hutchins-marcus-energy curable coatings for automotive ...€¦ · jennifer mcclung....
TRANSCRIPT
![Page 1: Hutchins-Marcus-Energy Curable Coatings for Automotive ...€¦ · Jennifer McClung. Hutchins-Marcus-Energy Curable Coatings for Automotive Interior](https://reader035.vdocuments.mx/reader035/viewer/2022062507/5fc0f0063932fd60667db471/html5/thumbnails/1.jpg)
www.allnex.com
EnergyCurableCoatingsforAutomotiveInterior
- MarcusHutchinsandJenniferMcClung
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Content
2
• Technology/ProcessComparison• ChallengesofUVCure• Products– 100%SolidsandWaterborneUV• Experimentation• Results• Conclusion– 100%SolidsUVandWaterborneUV• NextGeneration• TechnologyComparison• Experimentation• Results• Conclusion
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AutomotiveInteriorTechnologyComparison
4May2018 3
1Kor2KConventional(NCO- OH)
+Fullcurefordifficultshapeofpart+Lowershrinkage+Outstandingweatherability
- Spaceandtime- Slowcure- Highenergyconsumptionfordrying
UVCuring
+Fastcure(highproductivity)+Highscratch&chemicalresistance+Smallfootprint&easylineretrofits
- 3Dshape=>NOUV=NOCure- Volumetricshrinkage- Adhesionisnotrobust
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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
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TechnolgoyComparison
5
0
5
10
15
20
25
30
35
40
1K/2KSolventborne 1K/2KWaterborne SolventborneUV WaterborneUV
Minutes
Coat(Spray) SolventorWaterRemoval Cure
CureTemperature80oCAdditional4,000minutesbeforefullpropertiesdevelop
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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
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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
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Testing
- Abrasion: TaberHaze- 100cyclesonPCsheetwith500gload,CS10Fwheels
- Scratch:SteelWool- 0000and1kgweight
- AutomotiveChemicalTesting- Sunlotionandhandcreamareappliedonabandage
- Thesampleisputinaventilatedovenfor24hoursat80°C- Lotionandcreamremovedandsampleareleftfor4hoursatroomtemperature
beforemakinganassessment- Visualassessmentandrating
- 0noattack- 1visualglosschange- 2changeinsurfaceappearance- 3delamination,blistering,lossofadhesion
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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
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%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
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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
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Conclusion:100%SolidsandWaterborneUV
• UV/EBsystemcanmeetmorestringentautomotivechemicaltest• WaterborneUVcanbedesignedtohaveequivalentperformancetohigherfunctionalacrylatesystem
• Bio-basedresincanbedesignedtodeliverynotonimprovesustainabilitywithoutsacrificingperformance
⁻ Ideaforflatsubstrates⁻ Glasstransitionandcross-linking(higher)importantforsunlotionandhandcreamresistance
⁻ Adhesionvariedbasedonsupplierandtype⁻ 100%solidsisnotidealforcurrentcoatingprocessingconditionsØDualCuretechnologycouldpossiblebridgethebetweenconventionalandenergycurablechemistries
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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
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NextGeneration:DualCure
14
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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
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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
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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
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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
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Testing
- AutomotiveChemicalTesting- Sunlotionandhandcreamareappliedonabandage
- Thesampleisputinaventilatedovenfor24hoursat80°C- Lotionandcreamremovedandsampleareleftfor4hoursatroomtemperatureandretested
- Crosscutadhesion- Glossmeasured- Erichsen penhardness
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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
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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
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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
22
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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
24
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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)
25
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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
26
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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
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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
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Conclusions
•DifferentcombinationsofUVcurableproductsenableformulatorstocreatingidealcoatingsolutionsforautomotiveinteriorbenefitingfromintrinsicnatureoftheUVchemistry
•DualCureexpandsthetoolbox;benefitingfromthebestofbothworlds
29
• Dryingconditions(e.g.catalystamount,thermaltemperature)caninfluenceperformance!
DuctilebehaviorforhighscratchresistancecoatingsExcellentadhesiontoABS,PC,ABS/PCblendsShorterprocessingtimeincludingfasterfinalpropertydevelopment
Outstandingscratch,abrasionandchemical(sunlotionandhandcream)ExcellentWeatherability
• NCOfunctionalacrylatesNOTimpactedbyNCOrestrictions!
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www.allnex.com
MarcusHutchins([email protected],770-280-8391)JoinusatBooth301
ThankyouSpecialThanks
JenniferMcClungStevenCappellePaulGevaert