A L M A T E X®

A C R Y L I C R E S I N S

Premium Performance Durable Novel Dependable

P R E M I U M

Printed with permission of BMW AG

Keeping that shine on your automobile is important to you.Our products help you maintain it.  

Our innovative acrylic resins are used extensively in powder coating applications in the automotive industry.  Other  markets  include  aluminum wheels,  outdoor  furniture,  lawn  and  garden equipment, and various architectural uses.

These resins contain glycidyl functional groups which, when combined with polycarboxylic acid compounds as the curing agent, exhibit excellent properties for coating materials. 

Powder  coating  made  from  Almatex® GMA acrylics  is  especially  noted  for  weatherability, gloss, crystal clarity, chemical  resistance, and smooth  finish.  The  resins  exhibit  excellent over  bake  tolerance,  good  caking  stability, excellent  electrical  insulation  properties,  and an  outstanding  performance  in  electrostatic spraying equipment.  These products are also more  environmentally  friendly  than  solvent based products.

Acrylic Resins

Applications:

Automotive Wheel

Clear Top Coats

Auto Primer

Pigmented Coatings

Architectural

Outdoor Furniture

Powder on Plastic

Wood and MDF

UV Curable Coatings

Plumbing Fixtures

Industrial

Plastics and other Heat Sensitive Substrates

Lawn & Garden

Agricultural Machinery

PERFORMANCE Almatex®  GMA Acrylic Resins are made by free radical, solution copolymerization  of  Glycidyl  methacrylate  (GMA)  with  other acrylic or vinyl aromatic co-monomers.

The  stable  -C-C-  polymer  backbone  of  GMA  resins  confers good outdoor weathering & chemical resistance.  Unlike liquid coatings,  powder  coating  resins  are  restricted  to  monomer selection and molecular weight  (MW)  to  inhibit  sintering and provide good flow during melt and cure. Hence, the glass transition temperature (Tg) of the final resin is designed to be above some minimum value (usually 40-45 oC) to insure physical stability of the powder coating.  Tg of GMA acrylic powder resin is controlled by two equations:

By controlling monomer compositions and molecular weight, Almatex  GMA  resins  can  be  designed  with  a  wide  range  of melt viscosities, Tg, epoxy equivalent weight, and functionality for different application needs. The selection of monomers and polymer modification processes can produce Almatex®  GMA acrylic  resins  with  a  variety  of  properties  such  as  enhanced pigmentation, compatibility and flexibility.

Removal  of  solvent  and  unreacted  monomers  from  resin product syrup is important to maintain the essentially zero VOC advantage of powder coatings.  The volatile contents of Almatex resins are well controlled to below 0.5%.  Anderson Development Company is installing a revolutionary continuous devolatilization capability in 2007 to further cut the residuals and low molecular weight portion (LMWP) in Almatex® GMA Acrylic Resins.

ADC and  its parent company Mitsui Chemicals  Inc. have full capability to tailor-make Almatex GMA acrylic powder resins to fit various special application needs.

Chemistry of GMA Acrylic Resins

1 w1 w2 w3

Tgc Tg1 Tg2 Tg3

______ ______ ______ ______

∞ ∞ ∞ ∞= + + + ... Tgc = Tgc_ C

____

∞

MW

O

O

CH3

C

CH2

C

O

O

CH2

CHCH2

O

Acrylate or Methacrylate Monomers

and other Unsaturated Monomers

Free Radical Copolymerization

+

Variables:Degree of Functionality

Monomer Composition

Initiator Type

Molecular Weight

Glass Transition Temperature

Advantages:Excellent Long-term Weatherability & UV Durability

Superb Chemical Resistance

Crystal Clarity

Outstanding Hardness

Low to High Gloss

Superb Smoothness & Appearance

Printed with permission of Goodrich Technology Corporation

D U R A B L EFormulation Process:PREMIXALMATEX® GMA acrylic resin is initially mixed with crosslinking agents, pigments, other additives and thoroughly dry blended.

MELT-BLENDINGThe premix is then milled and blended with an extruder in a molten state. Properties of acrylic powder coating may vary depending on the compounding technique used.

PULVERIZINGAfter cooling the melt blended compound is crushed and passed through classification process for desirable particle size (typically 150-200 mesh).

APPLICATIONThe powder is charged and sprayed with an electrostatic spray gun on a grounded substrate. Typical substrates include aluminum, steel, wood, MDF, plastic and other heat sensitive substrates.GMA powder coatings are typically baked at 130 to 180OC for 10 to 40 minutes depending on the powder formulation.

Since GMA acrylic powder coating resins are epoxy functional, any curing mechanism for epoxy resins will also function with GMA resins.  At this time the preferred curative  for  GMA  acrylic  powder  resins  is  1,12-dodecanedioic acid (DDDA) due to its combination of favorable melting point, cure rate & viscosity reduction.  DDDA  also  provides  cured  coatings  with  excellent clarity, chemical resistance and weatherability.  Other polycarboxylic acids or anhydrides may be used as curatives or additives  to modify cure rate or coating properties. 

Many additives used  in  the powder coating  industry may also be used in GMA acrylic powder formulations. These additives include: flow control agents (FCA), de-gassing agents, UVAs, and HALS. For clearcoat applications, non-silica dispersed FCA’s or special solid FCA’s are preferred. The selection of UVA/HALS can also effect  the yellowing and degree of outdoor durability.

Anderson  has  tackled  many  of  the  misnomers  that surround GMA powder coatings.  Our resin designs and powder coating formulations have improved flexibility, allowed robust pigmentation, proved to be effective in obtaining a wide range of matte and gloss finishes and can be combined with other powder chemistries.

Anderson  Development  Company  and  its  parent company Mitsui Chemicals  Inc. have over 30 years experience  with  GMA  powder  coatings  for  various applications,  and  would  be  glad  to  design  private label resins or assist in formulating for specific coating applications.

GMA Powder Coating Formulation

N O V E L

Printed with permission of Smart GmbH

AndersonR&D Support Capabilities:

Global Support

Complete Powder Coating Laboratory ● Premix through Oven Cure

Complete Powder Testing Facility ● Thermal Analysis ● GPC ● GC ● FTIR

Formulation Development

Problem Solving

Lab to Pilot Scale

Typical DSC Thermogram of GMA Powder Coating

Hea

t Fl

ow E

ndo

Up

(mW

)

62

60

58

56

54

52

50

48 15                   40                  60                  80                  100                120               140                 160                180                200

Heating Conditions: 10oC/min

Glass Transition Region

Powder Softening RegionCuring Reaction Region

Inherent nature of Low Temp. Cure (<140oC)and good storage stability

Temperature (oC)

DDDA Melt Region

®

GMA vs 2K Clearcoat

Functional Quality(Mechanical / Chemical)

10

8

6

4

2

Cleaning &Chemicals

Actual Cost (Material, Operation 

& Maintenance)

ProcessStability

OpticalQuality

Material Utilization &Recyclability

No SolventEmissions

No Waste Water

GMA PCC

2K CC

D E P E N D A B L EAnderson Production Capabilities:

Continuous Devolatilization ● Heat Sensitive & UV Curable Resins

Masterbatching

Bulk Packaging ● Supersacks ● Drums

Private Label Manufacturing ● Solid Acrylic Resins ● Liquid Acrylic Toll Resins

Iso 9001:2000Certified

Comparison of Powder Melting-Curing Profile of GMA & Polyester Powder Coatings

Com

plex

Vis

cosi

ty. P

aS

1E+6

1E+5

1E+4

1E+3

1E+2

1E+1

1E+0  0                 120               240              360              480              600               720               840              960              1080             1200           

Time, sec

Heating Conditions: Ramp from 80oC to 145oC @ 10oC/min & hold @ 145oC

Higher cross-linking density

Rapid melt & Lower flow viscosity

GMA Powder CoatingPolyester Powder Coating

GMA vs Other Powder CoatingChemistry in Weatherability

Per

cent

60

Glo

ss R

eten

tion

120

100

  80

  60

   40

  20

     0                  500               1000              1500              2000              2500              3000              3500              4000              4500 

Xenon Arc Weatherometer (KJ/m)

GMA AcrylicSuperdurable PolyesterHFA AcrylicSemidurable PolyesterStandard Polyester

Developmental (Semi-Commercial) Almatex® Resins• UV Curable Solid Acrylic Resins (AP-4410, AP-4414, AP-4416)• Polyester Powder Coating Compatible GMA Resins (AP-4411)• Hydroxy Functional Acrylic Resin (HA-2001)• Crystalline Aliphatic Polyester for High Flexibility (AP-8500)• Other Experimental Resins (AP-XXXX)

General Purpose Almatex® ResinsHigh Tg

Short Gel-time

Better PigmentationBetter Adhesion

Lower GMA Content

Dual FunctionalityGMA-Hydroxy

Polyester Compatible& Better Pigmentation

Higher Reactivity

Improved Flow

Lower Odor & Cost

PD-7610 PD-6300

PD-7690

PD-4219

PD-9200

PD-1700 PD-4409

PD-4411

High Performance Almatex® Resins

Higher Cross-linking Density

Better Flow

Higher AcidEtch Resistance

PD-3402X

PD-4408

PD-4418 PD-4421

PD-3402

ALMATEX® Resin

Epoxy Equivalent

(g/eq)

Tg (oC)

Melt Index (g/10 min)(@ 125oC)

Melt Viscosity

(poise) (@ 150oC)

Applications

PD-7610 510-560 42-46 46-54 200-240 General Purpose, Wheel, Auto Trim, Auto Primer, High Durability

PD-6300 510-560 55-58 10-16 >500 Wheel, Polyester Matting Indoor or Outdoor

PD-6400 385-415 46-51 30-43 240-310 General Purpose, Polyester Matting

PD-7690 450-500 44-46 43-54 200-250 General Purpose, Wheel, Auto Trim, Auto Primer, High Durability

PD-4219 430-470 44-46 45-60 180-260 General Purpose, Wheel, Auto Trim, Auto Primer, High Durability

PD-9200 650-690 43-48 45-60 180-280 Lower Cost, General Purpose

PD-1700 570-625 950-1150* 48-50 35-45 250-310 Pigmented PC, Polyester Additive,

Dual Functional

PD-4409 720-760 950-1200* 38-42 >110 75-120 Cationic UV Curable PC,

Thermoset PC, Dual Functional

AP-4411 500-550 2900-3200* 42-46 45-60 180-250 Polyester compatible, Dual Functional

AP-2025 280-310 66-70 1-2 >500 Low Gloss GMA PC

PD-3402 360-400 45-50 50-70 180-250 Automotive CC, Wheel

PD-4408 350-380 42-46 60-80 125-175 Automotive CC

PD-4418 300-330 41-45 >110 85-125 Automotive CC

PD-4421 300-330 40-43 >110 85-125 Automotive CC

AP-4410 730-770** 40-45 90-110 90-140 Free Radical UV Curable PC

AP-4414 520-560** 40-45 >110 75-130 Free Radical UV Curable PC

AP-4416 740-780 42-46 NA 80-120 Cationic UV Curable PC

HA-2001 652-748* 45-50 40-60 200-250 Hydroxy Functional Acrylic, Urethane-Acrylic PC

* Hydroxy Equivalent Weight **Double Bond Equivalent Weight

ALMATEX® GMA resins contain the lowest volitiles available in the industry (<0.5%). Color (Gardner) <2

Almatex® Resin Properties

The resin data shown in this table is only for resin selection guideline not for QC specification. “AP” and “HA” indicates the Almatex grade is a developmental or semi-commercial resin.

PD-7610

PD-9200PD-3402 (MI=56)

PD-6300

PD-1700PD-3402 (MI=77)

PD-7690

AP-4411

PD-4219

AP-4418

0 50 100 150 200 250 300

400

350

300

250

200

150

100

50

0

Time, seconds

Visc

osity

, pois

eSelect Cure-curve of Almatex® GMA Resins

1. US3752870 “Powder Coating Compositions Containing Polymer of Ethylenically Unsaturated Glycidyl Esters, Dicarboxylic Acids, and Flow Control Agents” by Ford; 1973.2. JP78 105,533 “Metallic Finish Powder Coating Utilizing Commercial Almatex PD-2310 Resin and Aluminum Powder” by Kansai Paint; 1978.3. US4091048 “Powder Coating Compositions Containing Glycidyl Ester Copolymers and Organic Carboxylic Acid Anhydride Crosslinking Agent” by Ford; 1978.4. US Re32,261 “Process for Producing Thermosetting Finishing Powder” by Mitsui Toatsu Chemicals; 1986.5. US5270391 “Composition for Thermosetting Powder Coatings” by Mitsui Toatsu Chemicals; 1993.6. “New Generation Body Powder Primer Surfacer and Body Pillar Blackout Material” by General Motors; IBEC-94, Automotive Body Painting; p82-85.7. “Acrylic Powder Clear Coat for Automotive OEM” by Hoechst AG; EuroCoat 9/1994; p574-579.8. “Physical Chemistry of Acrylic Powder Coatings” by Zeneca Resins, Waterborne & High-solids, and Powder Coatings Symposium; 1995; p310-319.9. US5407747 “Filiform Corrosion Resistance Aluminum Automotive Road Wheel” by Morton; 1995.10. US5744522 “Low Gloss Coating Compositions” by Mitsui Toatsu Chemicals/Anderson Development Company; 1998.11. “Advances in High-Performance Powder Coatings for Automotive Exterior Trim” by Ferro; Metal Finishing May 1999; p14-18.12. “Development Status of Powder Coatings for OEM Automotive Applications” by Seibert Powder Coatings, Powder R&D Winter/2000; p3-7.13. US6077608 “Multilayered Coating with Powder Clear Coating and Substrates Therewith and Method” by PPG; 2000.14. “Automotive OEM Powder Clearcoat” by PPG; PCI, Paint & Coating Industry; April 2000.15. “Powder Clearcoat, a Leap in Paint Technology” by Editor of Aei Feb 2001; p204-208.16. “Technology Broadens Horizons for Acrylic Powder Coating” by PPG; Powder Coatings March 2001; p25-32.17. “GMA Powder Coatings: Driving the Future of Automotive Clear Topcoats” by Editor of Paint & Coatings Industry; May 2001; p54-56.18. US6479588 “Graft Copolymer of Polyamide and A Glycidyl Group-containing Acrylate Copolymer, Process for Preparation and Coating Composition Containing the Graft Copolymer” by Anderson Development Company, 2002.19. US6670411, WO02/28945A1 “Process for Devolatilizing an Acrylic Resin for Preparing a Powder Coating Composition and Composition Capable of Being Formed into a Powder Coating Comp” by Anderson Development Company, 2003.20. US2003/0212216 “Thermosetting Powder Coating Composition, Method for Forming Coating Film of the Composition, and Coating Film” by Mitsui Chemicals, Inc., 2003.21. US6762259 “Process for the Production of Living (co)Polymers and Use of the (co)Polymers” by Mitsui Chemicals, Inc., 2004.22. US2004/0265494 “Glycidyl (meth)Acrylate Powder Coating Compositions Containing Caprolactone- derived Side Chain” by Anderson Development Company, 2004.

Bibliography

ALMATEX® is a registered trademark of Mitsui Chemicals Inc.The information contained in this bulletin we believe to be accurate, but no warranty is given nor is anything to be construed as a recommendation to infringe upon any existing patent. Since conditions of use are beyond our control, all risks of use are assumed by the user.

A L M A T E X®

A C R Y L I C R E S I N S

Anderson Development • 1415 E. Michigan Road • Adrian, MI 49221Tel: 517.263.2121 • Fax: 517.263.1000 • www.andersondevelopment.com