ALMATEX
®
A C R Y L I C
Premium
Performance
Durable
R E S I N S
Novel
Dependable
Acrylic Resins
P R E M I U M
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.
Printed with permission of BMW AG
Applications:
Automotive Wheel
Clear Top Coats
Auto Primer
Pigmented Coatings These resins contain glycidyl functional groups
which, when combined with polycarboxylic acid
compounds as the curing agent, exhibit excellent
properties for coating materials.
Architectural
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.
Wood and MDF
Outdoor Furniture
Powder on Plastic
UV Curable Coatings
Plumbing Fixtures
Industrial
Plastics and other Heat
Sensitive Substrates
Lawn & Garden
Agricultural
Machinery
PERFORMANCE
Chemistry of GMA
Acrylic Resins
Almatex® GMA Acrylic Resins are made by free radical, solution
copolymerization of Glycidyl methacrylate (GMA) with other
acrylic or vinyl aromatic co-monomers.
H3C
Free Radical Copolymerization
O
C
C
H2C
O
H2C
CH
O
+
CH2
Acrylate or
Methacrylate Monomers
and other
Unsaturated Monomers
1
w1 ______
w2 ______
w3 ...
______
+
∞=
∞+
∞+
Tgc Tg1 Tg2 Tg∞3
Printed with permission of Goodrich Technology Corporation
Degree of Functionality
Monomer Composition
O
Initiator Type
O
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:
______
Variables:
∞
C
Tgc = Tgc_ ____
MW
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.
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
D U R A B L E
GMA Powder
Coating 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 1,12dodecanedioic 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.
Formulation
Process:
PREMIX
ALMATEX® GMA acrylic
resin is initially mixed
with crosslinking agents,
pigments, other additives
and thoroughly dry
blended.
MELT-BLENDING
The 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.
PULVERIZING
After cooling the melt
blended compound is
crushed and passed through
classification process for
desirable particle size
(typically 150-200 mesh).
APPLICATION
The 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.
O
V
E
L
62
®
Heat Flow Endo Up (mW)
N
Typical DSC Thermogram of
GMA Powder Coating
DDDA Melt Region
Heating Conditions: 10oC/min
60
Inherent nature of
Low Temp. Cure (<140oC)
and good storage stability
58
56
54
Global Support
Glass Transition Region
Complete Powder
Coating Laboratory
52
Powder Softening Region
50
48
Anderson
R&D Support
Capabilities:
Curing Reaction Region
15 40 60 80 100 120 140 160 180 200
Temperature (oC)
● Premix through
Oven Cure
Complete Powder
Testing Facility
● Thermal
Analysis
● GPC
● GC
● FTIR
GMA vs 2K Clearcoat
Functional Quality
(Mechanical / Chemical)
GMA PCC
10
2K CC
Cleaning &
Chemicals
8
Formulation Development
Optical
Quality
6
Printed with permission of Smart GmbH
Problem Solving
4
2
Material
Utilization &
Recyclability
Actual Cost
(Material, Operation
& Maintenance)
Process
Stability
No Solvent
Emissions
No Waste Water
Lab to Pilot Scale
DEPENDABLE
GMA vs Other Powder Coating
Chemistry in Weatherability
Percent 60 Gloss Retention
120
Anderson
Production
Capabilities:
100
80
Continuous
Devolatilization
60
40
GMA Acrylic
Superdurable Polyester
HFA Acrylic
Semidurable Polyester
Standard Polyester
20
0 500 1000 1500 2000 2500 3000 3500 4000 4500
Xenon Arc Weatherometer (KJ/m)
● Heat Sensitive
& UV Curable
Resins
Masterbatching
Bulk Packaging
Comparison of Powder Melting-Curing
Profile of GMA & Polyester Powder Coatings
1E+6
Complex Viscosity. PaS
Higher cross-linking density
1E+5
1E+4
1E+3
GMA Powder Coating
Polyester Powder Coating
1E+2
1E+1
Rapid melt &
Lower flow viscosity
Heating Conditions:
Ramp from 80oC to 145oC @ 10oC/min
& hold @ 145oC
1E+0
0 120 240 360 480 600 720 840 960 1080 1200 Time, sec
● Supersacks
● Drums
Private Label
Manufacturing
● Solid Acrylic
Resins
● Liquid Acrylic
Toll Resins
Iso 9001:2000
Certified
General Purpose Almatex® Resins
PD-7610
High Tg
Short Gel-time
Better Pigmentation
Better Adhesion
Lower Odor & Cost
Higher Reactivity
Lower GMA Content
Dual Functionality
GMA-Hydroxy
Polyester Compatible
& Better Pigmentation
Almatex® Resin Properties
PD-6300
Epoxy
ALMATEX®
Equivalent
Resin
(g/eq)
PD-7690
PD-4219
PD-9200
PD-1700
Improved Flow
PD-4409
PD-4411
High Performance Almatex® Resins
PD-3402
Better Flow
Higher Crosslinking Density
PD-3402X
PD-4408
PD-4418
Higher Acid
Etch Resistance
PD-4421
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)
Tg
(oC)
Melt
Melt Index
Viscosity
(g/10 min)
(poise)
(@ 125oC)
Applications
o
(@ 150 C)
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
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.
Bibliography
Select Cure-curve of Almatex® GMA Resins
400
350
Viscosity, poise
300
250
200
150
100
50
0
0
50
100
150
Time, seconds
200 250
PD-7610
PD-6300
PD-7690
PD-4219
PD-9200
PD-1700
AP-4411
AP-4418
PD-3402 (MI=56)
PD-3402 (MI=77)
300
1.
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5.
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22.
US3752870 “Powder Coating Compositions Containing Polymer of Ethylenically Unsaturated Glycidyl Esters, Dicarboxylic Acids, and Flow Control Agents” by Ford; 1973.
JP78 105,533 “Metallic Finish Powder Coating Utilizing Commercial Almatex PD-2310 Resin and
Aluminum Powder” by Kansai Paint; 1978.
US4091048 “Powder Coating Compositions Containing Glycidyl Ester Copolymers and Organic
Carboxylic Acid Anhydride Crosslinking Agent” by Ford; 1978.
US Re32,261 “Process for Producing Thermosetting Finishing Powder” by Mitsui Toatsu Chemicals; 1986.
US5270391 “Composition for Thermosetting Powder Coatings” by Mitsui Toatsu Chemicals; 1993.
“New Generation Body Powder Primer Surfacer and Body Pillar Blackout Material” by General
Motors; IBEC-94, Automotive Body Painting; p82-85.
“Acrylic Powder Clear Coat for Automotive OEM” by Hoechst AG; EuroCoat 9/1994; p574-579.
“Physical Chemistry of Acrylic Powder Coatings” by Zeneca Resins, Waterborne & High-solids, and Powder Coatings Symposium; 1995; p310-319.
US5407747 “Filiform Corrosion Resistance Aluminum Automotive Road Wheel” by Morton; 1995.
US5744522 “Low Gloss Coating Compositions” by Mitsui Toatsu Chemicals/Anderson Development Company; 1998.
“Advances in High-Performance Powder Coatings for Automotive Exterior Trim” by Ferro; Metal
Finishing May 1999; p14-18.
“Development Status of Powder Coatings for OEM Automotive Applications” by Seibert Powder
Coatings, Powder R&D Winter/2000; p3-7.
US6077608 “Multilayered Coating with Powder Clear Coating and Substrates Therewith and Method” by PPG; 2000.
“Automotive OEM Powder Clearcoat” by PPG; PCI, Paint & Coating Industry; April 2000.
“Powder Clearcoat, a Leap in Paint Technology” by Editor of Aei Feb 2001; p204-208.
“Technology Broadens Horizons for Acrylic Powder Coating” by PPG; Powder Coatings March 2001; p25-32.
“GMA Powder Coatings: Driving the Future of Automotive Clear Topcoats” by Editor of Paint &
Coatings Industry; May 2001; p54-56.
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.
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.
US2003/0212216 “Thermosetting Powder Coating Composition, Method for Forming Coating Film of the Composition, and Coating Film” by Mitsui Chemicals, Inc., 2003.
US6762259 “Process for the Production of Living (co)Polymers and Use of the (co)Polymers” by Mitsui Chemicals, Inc., 2004.
US2004/0265494 “Glycidyl (meth)Acrylate Powder Coating Compositions Containing Caprolactonederived Side Chain” by Anderson Development Company, 2004.
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.
ALMATEX
®
A C R Y L I C
R E S I N S
Anderson Development • 1415 E. Michigan Road • Adrian, MI 49221
Tel: 517.263.2121 • Fax: 517.263.1000 • www.andersondevelopment.com