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EnergyCurableCoatingsforAutomotiveInterior

- MarcusHutchinsandJenniferMcClung

Content

2

• Technology/ProcessComparison• ChallengesofUVCure• Products– 100%SolidsandWaterborneUV• Experimentation• Results• Conclusion– 100%SolidsUVandWaterborneUV• NextGeneration• TechnologyComparison• Experimentation• Results• Conclusion

AutomotiveInteriorTechnologyComparison

4May2018 3

1Kor2KConventional(NCO- OH)

+Fullcurefordifficultshapeofpart+Lowershrinkage+Outstandingweatherability

- Spaceandtime- Slowcure- Highenergyconsumptionfordrying

UVCuring

+Fastcure(highproductivity)+Highscratch&chemicalresistance+Smallfootprint&easylineretrofits

- 3Dshape=>NOUV=NOCure- Volumetricshrinkage- Adhesionisnotrobust

Water-orSolvent-borne(1K/2K,UV)

• Water orSolventevaporation• Physical drying• Higher MW – Low Viscosity

Heat

TechnologyComparison

Tackyor

Tack-free !

UVorEB

Liquidmixture

DRYFILM

UVorEBOligomersMonomersPhotoinitiator

100%Solids

UV/EB:Readyforimmediateuseaftercure 1K/2K:Oktohandle,hoursanddaysbeforefullproperties

TechnolgoyComparison

5

0

5

10

15

20

25

30

35

40

1K/2KSolventborne 1K/2KWaterborne SolventborneUV WaterborneUV

Minutes

Coat(Spray) SolventorWaterRemoval Cure

CureTemperature80oCAdditional4,000minutesbeforefullpropertiesdevelop

ChallengesofUVCure

6

UV-AUV-BUV-C UV-V

Coating

Substrate

100– 280nm280– 315nm

315– 400nm400– …nm

Electrons(EB)

• DifferentpartsoftheUVspectrumcanpenetratetodifferentdepthsofthecoating.• Therightphotoinitiatorchoicewillinitiatethereactionintheentirecoating.• UVLEDistypically385nm,395nm,405nm.(365nmisavailableatlowenergy

output)

O2O2

O2O2

O2

O2O2 O2

O2O2

O2O2

O2 O2 O2O2

O2

O2O2

O2

O2

O2

O2

O2

O2O2O2O2

O2 O2

O2O2 O2 O2

O2O2

O2O2

O2

O2

O2

O2

O2O2

O2

O2O2

O2

O2O2

O2

–O–C–CH=CHO

Products

Functionality,Acrylate

HydroxylValue(NCO,%)

Viscosity,cPat25oC Non-volatile,%

Bio-basePolyester 2 - 450 100

UrethaneHexa-acrylate 6 - 85000 100

RX 81100 4 - 1500 100

UVCurablePUD 6 - 50 40

Hexa-acrylate Emulsion 6 - 500 65

1K PolycarbonatePUD - 170 200 40

1KThermal Silicone - 10 20

Testing

- Abrasion: TaberHaze- 100cyclesonPCsheetwith500gload,CS10Fwheels

- Scratch:SteelWool- 0000and1kgweight

- AutomotiveChemicalTesting- Sunlotionandhandcreamareappliedonabandage

- Thesampleisputinaventilatedovenfor24hoursat80°C- Lotionandcreamremovedandsampleareleftfor4hoursatroomtemperature

beforemakinganassessment- Visualassessmentandrating

- 0noattack- 1visualglosschange- 2changeinsurfaceappearance- 3delamination,blistering,lossofadhesion

FormulationsforTesting

• 100%resin• UVcuredsystemsinitiated- 100%solids:4%basedontotalweightofsolids,1-hydroxy-cyclohexylphenyl-ketone- WaterborneUV:4%basedontotalweightofsolidsofablendof1-hydroxy-cyclohexylphenyl-ketoneandbenzophenone (1:1)

- Dryfilmtarget12-14g/m2

• WaterandSolventremoval- 80oCfor10minutesforwaterremoval- 80oCfor10minutesforsolventremoval

• 1K/2KandThermalSilicone:ThermalCuring- 80oCfor30minutes- Sampleskeepatroomtemperaturefor72hoursbeforetesting

9

%HazeAfterAbrasion(CS10F,500g,100cycles)

Sun LotionandHandCream

(80oC,24hr)

SteelWoolScratch

(0000,1kg)

Bio-basePolyester 10 1 100doublerubs

UrethaneHexa-acrylate 7 0 100doublerubs

RX81100 15 0 3double rubs

Thermal Silicon 6 0 100doublerubs

1K:PCPUD 25 3 0

2K:PCPUD +HDITrimer 15 0 3

Results:UVCurableResins– 100%Solids

PercentHazeAfterAbrasion

(CS10F,500g,100cycles)

Sun LotionandHandCream(80oC,24hr)

SteelWoolScratch(0000,1kg)

UVCurablePUD 12 1 5doublerubs

Hexa-functionalUrethaneAcrylateEmulsion 6.5 0 100doublerubs

1KWater-basedPolycarbonatePUD 25 3 0rubs

1KPCPUD+HDITrimer 15 0 5doublerubs

1K PCPUD+UVPUD(DualCure) 18 1 0rubs

Results:UVCurableResins– Waterborne

Conclusion:100%SolidsandWaterborneUV

• UV/EBsystemcanmeetmorestringentautomotivechemicaltest• WaterborneUVcanbedesignedtohaveequivalentperformancetohigherfunctionalacrylatesystem

• Bio-basedresincanbedesignedtodeliverynotonimprovesustainabilitywithoutsacrificingperformance

⁻ Ideaforflatsubstrates⁻ Glasstransitionandcross-linking(higher)importantforsunlotionandhandcreamresistance

⁻ Adhesionvariedbasedonsupplierandtype⁻ 100%solidsisnotidealforcurrentcoatingprocessingconditionsØDualCuretechnologycouldpossiblebridgethebetweenconventionalandenergycurablechemistries

12

NextGeneration:DualCure

13

Conventional1Kor2KSB(NCO- OH)+Fullcurefordifficultshapeofpart+Lowershrinkage+Outstandingweatherability

- Spaceandtime- Slowcure- Highenergyconsumptionfordrying

UVCuring+Fastcure(highproductivity)+Highscratch&chemicalresistance+Limitedspaceneeded

- 3Dshape=>NOUV=NOCure- Moreshrinkage(adhesionsometimeschallenging)

+Fastcure(highproductivity)+Lowshrinkage– goodadhesion+Goodscratch&chemicalresistance+3Dshape:NOUV=Cure(NCO-OH)+Lessspaceoccupation

NextGeneration:DualCure

14

ProcessingComparison

15

0

5

10

15

20

25

30

35

1K/2KSolventborne 1K/2KWaterborne SolventborneUV WaterborneUV DualCureUVSolventborne

Minutes

Coat(Spray) SolventorWaterRemoval Cure UVCure

CureTemperature80oCfor25minutesAdditional4,000minutesbeforefullpropertiesdevelop

DualCureCuringTemperature80oCfor5minutesAdditional5minutesbeforefullpropertiesdevelop

Products

Functionality,Acrylate(NCO)

HydroxylValue(NCO,%)

Viscosity,cPat23oC Non-volatile,%

OHFunctional Acrylic - 100 3000 55

NCOAcrylate 1.5(1.5) - 20000 90

Urethane acrylate 6 - 8500 (25oC) 100

Testing

- Abrasion: TaberHaze- 100-300-500cyclesonPCsheetwith500gload,CS10Fwheels

- Curl uponcure- CoatingwasappliedtoPETfilm(12.5microns)at12microns- 4”x4”samplewastakenandtheheightofcurlwasmeasuredateachcornerand

fourcornerswereaveraged

- Adhesion:crosshatch- 0=noadhesion,5=fulladhesion

- Erichsen (pen318withtipof0.75mm)pass/fail

Testing

- DoublebondandNCOconversion- MeasuredusingFTIRspectrophotometer

- ~810cm-1 absorbancefordoublebondconversion- ~2270cm-1 absorbanceforisocyanateconversion

- AcceleratedOutdoordurability(ASTMG154-UVA)- 8hoursat60oCatanirradianceof0.89W/cm2

- 4hoursdarkat50oC

- Humidityresistance:VWTL226Agingstability- hydrolysis(72h,90°C,95%humidity)- Crosshatchadhesionafterhumiditytest

Testing

- AutomotiveChemicalTesting- Sunlotionandhandcreamareappliedonabandage

- Thesampleisputinaventilatedovenfor24hoursat80°C- Lotionandcreamremovedandsampleareleftfor4hoursatroomtemperatureandretested

- Crosscutadhesion- Glossmeasured- Erichsen penhardness

StartingPointFormulation

4May2018 20

*1-hydroxy-cyclohexylphenyl-ketone**Dibutyltindilaurate(DBTL)

• ComponentsIand IIaremixedjust beforeapplication

• Viscosity@25°C~200mPa.s• Solidcontent~58%• Substrate:plasticpanel• Targetdryfilmthickness(DFT):20g/m²• 30’@80°C:flashoffandthermalstep***• UVcuring:2x10m/min.with120W/cmHglamp(~2000mJ/cm²)

• Testingafter1weekstorageatroomtemperature

wt% wt%ComponentI IV.1 IV.2OHFunctionalAcrylic 38.9 31.9Alphatic urethane acrylate 7.8Butylacetate 15.0 15.0Flow andLevelingadditive 0.5 0.5Photoinitiator* 4.2 4.2Catalyst** 0.02 0.02

ComponentII wt%NCOFunctionalAcrylate 56.2

***tobeadjustedbytheamountofcatalysttotherequirementsoftheline/machine

Results– LowCurlUponCure

0

0.2

0.4

0.6

0.8

1

1.2

AliphaticUrethaneAcrylate

NCO-Acrylate+OHFunctionalAcrylic(Thermal+UV)

NCO-Acrylate+OHAcrylic(Thermal)

AverageCu

rl,m

m

21

Results:HazeafterAbrasion

0

10

20

30

40

50

60

OHFunctionalAcrylic OHFunctionalAcrylic+NCO-Acrylate(Thermalonly)

OHFunctionalAcrylic+NCO-Acrylate(Thermal+UV)

UrethaneAcrylate

Percen

tHaze

100cycles 300cycles 500cycles

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Results:HazeafterAbrasion– AdditionalProcessingTime

IV.1 IV.2

2x5m/m 2x10m/m 2x5m/m 2x10m/m

after1week

+48hrs60°C

after1week

+48hrs60°C

after1week

+48hrs60°C

after1week

+48hrs60°C

Uncoated

%start 0 0.2 0.2 0.1 0.2 0.2 0.2 0.2 0.2

%after100cycles 24.5 6.4 6.1 6.2 6.2 6 5.9 6.5 5

%after200cycles 25.8 9.1 8.8 9 9 8.7 8 8.8 7.4

%after300cycles 28 11.8 11.5 12.5 11.5 11.3 11 12.4 10.6

%after500cycles 30 15.6 15.4 16 14.9 14.5 15.1 15.6 13.9

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Results:NCOandDouble(=)Conversion

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Results:DualCure– StainResistance

IV.1 IV.2 UrethaneAcrylate

2x5m/m 2x10m/m 2x5m/m 2x10m/m 2x10m/m

mustard 4 3 5 3 5

eosine 5 4 5 4 5

coffee 5 5 5 5 5

isobetadine 4.5 3.5 4.5 4 5

NH10% 5 5 5 5 5

ethanol50% 5 5 5 5 5

N70blackmarker 5 5 5 5 5

Average 4.8 4.4 4.9 4.4 5

NCOconv(1week) 86 90 81 82 Notapplicable

=conv(1week) 86 79 81 76 79(nochange)

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Results:ChemicalResistance

IV.1 IV.2 UrethaneAcrylate

2x5m/m 2x10m/m 2x5m/m 2x10m/m 2x10m/m

SUNcreamlotion

Initialgloss20° 85.6 87.8 88.9 88.5 100

60° 93.2 93 93.1 92.6 100

Gloss(aftertest)

20° 87.2 86.6 87.7 87.2 99.32

60° 92.1 92.8 92.8 92.5 98.83

InitialAdhesion(crosshatch) 5 5 5 5 5

Adhesion(crosshatch) 5 5 5 5 5

Erichsenpen10N pass pass pass pass pass

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Results:DualCure– ChemicalResistance

27

IV.1 IV.2 UrethaneAcrylate

2x5m/m 2x10m/m 2x5m/m 2x10m/m 2x10m/m

Handcreamlotion

Initialgloss20° 85.6 87.8 88.9 88.5 100

60° 93.2 93 93.1 92.6 100

Gloss(aftertest)

20° 84.1 83.9 83.8 82.9 97.62

60° 91.8 91.5 91.3 91.6 94.74

InitialAdhesion(crosshatch) 5 5 5 5 5

Adhesion(crosshatch) 5 5 5 5 5

Erichsenpen10N pass pass pass pass pass

Results:DualCure– Weathering

0

20

40

60

80

100

120

0 100 300 500 750 1000 1250 1500 2000 2500 3000 3500Hours

OHAcrylic

Hexa-functionalUrethaneAcrylate

NCO-Acrylate+OHAcrylic

UncoatedPanel

Percen

tGlossReten

tion

28

Conclusions

•DifferentcombinationsofUVcurableproductsenableformulatorstocreatingidealcoatingsolutionsforautomotiveinteriorbenefitingfromintrinsicnatureoftheUVchemistry

•DualCureexpandsthetoolbox;benefitingfromthebestofbothworlds

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• Dryingconditions(e.g.catalystamount,thermaltemperature)caninfluenceperformance!

DuctilebehaviorforhighscratchresistancecoatingsExcellentadhesiontoABS,PC,ABS/PCblendsShorterprocessingtimeincludingfasterfinalpropertydevelopment

Outstandingscratch,abrasionandchemical(sunlotionandhandcream)ExcellentWeatherability

• NCOfunctionalacrylatesNOTimpactedbyNCOrestrictions!

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MarcusHutchins(marcus.hutchins@allnex.com,770-280-8391)JoinusatBooth301

ThankyouSpecialThanks

JenniferMcClungStevenCappellePaulGevaert