Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February...

43
DSM Coating Resins Powder Coating - February 05 - Introduction into powder coatings

Transcript of Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February...

Page 1: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

DSM Coating ResinsPowder Coating - February 05 -

Introduction into powder coatings

Page 2: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

DSM Coating Resins

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Powder Coating - February 05 -

Introduction into powder coatingsIntroduction into powder coatings

• Polymerisation• Chemistries

• chemical reaction• advantage/disadvantages

• Application• Melting/Curing process• Matting

Page 3: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Powder Coating - February 05 -

Two types of Polymerisation processesTwo types of Polymerisation processes

� Addition polymerisation-A polymerization in which the growth of polymer chainsproceeds by addition reactions between molecules ofall degrees of polymerization (e.g. acrylics)

� Condensation polymerisation- A polymerization in which the growth of polymer chains

proceeds by condenstation reactions between molecules ofall degrees of polymerization with loss of small molecules like water. (e.g. polyesters)

Page 4: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Raw materialsRaw materials

� Diols (glycols)�Neopentylglycol

�Ethyleneglycol

�propyleneglycol-1,2

� Polyalcohols�Trimethylolpropane

�glycerol

� Dicarboxylic acids�terephthalic acid

�isophthalic acid

� Polycarboxylic acids�trimellitic anhydride

Page 5: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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EsterificationEsterification

� Esterification:

� Acid + Alcohol Ester + Water

� Polyacid + Polyalcohol Polyester + Water

� Hydrolysis:

� Polyester + Water Polyacid + Polyalcohol

� Overall:

� Polyacid + Polyalcohol Polyester + Water

Page 6: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Powder Coating - February 05 -

Main reactionMain reaction

Excess of OH OH-functional polyester

Excess of COOH COOH-functional polyester

Page 7: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Powder Coating FormulationPowder Coating Formulation

� Resin (polyester)

� Crosslinker

� Pigments / Fillers

� Flow agents

� Degassing agents

� Catalysts

Page 8: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Powder Coating - February 05 -

Chemistries (Binder systems)Chemistries (Binder systems)

• Interior(hybrid)

• Exterior

• bisphenol A epoxies

• Araldite PT 810 (TGIC)• Primid XL 552 / QM 1260• Araldite PT 910• Mix crosslinker• Uranox

• (blocked) Isocyanates• glycoluril

• Carboxylic polyester

• Carboxylic polyester

• Hydroxyl polyester

Page 9: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Overview of the characteristics of binder Overview of the characteristics of binder systemssystems

Polyester/ Epoxy

Polyester/ TGIC

Polyester/ Primid

Polyester/

PT 910

Uranox Uranox/Primid

Polyester/Isocyanateno split-off

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

Flow adjustability

++ ++ ++ ++ + ++ ++

Exterior durability

-- ++ ++ ++ + ++ ++

Powder stability

++ + + +/± ± + +

Colour stability- overbake- direct gas

oven

++

++++

++++

±+

±+

++

Processing ++ ++ + + ++ ++ +/++

Split-off products

++ ++ - ++ ++ + ++

Blister-freelayer thickness

++ ++ - ++ ++ + +

Labelling ++ -- ++ ± ++ ++ ++

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HybridsHybrids

OHO

O

OH

O

OHHC

O

CH2

CH2

OO C

CH3

CH3

OCH2CH

CH2

O C

CH3

CH3

O

CH2

OH

HC

CH3

+

+CarboxylatedPolyester

Bisphenol A diglycidyl ethers

R1 O

O

OH

R2

Page 11: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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HybridsHybrids

- Disadvantage• Outdoor durability

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

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Carboxyl Polyesters for HybridsCarboxyl Polyesters for HybridsCrosslinkerCrosslinker: : bisphenolbisphenol A epoxiesA epoxies

• 50/50 systems

• 60/40 systems

• 70/30 systems

• Acid value 70-85

• Acid value 48-55

• Acid value 32-38

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Outdoor durable Outdoor durable CrosslinkersCrosslinkers

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

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TGICTGIC

O

OO

O CH 2

CH

H2C C

H2C CH

CH 2

N

C

N

CH 2

HC CH 2

C

N

O

O

OHO

O

OH

O

OH

+

TGIC (triglycidylisocyanurate)

+CarboxylatedPolyester

R1 O

O

OH

R2

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TGICTGIC

- Disadvantage• Labeling

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

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Primid (XL 552, QM 1260)Primid (XL 552, QM 1260)

OHO

O

OH

O

OH

OH

N

O

OH

N

OH

O

OH

Primid XL-552, ex-EMS Primid

+

CarboxylatedPolyester

+

R1 O

O

NR3

OH

OH2+

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Primid (XL 552, QM 1260)Primid (XL 552, QM 1260)

- Disadvantage• Yellowing tendency• Low blister-free layer thickness• Water sensitivity• Proces sensitivity

+ Advantages• Label free• System cost• Low curing temperatures• Outdoor durability• Powder stability

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PT 910 (PT 912)PT 910 (PT 912)

OHO

O

OH

O

OH

O

O OO

O O

O

OO

n

Araldite PT 910 and PT 912, ex-Vantico

0<n<1

+

CarboxylatedPolyester

+

R1 O

O

OH

R2

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PT 910 (PT 912)PT 910 (PT 912)

- Disadvantage• Xi Labeling• Lower cross-link density• Processing sensitivity

+ Advantages• Well-known chemistry• Excelent exterior durability• Thick layers• Colour stability

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Mixed cross linkerMixed cross linker

• Combination of carboxylated resin with 2 cross linkers

• e.g. PT 910/Primid• Primid/Uranox

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UranoxUranox

O

O

O

O

CH2

CH3

R

nOHO

O

OH

O

OH +

Uranox, ex-DSM Coating Resins

+CarboxylatedPolyester

R1 O

O

OH

R2

Page 22: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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UranoxUranox

- Disadvantage• Powder stability

(P7200 and P 7300)• Yellowing under extreme test

conditions

+ Advantages• No Hazard labelling• Processing properties• Pigment wetting

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PolyurethanesPolyurethanes

+

OH

OH OH

O H

NCO

H O

CN

O

O

R N N R R O

n

+ Internally blocked isocyanates

Hydroxylated polyester

R1 O NH

O

R2

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PolyurethanesPolyurethanes

- Disadvantage• Price• Caprolactam blocked types:• Split-off products

+ Advantages• Outdoor durability• Powder stability• Flow• Chemical resistance

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Polyester/cross linker ratio (Polyester/cross linker ratio (carboxylatedcarboxylatedresins)resins)

• Equivalent weight polyester• 56100 / AV = EW1

• Equivalent weight Cross-linker:EW2

• Stoichiometric resin ratio:• (EW1 / (EW1 + EW2))*100%

• Example: AV= 35• 56100 / 35 = 1600

• Primid XL 552: EW = 84

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

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Polyester/cross linker ratio (Polyester/cross linker ratio (HydroxylatedHydroxylatedresins)resins)

• - Equivalent weight polyester• 56100 / HV = EW1

• - Equivalent weight Cross-linker:EW2

• Stoichiometric resin ratio:• (EW1 / (EW1 + EW2))*100%

• Example: HV= 42• 56100 / 42 = 1336

• BF 1540: EW = 280

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

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Polyester / Polyester / crosslinkercrosslinker ratio several Acid ratio several Acid valuesvalues

93/7

95/5

96/4

95/5

75/25

28

91/9150Araldite PT 910

91/994/697/3100Primid QM 1260

93/795/597/384Primid XL 552

93/796/4110Araldite PT 810 (TGIC)

50/5060/4070/3080/20700Araldite GT 7004

80533520

AVEW

Ratio Polyester / crosslinker

Page 28: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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ApplicationApplication

CoronaAir + powder

High voltage supply

TriboAir + powder

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CoronaCorona PackagingPackaging

Page 30: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Powder Coating - February 05 -

CoronaCorona Faraday cageFaraday cage

Page 31: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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CoronaCorona Back ionisationBack ionisation

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Powder Coating - February 05 -

TriboTribo

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Melting / curing Melting / curing procesproces melt cure stagesmelt cure stages

200°Chigh viscosityflow stopsx-linked film

25°Chigh viscosity

100°Cstart meltingdecrease viscosityincrease flowing

150°Cstart reactionincrease viscositydecrease flow

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Viscosity curvesViscosity curves

1

10

100

1000

10000

0 100 200 300 400 500 6000

50

100

150

200

250

high reactive low reactivenon reacting temperature profile

Page 35: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Influence of melting rate on viscosityInfluence of melting rate on viscosity

0

5 0 0

1 0 0 0

1 5 0 0

2 0 0 0

2 5 0 0

3 0 0 0

3 5 0 0

4 0 0 0

4 5 0 0

0 1 2 3 4 5 6 7 8 9 10

Time (min)

visc

osity

80°C/min

20°C/min

40°C/min

Page 36: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Powder Coating - February 05 -

Simplified DSC curveSimplified DSC curve

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Powder Coating - February 05 -

Influence of particle sizeInfluence of particle size

Page 38: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Powder Coating - February 05 -

Tg versus physical stabilityTg versus physical stability

0123456789

10

20 30 40 50 60 70

Powder Tg

Phys

ical

sta

bilit

y

Page 39: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Powder Coating - February 05 -

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

Influence % cross-linker on Tg

0

2

4

6

8

10

12

5 10 15 20 25 30 35 40

Acid Value

% c

ross

-link

er

5052545658606264666870

Pow

der T

g (C

) %TGIC

%PT 910

Resin Tg 64icw TGICResin Tg 68icw PT 910

Page 40: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Relation viscosity and resin TgRelation viscosity and resin Tg

0200

400600800

10001200

14001600

20 40 60 80

resin Tg

Visc

osity

dPa

s

Page 41: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Powder Coating - February 05 -

MattingMatting

• Powders are more difficult to matt than wet paints

• Techniques• matting agents• dry blend

Page 42: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Mat powder coatings (Dry blend systems)Mat powder coatings (Dry blend systems)

• fast with slow,different AV or different chemistries• In generally wheatherability and mechanical properties

are OK• Sparkling effect• Extra processing step involved

• TGICE.g. P2220/P4800 with wax• Freedom of formulation

• TGIC/PUR• Freedom of formulation

Page 43: Introduction into powder coatings - · PDF fileDSM Coating Resins 1 Powder Coating - February 05 - Introduction into powder coatings • Polymerisation • Chemistries • chemical

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Powder Coating - February 05 -

Mat powder coatingsMat powder coatings

• PrimidE.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

• PT910E.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