Introduction into powder coatings

DSM Coating Resins

Powder Coating - February 05 -
Introduction into powder coatings 1

• Polymerisation
• Chemistries
• chemical reaction
• advantage/disadvantages
• Application
• Melting/Curing process
• Matting

DSM Coating Resins

Powder Coating - February 05 -
Two types of Polymerisation processes 2

· Addition polymerisation
-A polymerization in which the growth of polymer chains
proceeds by addition reactions between molecules of
all degrees of polymerization (e.g. acrylics)

· Condensation polymerisation
- A polymerization in which the growth of polymer chains
proceeds by condenstation reactions between molecules of
all degrees of polymerization with loss of small molecules
like water. (e.g. polyesters)

DSM Coating Resins

Powder Coating - February 05 -
Raw materials 3

· Diols (glycols) · Dicarboxylic acids

·Neopentylglycol ·terephthalic acid
·Ethyleneglycol ·isophthalic acid
·propyleneglycol-1,2

· Polyalcohols · Polycarboxylic acids

·Trimethylolpropane ·trimellitic anhydride
·glycerol

DSM Coating Resins

Powder Coating - February 05 -
Esterification 4

· Esterification:

· Acid + Alcohol Ester + Water

· Polyacid + Polyalcohol Polyester + Water

· Hydrolysis:

· Polyester + Water Polyacid + Polyalcohol

· Overall:
· Polyacid + Polyalcohol Polyester + Water

DSM Coating Resins

Powder Coating - February 05 -
Main reaction 5

Excess of OH OH-functional polyester

Excess of COOH COOH-functional polyester

DSM Coating Resins

Powder Coating - February 05 -
Powder Coating Formulation 6

· Resin (polyester)

· Crosslinker

· Pigments / Fillers

· Flow agents

· Degassing agents

· Catalysts

DSM Coating Resins

Powder Coating - February 05 -
Chemistries (Binder systems) 7

• Interior • bisphenol A epoxies • Carboxylic polyester

(hybrid)

• Exterior • Araldite PT 810 (TGIC) • Carboxylic polyester

• Primid XL 552 / QM 1260
• Araldite PT 910
• Mix crosslinker
• Uranox

• (blocked) Isocyanates • Hydroxyl polyester

• glycoluril

DSM Coating Resins

Powder Coating - February 05 -
Overview of the characteristics of binder
8
systems
Polyester Polyester Polyester Polyester Uranox Uranox/ Polyester/
/ Epoxy / TGIC / Primid / Primid Isocyanate
PT 910 no split-off

Flexibility ++ ++ ++ ++ ++ ++ ++

Flow ++ ++ ++ ++ + ++ ++
adjustability

Exterior -- ++ ++ ++ + ++ ++
durability

Powder ++ + + +/± ± + +
stability

Colour stability
- overbake + ++ + ++ ± ± +
- direct gas + ++ ± ++ + + +
oven
Processing ++ ++ + + ++ ++ +/++

Split-off ++ ++ - ++ ++ + ++
products

Blister-free ++ ++ - ++ ++ + +
layer thickness

Labelling ++ -- ++ ± ++ ++ ++

DSM Coating Resins

Powder Coating - February 05 -
Hybrids 9

CH3 CH3
O O

OH + CH CH2 O C O OH O C O
O
CH2
CH3 CH2 HC CH3 CH2 HC
CH2
CH3
OH

O OH

Carboxylated + Bisphenol A diglycidyl ethers

Polyester

O
R2
R1 O
OH

DSM Coating Resins

Powder Coating - February 05 -
Hybrids 10

+ Advantages - Disadvantage
• Price/performance • Outdoor durability
• Flexibility
• Large curing window
• Ease of processing
• Powder stability
• Chemical resistance

DSM Coating Resins

Powder Coating - February 05 -
Carboxyl Polyesters for Hybrids 11
Crosslinker: bisphenol A epoxies

• 50/50 systems • Acid value 70-85

• 60/40 systems • Acid value 48-55

• 70/30 systems • Acid value 32-38

DSM Coating Resins

Powder Coating - February 05 -
Outdoor durable Crosslinkers 12

Araldite PT 810 Huntsman

XL 552 / QM 1260 EMS
PT 910/PT 912 Huntsman

Uranox DSM Resins

BF 1540 / BF 1320 Creanova
LS 2147 Bayer

DSM Coating Resins

Powder Coating - February 05 -
TGIC 13

O O CH 2

+ CH O
O
OH

H 2C C CH 2
OH
N N HC CH 2
O OH

O
C C
O N O
Carboxylated + TGIC
Polyester (triglycidylisocyanurate)
CH 2
H 2C CH

O
R2
R1 O
OH

DSM Coating Resins

Powder Coating - February 05 -
TGIC 14

+ Advantages - Disadvantage
• Flexibility • Labeling
• Large curing window
• Outdoor durability
• Colour stability
• Processing
• Powder stability

DSM Coating Resins

Powder Coating - February 05 -
Primid (XL 552, QM 1260) 15

O OH

O
O
OH
+
HO N
OH N OH
O OH
O

Carboxylated + Primid XL-552, ex-EMS

OH
Polyester Primid

HO

O + H2O
N
R1 O R3

DSM Coating Resins

Powder Coating - February 05 -
Primid (XL 552, QM 1260)
+ Advantages
• Label free
• System cost
• Low curing temperatures
• Outdoor durability
• Powder stability
DSM Coating Resins
Powder Coating - February 05 -
16
- Disadvantage
• Yellowing tendency
• Low blister-free layer thickness
• Water sensitivity
• Proces sensitivity
PT 910 (PT 912) 17

O O O
O
OH
+

OH

O OH O O 0<n<1
O
n

Carboxylated + O O O
Polyester Araldite PT 910 and PT 912, ex-
Vantico

O
R2
R1 O
OH

DSM Coating Resins

Powder Coating - February 05 -
PT 910 (PT 912) 18

+ Advantages
• Well-known chemistry
• Excelent exterior durability
• Thick layers
• Colour stability
- Disadvantage
• Xi Labeling
• Lower cross-link density
• Processing sensitivity

DSM Coating Resins

Powder Coating - February 05 -
Mixed cross linker 19

• Combination of carboxylated resin with 2 cross linkers

• e.g. PT 910/Primid
• Primid/Uranox

DSM Coating Resins

Powder Coating - February 05 -
Uranox 20

O O O

O H3C O
OH
+ CH2

OH
R
O OH O n

Carboxylated + Uranox, ex-DSM Coating

Polyester Resins

O
R2
R1 O
OH

DSM Coating Resins

Powder Coating - February 05 -
Uranox 21

+ Advantages
• No Hazard labelling
• Processing properties
• Pigment wetting
- Disadvantage
• Powder stability
(P7200 and P 7300)
• Yellowing under extreme test
conditions

DSM Coating Resins

Powder Coating - February 05 -
Polyurethanes 22

HO OH O

+
H O O H

R N N R N C O R O C N
OH
n

Hydroxylated polyester + Internally blocked

isocyanates

R1 O NH

R2

DSM Coating Resins

Powder Coating - February 05 -
Polyurethanes 23

+ Advantages
• Outdoor durability
• Powder stability
• Flow
• Chemical resistance
- Disadvantage
• Price
• Caprolactam blocked types:
• Split-off products

DSM Coating Resins

Powder Coating - February 05 -
Polyester/cross linker ratio (carboxylated
24
resins)

• Equivalent weight polyester • Example: AV= 35

• 56100 / AV = EW1 • 56100 / 35 = 1600

• Equivalent weight Cross-linker: • Primid XL 552: EW = 84

EW2

• Stoichiometric resin ratio:

• (EW1 / (EW1 + EW2))*100% • (1600 / (1600 + 84))*100% =
• 95% Polyester
• 5% Primid XL 552

DSM Coating Resins

Powder Coating - February 05 -
Polyester/cross linker ratio (Hydroxylated
25
resins)

• - Equivalent weight polyester • Example: HV= 42

• 56100 / HV = EW1 • 56100 / 42 = 1336

• - Equivalent weight Cross-linker: • BF 1540: EW = 280

EW2

• Stoichiometric resin ratio:

• (EW1 / (EW1 + EW2))*100% • (1336 / (1336 + 280))*100% =
• 82% Polyester
• 18% BF 1540

DSM Coating Resins

Powder Coating - February 05 -
Polyester / crosslinker ratio several Acid
26
values

Ratio Polyester / crosslinker

EW AV

20 28 35 53 80

Araldite GT 7004 700 80/20 75/25 70/30 60/40 50/50

Araldite PT 810 110 96/4 95/5 93/7

(TGIC)
Primid XL 552 84 97/3 96/4 95/5 93/7

Primid QM 1260 100 97/3 95/5 94/6 91/9

Araldite PT 910 150 93/7 91/9

DSM Coating Resins

Powder Coating - February 05 -
Application 27

Air + powder Corona

High voltage
supply

Air + powder Tribo

DSM Coating Resins

Powder Coating - February 05 -
Corona Packaging 28

DSM Coating Resins

Powder Coating - February 05 -
Corona Faraday cage 29

DSM Coating Resins

Powder Coating - February 05 -
Corona Back ionisation 30

DSM Coating Resins

Powder Coating - February 05 -
Tribo 31

DSM Coating Resins

Powder Coating - February 05 -
 Melting / curing proces melt cure stages 32

25°C 100°C 150°C 200°C

high viscosity start melting start reaction high viscosity
decrease viscosity increase viscosity flow stops
increase flowing decrease flow x-linked film

DSM Coating Resins

Powder Coating - February 05 -
Viscosity curves 33

10000 250

200
1000

150

100

100

10
50

1 0
0 100 200 300 400 500 600

high reactive low reactive

non reacting temperature profile

DSM Coating Resins

Powder Coating - February 05 -
Influence of melting rate on viscosity 34

4 5 0 0

4 0 0 0

3 5 0 0

3 0 0 0
viscosity

2 5 0 0 20°C/min

2 0 0 0

40°C/min
1 5 0 0

1 0 0 0

80°C/min
5 0 0

0 1 2 3 4 5 6 7 8 9 10

Time (min)

DSM Coating Resins

Powder Coating - February 05 -
Simplified DSC curve 35

DSM Coating Resins

Powder Coating - February 05 -
Influence of particle size 36

DSM Coating Resins

Powder Coating - February 05 -
Tg versus physical stability 37

10
9
8
Physical stability

7
6
5
4
3
2
1
0
20 30 40 50 60 70
Powder Tg

DSM Coating Resins

Powder Coating - February 05 -
Influence % cross-linker on Tg
(only TGIC and PT 910, Primid XL 552 and Epoxy resin Powder Tg 38
not (hardly) influenced)

Influence % cross-linker on Tg

12 70
68
10 66
64 %TGIC

Powder Tg (C)
% cross-linker

8
62
6 60 %PT 910
58
4 56 Resin Tg 64
icw TGIC
2 54
Resin Tg 68
52
icw PT 910
0 50
5 10 15 20 25 30 35 40
Acid Value

DSM Coating Resins

Powder Coating - February 05 -
Relation viscosity and resin Tg 39

1600
1400
1200
Viscosity dPas

1000
800
600
400
200
0
20 40 60 80
resin Tg

DSM Coating Resins

Powder Coating - February 05 -
Matting 40

• Powders are more difficult to matt than wet paints

• Techniques
• matting agents
• dry blend

DSM Coating Resins

Powder Coating - February 05 -
Mat powder coatings (Dry blend systems) 41

• fast with slow,different AV or different chemistries

• In generally wheatherability and mechanical properties
are OK
• Sparkling effect
• Extra processing step involved
• TGIC
E.g. P2220/P4800 with wax
• Freedom of formulation

• TGIC/PUR
• Freedom of formulation

DSM Coating Resins

Powder Coating - February 05 -
Mat powder coatings 42

• Primid
E.g. P870/P833, P873/P835 (optional with DT3329 )
+ gloss setting, mechanical properties
• water split off can give disturbances, gloss variations per layer thickness,
very low gloss is difficult

• PT910
E.g. P2240/P3487 with wax (DT 3329)
+ no splitt off
• moderate mechanicals, powder stability, not very low gloss

• PT910/Primid
+ low gloss possible
• bad mechanicals

DSM Coating Resins

Powder Coating - February 05 -