant influence on latex properties, film drawdowns were prepared on Leneta paper. The films were 2.5 mils wet and were initially dried for 1 min at room temperature and then placed in an oven at 107 °C for 5 min. The AEROSOL 22 was continuous and transparent, and the AEROSOL MA-80 film was hazy and continuous. All films based on the other surfactants evidenced some degree of mud cracking (i.e. leaf type morphology). Latex film adhesion to glass and Leneta paper was investigated per ASTM D 7234-05, and all films evidenced excellent adhesion. The surfactant influence on the freeze/thaw (F/T) stability of the latex was assessed. Only the latex based on the 18P passed the desired 3 F/T cycles.

Latex Water Uptake Latexes used as binders in exterior paints require good water resistance, and surfactants can greatly influence water intake. To assess various surfactants’ influence on this property, 1 mil dry films were prepared on glass, and film samples were dried at 107 °C for 5 min and then aged overnight in a controlled humidity and temperature room (CHT-50% humidity at 24 °C). The glass panels were then submerged into a water bath and observed and monitored over a 4-h period. Results are shown in Table 6. The good to excellent water resistance properties of these latexes could be due to: (a) lower surfactant use; (b) surfactant and polymer compatibility and (c) ultrafine particles.

Latex Gloss Properties Dry latex films (1 mil) were prepared on Leneta paper.

FIGURE 2 | Gloss properties at 20°, 60° and 85°.

FIGURE 4 | Semigloss paint gloss – latexes prepared from various surfactants.

120

100 90

80

80

 

60

   Paint Gloss

Film Gloss

100

40 20

70 60

Paint 20º gloss

50

Paint 60º gloss

40 30

0 20º gloss 60º gloss 85º gloss

  AEROSOL    AEROSOL    AEROSOL AEROSOL AEROSOL MA-80 EF-800 A-102 18P 22 63 59.5 64 67 13   86 82.7 73 83 55 97 96.8 90 90 89.5

DPOS 59 86 81

Paint 85º gloss

20 10 0 D

FIGURE 3 | Semigloss paint block – latexes prepared from various surfactants.

PO

S

AE

RO

SO

L

22

R AE

O

SO A

L

18

O ER

P

SO

Paint  block  "0" no  block,  and "10"  perfect  block 

L

AE

A-

10

RO

2

SO

L

EF

AE

-8

RO

00

SO

L

M

A-

80

10

in a CTR room. Paint films were continuous and their surfaces smooth. These paint films were then tested for block, gloss and adhesion properties.

9

9 8

8

Paint Block Performance

7 6

6

5 4 3 2

2

2 1

1 0 DPOS

AEROSOL AEROSOL AEROSOL AEROSOL AEROSOL MA-80 EF-800 A-102 18P 22

The films were dried 60 s at RT, and then dried in an oven above 90 °C for 5 min. Films were aged in the CHT room. For each film, 20°, 60° and 85° angle gloss was measured (Figure 2). The AEROSOL 18P and AEROSOL 22 surfactants yielded the best overall results and were closely followed by AEROSOL A-102, EF-800 and DPOS products. The AEROSOL MA-80 latex did yield a smooth and continuous film. However, it also yielded the poorest 20° gloss performance, and this lower gloss is attributable to large latex particle size.

Semigloss Paint Preparation – Attributes and Properties The latex pH was raised to 8 and the latex was added to the semigloss grind to prepare paints (51.7 % solids and 24% PVC). Paint films, 2.5 mil wet and 1 mil dry, on Leneta paper and glass surfaces were prepared. Paint films were then conditioned for 1 day and for 1 week

Coupons were prepared and used for block resistance properties at 24 °C and 40 °C. Block performance is rated on a scale of 0 to 10, with 0 meaning no separation and 10 meaning complete separation. The data is presented in Figure 3. Paints prepared from AEROSOL 18P and AEROSOL 22 showed the best performances and these were followed by DPOS-containing latex. The block property associated with the AEROSOL MA-80, AEROSOL EF-800 and AEROSOL A-102 was poor. It is hypothesized that AEROSOL 18P and 22 are more compatible in the polymer matrix.

Paint Gloss Properties Paint gloss can be influenced from various components of the paint formulation. To assess the influence of surfactant type and amount, as well as latex particle size on paint gloss, gloss was measured (Figure 4). The 20°, 60° and 85° gloss evidenced similar ranges. Thus, the latex particle size between 80 nm and 120 nm had no apparent effect on paint gloss properties.

Paint Adhesion Properties Semigloss paint adhesion was measured via ASTM D 7234-05 cross-hatch method. Adhesion performance is rated on a scale of 0 to 10, with 0 meaning no adhesion and 10 meaning nothing was removed. After 8 days of CRT conditioning, both the sulfosuccinamates (AEROSOL 18P and AEROSOL 22) and sulfosuccinates (AEROSOL A-102, AEROSOL EF-800 and AEROSOL MA-80) surfactant-containing paints exhibited excellent adhesion. The adhesion of the DPOS control was also good, but slightly lower (Figure 5). PA I N T & C O A T I N G S I N D U S T R Y



35

Surfactant Evaluation in Preparing Acrylic Ultrafine Latexes

Conclusions and Summary Nano-size seeds of ≤ 50 nm and 20% solids were successfully prepared utilizing AEROSOL 22, AEROSOL 18P, AEROSOL A-102 and DPOS surfactants. A semi-continuous polymerization process was successfully exploited to

FIGURE 5 | Semigloss paint adhesion – latexes prepared from various surfactants. 12

  Paint Adhesion Rating 10

prepare ultrafine (nano) latexes of ) 100 nm at ultralow (0.45 phm) surfactant use levels with AEROSOL 22, 18P, A-102 and EF-800. 18P latex also offered better F/T stability opposite to DPOS. These ultrafine latex films evidenced excellent aesthetics, gloss, adhesion and low water intake. Latexes of both less or greater than 100 nm particle size offered excellent suitability with and compatibility towards the semigloss paint grind. Paint film surfaces were smooth and glossy, and cross-hatch adhesion performance was also exceptional. Paints prepared from AEROSOL 22 and AEROSOL 18P-based latexes also yielded excellent block resistance properties. 

References

8

1

6 2

4 2

For more information, e-mail [email protected].

0 DPOS

36



Daniels, E.S.; Sudol, E.D.; El-Aasser,M.S. Polymer Latexes, Preparation, Characterizations, and Applications, ACS Symposium Series, 492, ACS, Washington, DC 1992. Lovell, P. In Emulsion Polymerization and Emulsion Polymers, El-Aasser, M.S; and Lovell, P., Eds., John Wiley & Sons London, 1997.

AEROSOL AEROSOL AEROSOL AEROSOL AEROSOL MA-80 EF-800 A-102 18P 22

NOV EMBER 2011 | W W W . P C I M A G . C O M

This article was presented at the 38th Annual Waterborne Symposium in New Orleans, LA.

INNOVATION = VALUE COATINGS:

Go ‘green’ with innovative binder and additive technologies.

ADHESIVES & SEALANTS: Conserve energy in production and product use.

ELASTOMERS:

Formulate with alternative raw materials, and do it competitively.

YOUR CUSTOMERS DEMAND ENVIRONMENTALLY-FRIENDLY PRODUCTS. LET UNIVAR SHOW YOU HOW YOU CAN GO GREEN. Univar supplies the CASE Specialties industry with much more than a comprehensive line of sustainable ingredients — we can provide you with an innovative approach to your green formulation challenges, offering you technical expertise from concept to production. Consider Univar your partner in sustainable product development. We connect you to the latest materials and technologies, and help you bring environmentally-friendly products to market. Innovation, sustainability, expertise — it all adds up to value.

INNOVATION > TECHNICAL EXPERTISE > MARKETING > SALES > LOGISTICS > DISTRIBUTION

1.877.203.0045 | [email protected] www.univarcorp.com

Formulation Optimization Utilizing DOE Mixture Statistics

M

aintaining maximum color development throughout the production process for cellulose acetate butyrate/acrylic-based automotive refinish formulations with high-strength carbon black has always been an issue. Formulators have found that the order of addition can impact the final color of the applied coating. For this reason, it is imperative that the grind formulation provides the highest possible color strength, as it is likely to lose some color development in the course of processing. This problem can be studied using the traditional scientific approach of isolating independent variables and examining their impact on the desired properties. However, when this is done, it quickly becomes apparent that something is being missed. One by one, the optimal

TABLE 1 | Generic automotive refinish black basecoat formulation. Grind

Weight %

CAB 381-2 Toluene Borchi Gen 0451 FW200

2.15 42.95 5.48 8.53

Letdown

Weight %

Acryloid A-21 100% Santicizer 160 n-Butyl acetate Isopropanol MIBK

10.20 1.30 13.39 11.50 4.50 100.00

TABLE 2 | Constraints for factors in mixture DOE. Low

Constraint

High

3.00 81.50 10.50

A: CAB 381-2 B: Toluene C: Gen 0451 A+B+C

6.00 86.50 12.50 100.00

amount of each formulation component is empirically determined through experimentation, but when these components are combined at the determined ratios, the results are far less desirable than predicted. When evaluating Borchi® Gen 0451 pigment dispersant in CAB/TPA automotive refinish applications, this phenomenon was experienced. Laboratory trials to evaluate Borchers® dispersants produced inconclusive and even conflicting results. The problem lies in the fact that the separate components could have interactions with each other with respect to the desired properties. For example, when the formulator changes the level of dispersant in the grind formulation, the loading of the other components is also changed. If all the components have interactions with the responses, how can you conclude that changes in the desired properties are due only to the change in dispersant level – even if the ratio for the other components remains constant? If one plans traditional experiments, altering the ratios of each component individually and in combination with the other components, the number of trials adds up quickly, and this approach is simply not feasible. There is a powerful statistical approach that is well suited for formulation optimization. It is a subset to the design of experiment (DOE) technique called mixture statistics. This statistical technique is designed to allow the experimenter to account for all component interactions, and calculate a formulation that is most likely to maximize the desired properties.1 Unfortunately, a common response to the mere mention of DOE is skepticism and resistance. It is true that a traditional factorial DOE is very limited in value when applied to formulation development. However, a DOE need not be the all-encompassing, labor-intensive exercise that many have encountered. In fact, the proper application of DOE methods should minimize the amount of time and resources needed to achieve the desired goals.2-4

The Formulation To illustrate the use of mixture statistics, a generic automotive refinish black basecoat formulation was

By Kip A. Howard, Research and Development Laboratory Manager | OMGroup Paint and Coatings Additives, Westlake, OH 38



NOV EMBER 2011 | W W W . P C I M A G . C O M

A: CAB 381-2 %

B: Toluene %

C: Gen 0451 %

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

6.00 3.33 3.00 4.65 5.44 6.00 4.98 4.00 5.44 4.00 3.00 3.00 4.65 3.00 3.80 4.25

83.50 85.55 86.50 84.01 82.76 81.50 84.52 83.50 82.76 83.50 85.02 86.50 84.01 85.02 84.36 85.25

10.50 11.11 10.50 11.33 11.80 12.50 10.50 12.50 11.80 12.50 11.98 10.50 11.33 11.98 11.84 10.50

TABLE 4 | Measured responses for mixture DOE grind formulation trials.

Run

60° Gloss

L*

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

92.65 104.35 98.35 108.50 98.30 98.55 96.05 106.15 98.55 103.35 98.20 100.10 104.90 103.25 95.65 94.90

24.38 27.04 24.90 27.67 25.07 25.27 24.34 27.48 25.63 27.91 25.05 25.85 26.50 26.46 24.29 24.51

TABLE 5 | Constraints for mixture optimization calculation. Name A: CAB 381-2 B: Toluene C: Gen 0451 60° gloss L*

Goal

Limit

Limit

Is in range Is in range Is in range Maximize Minimize

3.00 81.50 10.50 92.65 24.29

6.00 86.50 12.50 108.50 27.91

TABLE 6 | Calculated optimal grind formulations based on DOE mixture results. CAB 381-2 Toluene

5.25 82.25

Borchi Gen 0451

12.50

60° Gloss L* Desirability

102.47 25.23 0.68

FIGURE 1 | 3-D surface of L* as a function FIGURE 2 | 3-D surface of 60° gloss as a of the three factors. function of the three factors. 34 32 30 28 26 24 22

60º Gloss

Run

L*

TABLE 3 | Grind formulation mixture design.

C (10.500)

B (86.500)

A (3.000)

A (8.000)

120 115 110 105 100 95 90

A (8.000) C (10.500)

B (81.500) C (15.500)

B (81.500) B (86.500)

A (3.000)

C (15.500)

chosen (Table 1). Design Expert ® by Stat-Ease, Inc. was used to develop the mixture DOE. This project focused on optimizing the grind formulation for maximum color development and gloss.

Mixture DOE Three components were included in the mixture, keeping the level of carbon black constant for each trial: A: CAB resin; B: Toluene; C: Borchi Gen 0451. In a mixture DOE, all of the components are varied based on a statistical model, with the total adding up to a predetermined constant (in this case, 100 parts or percent). However, it is not useful to include trials that are not feasible. For instance, one would not want to include trials where the level of CAB resin is higher than the maximum soluble amount. These are called constraints. The constraints for the grind mixture DOE are listed in Table 2. The responses (desired properties) were defined as R1: 60° Gloss, and R2: L* value. Using the quadratic design model, the trials were generated as listed in Table 3. Each of these trials was used to disperse 12.66% carbon black and processed simultaneously for 2 h on a LAU DAS-200 disperser. The resulting paint samples were drawn down at 5 mils wet thickness and allowed to dry for 12 h at 25 °C, 50% relative humidity. The drawdowns were then measured for color and 60° gloss; the results can be found in Table 4. After analyzing the results, it was determined that this mixture has A:B:C interactions for each component, confirming the theory that complex synergies exist in this formulation. After selecting a model that best fit our data and accounted for these interactions (in this instance the cubic model), we generated a visual representation of our three-component mixture with respect to each response (Figures 1 and 2). Examining these graphs, it was apparent that our responses had conflicting optimal formulations. Mixtures that maximized gloss also minimized color strength and vice versa. The goal now was to find the optimum formulation that provided the best color strength in combination with the best gloss. The good news was that we had all the data necessary to accomplish this. The optimum grind formulation could now be calculated by choosing the constraints found in Table 5. The Design Expert software then interpolated 40 additional responses based on the model, and provided the suggested optimized formulation (Table 6). PA I N T & C O A T I N G S I N D U S T R Y



39

Formulation Optimization Utilizing DOE Mixture Statistics

TABLE 7 | Optimized grind formulation validation test results. L*

60° Gloss

26.19

104.25

Validation The calculated optimal formulation from Table 6 was produced and tested using the same methodology as our trial grinds to validate the predicted responses by our model; the results are located in Table 7.

Conclusions The use of mixture statistics with formulation development is valuable because it provides a clear, concise path to obtain an optimum formula within a practical number of trials. However, this technique can also provide a complete understanding of interactions that exist between all of the ingredients with respect to the desired properties. Limitations of the formulation are also characterized, preventing the formulator from setting specification goals that are unachievable using current raw materials and processes. This information provides additional value to the time and resources expended developing the formulation that traditional trial work simply does not offer. 

References 1

2

3

4

Experimenting with Mixtures, Chemtech, Nov., 1979, pp 702-710. Jameel, Feroz and Hershenson, Susan. Formulation and Process Development Strategies for Manufacturing Biopharmaceuticals, John Wiley and Sons, 2010 pp. 320-327. Anderson, M.J. and Whitcomb, P.J. Mixture DOE Uncovers Formulations Quicker, Rubber and Plastics News, October 21, 2002.2. Scheffe, H. Experiments with Mixtures, J. of the Royal Society Series B, Vol. 20, No. 2, 1958, pp. 344-360.3.

E-mail [email protected] for more information, or visit www.omgi.com or www.borchers.com. The author would like to thank the following individuals for their contributions: Mary Hopkins, Nicholas Schady, Susan Vicha and Timothy Armistead.

Find On-Demand Webinars at webinars.pcimag.com or www.borchers.com. Visit ads.pcimag.com 40



NOV EMBER 2011 | W W W . P C I M A G . C O M

A New Way to Produce

Antimicrobial Coatings

A

nti ntimicrobial t i miicro obi bial a l coa coatings oati tin ti i ng ngs are used used d in i n many y applications, varying applications s, va vary ryin ry i ng from antifouling paints, coatings used in hospitals and on medical equipment, to algaecidal and fungicidal coatings in and around the house. A growing problem in our world is that, for reasons of health and the environment, more and more biocides are being prohibited, and at the same time, bacteria are becoming more resistant. AM Coatings has developed a unique and worldwide patented technology under the name of AM Inside®. This technology provides safe and durable protection against bacteria, algae, molds and fungi. Coatings with this new technology do not contain biocides. AM Inside operates differently than traditional antimicrobial coatings – mechanically rather than chemically. By using a double polymerization process, an antimicrobial binding agent is fabricated. This binding agent has a very special property, creating a kind of “nanotechnological barbwire” surface, during the curing process. When a microbe (or any micro-organism) comes in contact with this surface, its cell wall is punctured like a balloon, so the microbe dies (Figure 1). Apart from being completely safe for humans and the environment, this mechanical action has another big advantage: microbes will not become resistant to this kind of control, a phenomenon that appears to become a growing problem, for instance with the notorious MRSA infection in hospitals. Traditional antimicrobial coatings contain biocides that are gradually released (leach out). The resulting toxins then enter the microbe and kill it. Although this is an effective process, there are a few important drawbacks, which can be avoided by using this new technology. • Standard biocides may pose a health risk1 and may be environmentally hazardous.2 This is why application of these biocides is increasingly being restrained and subjected to strict and costly admission requirements. • Because the active ingredients leach out, these chemicals have only a short life span.3 The effects diminish in

FIGURE 1 | Schematic illustration of the anti-bacterial function of AM Inside.

Kille

Bacteria

d Bac

teria

Leakage of Cell Components

FIGURE 2 | Tomato test after 38 days.

Without Coating

Silver-Based Biocide

AM Inside

due course because the biocide concentration diminishes. • The direct surroundings are contaminated with higher concentrations of biocides. AM Inside technology has been proven, based on American ASTM E 2149 and Japanese JIS Z 2801 standard test methods. Practically, the technology has been proven as well. Figure 2 shows a tomato that did not deteriorate, decay or mold inside a beaker coated with AM Inside, even after 38 days. The other two beakers (one without a coating and one coated with a silver-based biocide), show clear deterioration.

Summary AM Coatings’ technology is not harmful to humans or animals; it can be applied everywhere and without special precautions. No special labeling or costly and time-consuming registration and admission procedures are required. AM Inside grafted on the polymer is made with common and widely available raw materials, and all are REACHcompliant. It is non-leaching, meaning there is no negative environmental impact and no loss of effectiveness. AM Inside is effective against a wide number of strains of bacteria including MRSA. Because it works mechanically, it is impossible to build up resistance against it. Waterborne paints based on this technology possess enhanced low-odor and nonbleeding properties, and are just as green and sustainable as common, unmodified paints not containing additional antimicrobial components. AM Coatings is expanding its range of binders modified with the technology, serving other coating applications and non-coatings segments. For more information, and to view an animated video on how this technology works, visit www.amcoatings.com and www.am-inside.com. 

References

AM Inside

1

2

Surface

3

The Role of Antimicrobial Silver Nanotechnology, Medical Device & Diagnostic Industry Magazine, August 2005. Chai, Joyce S. Water Conditioning & Purification Avoiding the Silver Lining, 12/2008. Anti-infective catheters: A difficult search for effective slow delivery systems.

By Hossein Mahmoud, Inventor and Director | AM Coatings, Ede, The Netherlands. PA I N T & C O A T I N G S I N D U S T R Y



41

Innovation and Sustainability Highlighted at

ABRAFATI 2011

A

BR AFAT BRAFATI BRAF ATII 2011 2011 will wil illl be held hel eld d from from NovemNov ovem em ber 21 - 23 at Transamerica Expo Center, in São Paulo, Brazil. The most important event in the coatings sector in Latin America will gather the 12th International Exhibition of Coatings Industry Suppliers and the 12th International Coatings Congress. Solutions to the future demands of the coatings industry will be highlighted both in the Congress and the Exhibition, which will present and discuss paths and trends in terms of raw materials, products, processes, technologies, applications, environmental impact and many other areas. Over 200 companies have already confirmed their participation in the Exhibition. The favorable growth perspectives for the Brazilian and Latin American coatings industry in the coming years are stimulating suppliers, who see ABRAFATI 2011 as an excellent opportunity to expand their businesses. As a result of the investments in oil exploitation, infrastructure improvement, preparation for the Soccer World Cup and the Olympic Games, it is estimated that the Brazilian market will double its current size in a few years. This will probably be the most international of the event’s editions, with significant presence of European, North American and Asian companies.

12th International Coatings Congress At the International Coatings Congress, experts will present ongoing research and recent developments, which open new possibilities for the formulation, production or use of coatings. Environmental aspects will be a highlight because of the growing relevance of the theme for society and for the future of the coatings industry. As with every edition of the Congress, many studies on technologies, raw materials and innovative processes will be presented under the form of lectures or posters addressing how to improve the performance of coatings,

costs produce add functionalities add func fu ncti tion onal alit litie ies to them, the hem m reduce red educ ucee co cost sts an and d pr prod oduc ucee le less impact on the environment. The Congress includes 72 oral presentations, the Poster Session and two special seminars, one on radiation-cure technology, and one on environmental and safety issues. The entire program is available at www.abrafati.com.br. One of the highlights of ABRAFATI 2011 are the Plenary Sessions, which offer comprehensive and privileged perspectives on key issues in the coatings chain. These sessions will be presented by professionals with a broad range of expertise and a tangible record of accomplishments.

Plenary Sessions November 21 – 1st Plenary (8:30 a.m. - 9:30 a.m.) The Performance of the Coatings Industry in 2011 and the Brazilian Scenario for the Decade Antonio Carlos de Oliveira Chairman of the Executive Board of ABRAFATI, Director of the division of DuPont Automotive Systems in Latin America, General Operation Manager of DuPont Performance Coatings Brazil November 21 – 2nd Plenary (6:00 p.m. - 7:00 p.m.) Coatings and Raw Materials: Perspectives on the Global Market John Klier Global Research and Development Director of Dow Coating Materials November 22 – 3rd Plenary (8:30 a.m. - 9:30 a.m.) Automotive Coatings and the Environment Lewis E. Manring Vice-President of Technology of DuPont Performance Coatings November 23 – 4th Plenary (8:30 a.m. - 9:30 a.m.) The Coatings Global Market: Dimension, Tendencies and Key Themes Louis McCulloch Specialized consultant in the coatings industry, with over 30 years as an executive in companies in the sector, former editor of The Coatings Agenda. 

ABRAFATI 2011 November 21 - 23, 2011 Exhibition: 7:00 a.m. to 4:00 p.m. Coatings Congress: 10:00 a.m. to 8:00 p.m. Location: Transamérica Expo Center, São Paulo, Brazil Information and registration: www.abrafati2011.com.br

42



NOV EMBER 2011 | W W W . P C I M A G . C O M

Novembro 2011

Paint

Coatings Industry

Biocida com Liberação Controlada Agente Umidificador para Adesivos Tecnologia de Poliuretano à Base de Água

P O N TO D E V I S TA

Brasil posicionado para o crescimento Recentemente, tive uma conversa telefônica muito interessante com David P. Nick, Presidente e CEO da DPNA International Inc. Durante a conversa sobre o evento da ABRAFATI realizado esse mês em São Paulo, Brasil, Dave me falou sobre a aliança dos países do BRIC. Eu sempre leio bastante sobre as economias em rápido crescimento e a expansão do setor de revestimentos no Brasil, Rússia, Índia, China e África do Sul (países do BRICS), mas eu não sabia que esses países tinham formado uma aliança comercial sem precedentes. O BRICS não é um bloco comercial formal, mas uma aliança econômica flexível, não baseada numa moeda, em política ou em diretrizes comerciais tradicionais. Cada um desses países tem alguma coisa que os outros querem. Para citar algumas delas, o Brasil tem terra, petróleo e produtos agrícolas; a Rússia tem petróleo e gás, a China tem uma mão de obra imensa e necessidade de petróleo e gás; a Índia tem amplo conhecimento e recursos de TI e a África do Sul tem metais preciosos e diamantes e é a porta para a África. Mais do que estabelecer acordos comerciais MOINHO HORIZONTAL PÉROLA PACOTE DE SELO MECÂNICO MULTILANGUAGE PLC CONTROLE DIFERENTES MATERIAIS DE CONSTRUÇÃO

PRODUÇÃO EM LOTES PROJETO SIMPLE, ROBUSTO TODA A CONSTRUÇÃO DE AÇO OPERAÇÃO AUTOMATIZADA AMPLA VARIEDADE TAMANHO

PROCESSAMENTO PERSONALIZADO DEIXE NOSSOS ESPECIALISTAS AJUDÁ-LO COM A SUA DISPERSÃO PROJETOS, APRESENTADA MOSTRA QUE VOCÊ PRECISA E COMECE AGORA

baseados em dólares ou euros, esses países criaram acordos de permutas. A China, por exemplo, pode concordar em construir um sistema rodoviário na África do Sul, incluindo o financiamento, mão-deobra e equipamentos, em troca de um contrato plurianual para o desenvolvimento dos recursos relacionados a metais ou carvão do país. Essa aliança pode tornar o crescimento contínuo desses países em algo real e sustentável. Ela não depende do que acontece na Europa ou nos Estados Unidos. De acordo com Nick, o BRICS representa uma transferência coletiva do poder econômico dos países desenvolvidos do G-7 para o mundo em desenvolvimento, e muitos outros países estão ansiosos para entrar para o clube. Espero ler mais sobre a BRICS e acompanhar o seu progresso nos próximos anos. Mesmo com a publicação recente de um informativo da ABRAFATI (Associação Brasileira de Fabricantes de Tintas) afirmando que o crescimento do setor de revestimentos caiu 10% no Brasil em relação à 2010, o futuro parece promissor. O crescimento total do setor de tintas no Brasil deve ser de 1,3% (devido ao clima econômico internacional questionável e a dúvida sobre reformar ou construir), alcançando 1.377 bilhões de litros, com expectativa de crescimento das vendas na ordem de 4% em 2012. Numa tentativa de promover o desenvolvimento econômico e social, o governo brasileiro lançou o programa habitacional Minha Casa, Minha Vida 2 e prorrogou a redução do IPI. De acordo com Dilson Ferreira, presidente executivo da ABRAFATI, “é importante frisar que, além dos grandes eventos que teremos até 2022 (como a Copa do Mundo da Fifa em 2014 e as Olimpíadas em 2016), que garantirão o crescimento sustentável, os aspectos estruturais que estimulam as vendas estarão presentes por muitos anos. Entre esses fatores, os mais notáveis são o investimento em habitação e infraestrutura, a ampliação dos segmentos relacionados à exploração e distribuição de petróleo, o fortalecimento do mercado interno e o crescimento da classe média.” Na tentativa de alcançar esse mercado em crescimento e os participantes do evento da ABRAFATI, a PCI apresenta o nosso primeiro suplemente em português nesta edição, que será distribuída na feira. Esperamos essas informações sejam úteis e esclarecedoras para os leitores da edição em português e que possamos publicar mais suplementos como esse no futuro.

CMC ARGENTINA, LTD. USA FLEETWOOD, PA 19522 1 (610) 926-0984 WWW. CMCMILLING.COM

ARGENTINA VILLA ADEUNA, BUENOS AIRES, AR (54-11)4717-0345 WWW.SPECHEM.COM.AR

VISTA EM ABRAFATTI—ESTANDE NÚMERO 244

Acesse ads.pcimag.com 44 NOVEMBRO 2011 |

WWW.PCIMAC.COM

Kristin Johansson, Editora | PCI

Inovação para Todos

Há mais de uma década, a Celanese é líder no desenvolvimento de emulsões para tintas amigáveis às pessoas e ao meio-ambiente. Na América do Sul, estamos atualmente tornando mais fácil a formulação de tintas decorativas de alto desempenho e com atributos amigáveis que todos possam apreciar. Venha nos visitar na Abrafati 2011 onde você poderá saber mais sobre as emulsões EcoVAE® para tintas com baixa emissão VOC, baixo odor, e livre de Alquilfenóis Etoxilados. Venha conhecer nossa tecnologia de emulsões e os recursos que a Celanese pode oferecer para inovar a forma de produzir tintas decorativas na América Latina. Venha nos visitar na

ABRAFATI Stand 176

Ligue agora: +55 11 8653 0490 www.Celanese-Emulsions.com/Brasil

Em todo o mundo…seu futuro é nosso foco.

Desempenho Superior de por meio do Controle da

B

iocidas são necessários para evitar a deterioração microbial de vários revestimentos industriais. As duas principais aplicações dos biocidas são (a) evitar a deterioração do produto em estado molhado durante o armazenamento e transporte (proteção na lata) e (b) garantir um desempenho duradouro do revestimento (proteção da película seca).1 Ao secar, tanto as tintas à base de água como de solvente ficam vulneráveis à formação de colônias de fungos e/ou algas. O crescimento de micro-organismos na película seca não somente afeta a aparência do revestimento (descoloração), mas também compromete o seu desempenho (biodegradação). Pode haver penetração de fungos nos revestimentos, causando trincas, bolhas e perda da adesão, levando à deterioração ou corrosão do substrato. Colônias de algas, que parecem crescer mais rapidamente sobre substratos porosos, como estuco, cimento e tijolos, ocluem água. O congelamento e degelo dessa água presa podem causar trincas ou aumentar a permeabilidade do revestimento, levando a defeitos. A presença de água pode também estimular a formação de colônias de outros micro-organismos que, por sua vez, podem causar biodegradação.2 O tipo de micro-organismo que consegue colonizar o revestimento depende de vários fatores, como teor de umidade da superfície, presença de nutrientes, substrato e composição do revestimento.3 A fim de ser mais eficaz, o biocida precisa estar presente na interface do revestimento. Isso faz com que ele seja suscetível à lixiviação por água. O controle da liberação do biocida por meio do encapsulamento pode garantir que uma concentração mínima de biocida seja sempre mantida na superfície da interface, prolongando a vida útil do revestimento. Além disso, essa liberação controlada pode reduzir a quantidade de biocida liberada no meio-ambiente ao longo do tempo. Este artigo descreve a liberação controlada de IPBC (3-iodo2-propinil butilcarbamato). Consegue-se uma proteção duradoura da superfície por meio da absorção entre o biocida e o portador.4,5 Isso faz com que o biocida se torne resistente à FIGURA 1 | Lixiviação Cumulativa de IPBC em películas. 14 13

IPBC

% IPBC

12 11

Fungitrol® 940CR

10 9 8 7

1

3

15

48

Hours Horas

lixiviação. O IPBC encapsulado foi liberado mais lentamente do que o não encapsulado, conforme medido por métodos analíticos e microbiológicos. O biocida encapsulado também ficou mais resistente à degradação ambiental causada pelos raios UV e pelo calor. Além disso, testes de exposição ao ar livre realizados com tintas que contêm IPBC encapsulado comprovaram uma melhor proteção da película seca.

Experimento Preparação da Amostra de Película de Tinta

IPBC encapsulado e não encapsulado foram injetados em vários níveis às amostras de tinta. Foram feitas aplicações de cima para baixo, formando películas de 3 mils em papel cartão apropriado (Lanetta), seguidas da secagem em temperatura ambiente por, pelo menos, 24 horas.

Medições do IPBC IPBC Presente na Água Lixiviada Amostras de tinta foram preparadas, conforme descrito acima, com 10.000 ppm de IPBC. As películas das tintas foram suspensas em 100 ml de água com agitação constante. A água lixiviada foi coletada em intervalos diferentes de tempo e o seu teor de IPBC foi analisado com um espectroscópio GC UV-Vis. A concentração de IPBC foi determinada por meio de uma curva IPBC padrão a uma absorvência máxima de 224-228 nm. Quantificação do IPBC em Películas de Tinta usando EFRX As amostras de tinta preparadas conforme descrito acima, contendo 2.000 ppm de IPBC, sofreram lixiviação em vários intervalos de tempo com uma taxa de lixiviação de 1 litro por hora. As amostras foram secas por, pelo menos 24 horas. O equipamento de fluorescência de raios X (FRX) Epsilon 5 foi usado para analisar o teor de iodo nas amostras.6 Uma curvapadrão de IPBC foi desenvolvida com concentrações diferentes de IPBC, sendo linear até 4.000 ppm de IPBC. A correlação linear não dependia da formulação da tinta usada para criar a película. Linhas de base de cada película de tinta foram obtidas antes e após a lixiviação. Medições Delta Y As amostras de tinta contendo 1.000 ppm de IPBC foram preparadas conforme descrito acima. As amostras foram colocadas em uma unidade QUV sob lâmpadas UVB por 24 horas. O índice de amarelamento (IA) foi medido com um espectrofotômetro (CM2500d da Konica Minolta) dentro de 1 hora após as películas serem retiradas da unidade QUV (ASTM E 313 – 10 – Método Padrão para Cálculo dos Índices de Amarelamento (IA) e Brancura para Medição Instrumental das Coordenadas de Cor). O Delta Y foi determinado subtraindo-se o IA da amostra tratada com biocida menos a amostra de controle não tratada após exposição no QUV.

Por Raman Premachandran, Cientista Sênior II, e Karen Winkowski, Diretora Técnica Sênior, Produtos Químicos de Desempenho & Biocidas Industriais | Ashland Specialty Ingredients, unidade comercial da Ashland Inc., Wayne, NJ

46

NOVEMBRO 2011 | W W W . P C I M A C . C O M

Películas Secas de Revestimentos Liberação de IPBC Ensaio Acelerado de Fungos A norma ASTM D 5590 (Determinação da Resistência de Películas de Tinta e Revestimentos Afins à Degradação por Fungos em Placa de Ágar em 4 semanas ) foi usada para medir a eficácia de vários tratamentos biocidas nas películas de tinta. As amostras de tinta foram preparadas, conforme descrito acima, adicionando-se, porém, 500 ppm de IPBC às amostras. As amostras foram lixiviadas, conforme descrito acima, e inoculadas com uma suspensão de fungos mistos contendo Aspergillus niger (ATCC 6275) e Penicillium funiculosum (ATCC 11797), com concentração final de 107 esporos/ml. Em seguida, as placas foram incubadas por 28 dias a 28°C e 85% UR. O crescimento de fungos na superfície da amostra pintada foi classificado numa escala de 0-4, na qual “0” representava zero crescimento; 1 representava traços de crescimento ( Verniz A. Após o intemperismo acelerado, observa-se uma diminuição da resistência a fraturas frágeis em todos os sistemas. Esse fenômeno é consistente com o “endurecimento” observado nas medições da nanoindentação, sendo mais pronunciados nos Vernizes A e C. Enquanto os resultados do Verniz A são, até um certo ponto, esperados e devidos à menor estabilidade da rede acrílico/ melamina em condições de intemperismo acelerado (em comparação aos poliuretanos), a diminuição, no caso do Verniz C, é mais surpreendente. No entanto, C ainda exibe um desempenho um pouco melhor entre os sistemas testados, mesmo após um envelhecimento acelerado. Os Vernizes B e D mostram o mesmo desempenho, o que é particularmente interessante, considerando-se o excelente desempenho do Verniz B, obtido no teste de lavagem de carro.

Resistência ao intemperismo e à corrosão ácida TABELA 7 | Resistência do verniz aos raios UV e à corrosão por ácido.

Verniz A

Verniz B

Verniz C

Verniz D

Retenção do brilho (20°) após 1500 horas no WOM

Referência