resins for improved coatings for lvt - radtech€¦ · • lvt is comprised of multiple layers of...
TRANSCRIPT
ResinsforImprovedCoatingsforLVT
JonathanShaw,PhDMay,2018
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Background
WhatisUltra-Violet(UV)curing?• UsingUVenergyorvisiblelight,asopposedtoheat,solvent
evaporation,oroxidation(air-drying),toconvertaliquidformulationintoasolidmaterial
• Typesofenergyused:UltraViolet(UV):200– 400nmVisiblelight:typically380- 450nm
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• Productivity,Productivity,Productivity- Secondstocurevs.minutesorhours
• LowerOverallCost(percuredpart)- 100%solids,curespeed,recyclingofcoating,etc.
• Singlecomponentformulas- Eliminatesmixingerrorsfoundin2componentsystems
• RegulatoryConcerns(VOCemission)- Avoidsolventuseinmostcases
• Smallerequipmentfootprint- Lessfloorspaceneeded
• Energycosts
Advantagesof100%SolidsUVCurableSystems
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• Lineofsightcuring- AllareasofthepartmustbeexposedtoUVenergy- Lampplacementcritical,butnotdifficult- Absorbanceofsystem:componentsthatabsorb/blockUVmayinterfere
withcure> Selectcomponentsthatdon’tabsorbUVorselectPIthatabsorbsinanother
regionoftheUVspectrum
• Shrinkage- Allreactionsgenerateshrinkage,whichmayleadtopooreradhesion> Mitigatewithselectionofdiluents,oligomers> UseofWBsystemscanreduceshrinkage(nomonomersneededtoreduce
viscosity)
Challengesin100%SolidsUVCurableSystems
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LuxuryVinylTile– Whatisit?
StainResistantLayer
WearLayer
PrintLayer
PVCLayer
Backing
• Luxuryvinyltile(LVT)isoneofmanytypesofresilientflooring,characterizedbyitssuccessfulcombinationofaestheticsandperformance.
• LVTusesthelatest3DimagingtechnologiesandembossingtoreplicaterealhardwoodsandstonestothepointwhereitisoftendifficulttodistinguishbetweenrealwoodorstoneandLVT.
• LVTiscomprisedofmultiplelayersofmaterial,andusuallyincludesoneortwolayersofPVCasthefoundation,aphotographicimagelayer,awearlayerandascratchandstainresistanttopcoat.
• ThisconstructionmakesLVTaverydurableflooringmaterial.• LVTistypicallythinnerthanmosthardwoodplanks,stone,orceramictilesandcanbeglueddown
orfloated– arelativelyeasyprocess,particularlyfordo-it-yourselfers.• Thefinalproductisbothaffordableandeasytomaintain.
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LuxuryVinylTile– Whyisitattractive?
Successfulcombinationofaestheticsandperformance:- AmazingRealism:latest3Dimagingtechnologies&embossing.Theabilitytoreplicaterealhardwoodsandstonesusingadvancedphotographictechnologiesisthefoundationofluxuryvinylflooringsystems andallowsforlimitlessdesignoptions
- EnhancedDurability:urethanetoplayerforincreasedprotection- MoreInstallationOptions:LVTistypicallythinnerthanmosthardwoodplanks,stone,orceramictiles.Floorscanbeglueddownorfloated– arelativelyeasyprocess,particularlyfordo-it-yourselfers.
- Easytomaintainandaffordable.
“Double-digitgrowth”numbersreported(WFCA)
Residentialmarketisembracingtheauthenticgoodlooksandprovendurability.
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LuxuryVinylTile– MarketNeeds
•EndusersaverysatisfiedwiththeperformanceofLVT.•LVTmanufacturersaretryingtodeterminewaystodifferentiatethemselvesfromcompetition- Consumersresearchon-linebeforebuying- Smalldifferencesinperformancecanresultinsale
•Focusonimprovementinstainresistance
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Resinscreeningofexistingproducts:ListofStains
Stain Description SevereStainLugol’s Iodine Solution Iodine/KI/water X
Wright’sStain Methyleneblue/EosinY/ethanol/water X
Betadine pNVP /Iodine/water X
BlackRITDye X
Ketchup
Mustard X
AntisepticSolution pNVP /Iodine/water X
BlueFoodColoring(blue,red)
Coffee
50% EthanolSolution
Bleach
SharpieMarkers (red,blue,green,black) X
KiwiBrownShoePolish X
Coal Tar X
Vinegar
Water
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Resinscreeningofexistingproducts:ListofResins
Oligomer Functionality Viscosity(25ºC)ALUA1 2 132,500ALUA2 2 23,000ALUA3 2 7,000ALUA4 3 7,000ALUA5 3 25,000ALUA6 3 2,300ALUA7 4 85,000ALUA8 6 15,780ALUA9 6 24,600ALUA10 9 86,000ALUA11 10 75,500ARUA1 2 7,000ARUA2 3 17,000ARUA3 3 3,200ARUA4 6 28,500ARUA5 6 6,000ModEA 2 190,000PEA1 2 5,000PEA2 3 40,000PEA3 3 36,000PEA4 3.5 580PEA5 4 14,000PEA6 4 450
ALUA=ALiphatic UrethaneAcrylateARUA=ARomatic UrethaneAcrylateModEA=MODified EpoxyAcrylatePEA=PolyEster Acrylate
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RawMaterial PartsOligomer 40
Monofunctional monomer 20Trifunctional monomer 5Difunctional monomer asneeded tohit750cps+/- 50
Silica 6(forMatteformulationonly)Aminesynergist 3Photoinitiator 3
Parameter: Value:
Substrate: “Chalk”coloredVCTsubstrate
DryFilmThickness: 1Mil
EnergyDensity: 700± 40mJ/cm2
SampleViscosity: 750± 90cps
DrawDownTool: 1MilBirdBar,6"Length
Formulation:
CoatingPreparation:
Resinscreeningofexistingproducts:InitialScreenforStainResistance
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Resinscreeningofexistingproducts:InitialScreenforStainResistance
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0 2 4 6 8 10 12
StainRa
ting
OligomerFunctionality
StainvsOligomerFunctionality
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0.00 100.00 200.00 300.00 400.00 500.00
StainRa
ting
FomulationEW
StainvsFormulationEW
Higherfunctionalitygenerallyequatestolowerstainratingbutthereisawiderangeeven
withinagivenfunctionality
Slightlybettercorrelationwhenplottingstainvs.equivalentweight(EW)withlowerEWresultinginlowerstainratingbutvariationstillexists
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Commentsoninitialresinscreening• Screeningworkdoneonglossformulations– LVTgenerallyhasmattefinish
• Highfunctionalityleadstohighshrinkage(internalstress)andcurl
• Targetviscositylowerthannecessary– influenceofoligomer“diluted”
Resinscreeningofexistingproducts:FullFormulationEvaluationforStainResistance
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Resinscreeningofexistingproducts– SPFforTesting
• Viscosity~1000,60° gloss~10• Dispersantisessentialinviscositycontrolforhighsilicaformulation• Combinationofsilicasgivesmuchlowerglossthanusingjustone• Ratioofthetwosilicasalsohassignificantimpactonglossandviscosity
RawMaterial Function Wt.%
Oligomer BulkFilmProperties 30.5
HDDA Viscosity control,filmproperties 34.0
TMPTA Viscosity control,filmproperties 3.0
Photoinitiator1 Cure 3.0
Photoinitiator 2 Cure 3.5
Silica1 Glosscontrol 11.3
Silica2 Glosscontrol 3.8
Wax1 Glosscontrol 4.5
Wax2 Glosscontrol 3.0
Additive1 Dispersant 3.4
Additive 2 Flowandleveling 0.1
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522-72-C 552-82-A
EB206(soft) 14.0%EB5129(hard) 16.5% 30.5Viscosity atshearrateof9.3/sec(25°C) 1385 2520Gloss(60°)onWhiteVCT 26 34Gloss(60°)onBrown uncoatedManningtonLVT 21 24StainTest Wright'sStainSolution 3 3Duration=2hours Mustard 2 1(0=nostain,3=severestain) Lugol'siodinesolution 3 3
AntisepticSolution 1 0BetadineSolution 1 1BlackRITdye 1 1
SharpieMarkers(R,B,G,Bk) 2 2CoalTar 0 0
AverageStain 1.6 1.4Flexibility(1”mandreltest) 1milcoatingonLVT pass passAdhesion(1"mandreltest) 1milcoatingonLVT pass pass
Resinscreeningofexistingproducts– SPFforTesting
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BaseStains• Wright’sstain• Lugol’sstain• Mustard• Antisepticsoln.• Betadine• BlackRITDye• Sharpie(4colors)• CoalTar
ExtraStains• Vinegar• Ketchup• BrownShoePolish• 50%EtOH• Chlorox• Coffee• RedFoodColoring• BlueFoodColoring
Resinscreeningofexistingproducts– SPFforTesting
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Resinscreeningofexistingproducts – TestProtocol
• Coating/Curing:1H-bulb,720mJ/cm2,• Rheology:Viscosityatvariousshearrates(targeted<1,500cpsat25C)• Gloss:20,60,and85degreegloss• StainTest:seepriorslide• Flexibility:1"and¼”mandrelbend(2"widecoatedLVT)• Adhesion(cross-hatch):Scotch898tape,rank0-5(0:noadhesion,5:
perfectadhesion)• Scratch:
• Steelwool(0,and0000),15DR• Sclerometer,Ntofirstgouge• ScotchBritepad(variouscolors)• Companyspecificproprietaryscratchtests
• Curl:80Cfor6hours,23Cfor8hoursandmeasureheightofedge
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Resinscreeningofexistingproducts– Highfunctionalityresins
• EvaluatealternatehighfunctionalityresinsinblendwithARUA3(tough,3f)> ARUA4(6f)> ALUA11(10f)> ALUA9(6f)> ALUA8(6f)
• Samestainresistance,ALUA8bestforviscosity• Allpassedadhesion,scratch(steelwool),mandrelbend
0
200
400
600
800
1000
1200
1400
1600
1800
2000
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
EB5129/206 EB220/206 EB225/206 EB8301R/206
Viscosity,cps
StainRe
sistan
ce
StainResistanceandViscosity
ALUA8
ARUA4
ALUA11
ALUA9
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Resinscreeningofexistingproducts– 4functionalresins
• Evaluate4fresins(PEA6,ALUA7,4,12,&13)witheitherARUA3orALUA8• ALUA8basedformulationsoutperformARUA3basedformulas• Allcoatingspass15DRusing0000steelwoolandhaveexcellentadhesion• Allcoatingspass¼”mandrelbend
0
500
1000
1500
2000
2500
3000
3500
0.0
0.3
0.5
0.8
1.0
1.3
1.5
1.8
2.0
2.3
2.5
264/40 264/8405 264/4201 264/4666 264/4680 5129/40 5129/8405
5129/4201
5129/4666
5129/4680
Viscosity
StainRe
sistance
StainResistanceandViscosity
EB264/4fresin ALUA8/4fresinARUA3/4fresin
PEA6
ALUA7
PEA6
ALUA4
ALUA13
ALUA12
ALUA4
ALUA7
ALUA13
ALUA12
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Resinscreeningofexistingproducts– 4functionalPEAresins
• EvaluatePEAs(PEA5(4f),PEA2(3f),PEA3(3f),PEA4(4f)withARUA3• Similarstainresistance(notquiteasgoodasALUA8/ARUA3)• PEA4bestforviscosity• Allcoatingspass15DRusing0000steelwoolandhaveexcellentadhesion
0
500
1000
1500
2000
2500
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
EB264/800 EB264/854 EB264/885 EB264/893
Viscosity,cps
StainRe
sistan
ce
StainResistanceandViscosity
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Resinscreeningofexistingproducts– EpoxyAcrylates
• EvaluateeitheranEAormodifiedEAwitheitherALUA8orARUA3• UseofEAgivesreasonablestainresistancebuthigherviscosity• UseofmodifiedEAgivegoodstainresistanceandviscosityonlywithALUA8• Allcoatingspass15DRusing0000steelwool
0.0
0.5
1.0
1.5
2.0
2.5
EB3418 EB3418/5129 EB3418/206 EB3720 EB3720/5129 EB3720/206
StainResistanceUsingEA/ModEA
0
500
1000
1500
2000
2500
3000
EB3418 EB3418/5129 EB3418/206 EB3720 EB3720/5129 EB3720/206
ViscosityUsingEA/ModEA
ModEA ModEA/ALUA8
ModEA/ARUA3
EA EA/ALUA8
EA/ARUA3
ModEA ModEA/ALUA8
ModEA/ARUA3
EA EA/ALUA8
EA/ARUA3
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Resinscreeningofexistingproducts– EffectofDiluent
• ReplaceHDDAwithalternatediluent@15%,30%,50%,100%• Littletonodifferencestainresistance,exceptwithhighlevelsofTMPTA,DPHA• ViscosityincreasesasHDDAdecreases• Littletonodifferenceinflexibility,adhesion,steelwoolscratch
0
0.5
1
1.5
2
2.5
StainResistance
15%Replacement
30%Replacement
50%Replacement
100%Replacement
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
Viscosity
15%Replacement
30%Replacement
50%Replacement
100%Replacement
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0.0
0.5
1.0
1.5
2.0
2.5
StainResistancevs.PI
Resinscreeningofexistingproducts– EffectofPI
• [email protected]%• EvaluateblendsofPI5plusaminoacrylates (AA)• EvaluatetotalPIconcentrationat2.5,6.5and10.5%• PI1bestbyitself,littledifferencebyadditionofamines
PI1 PI2 PI3 PI4 PI5 PI5/AA3
PI5/AA2
PI5/AA1
PI5/AA4
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Resinscreeningofexistingproducts– EffectofDispersant
• Evaluate3differentdispersants(offsetviscosityrisegeneratedbysilicaaddition)• Glossandstainresistancesimilarforall3dispersants,largedifferenceinviscosity
1.6 1.6 1.6
14
13
15
0
500
1000
1500
2000
2500
3000
3500
4000
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
Dispers688 Disperbyk2008 Disperbyk2013
Viscosity,cps
StainRe
sistan
ce,G
loss
EffectofDispersantonGloss,StainResistanceandViscosity
StainResistance
60Gloss
Viscosity
Dispersant1 Dispersant2 Dispersant3
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Resinscreeningofexistingproducts– Effectofsilica
• Evaluate8differentsilicablends• Stainresistanceremainsconstant,somevariationingloss,viscosity
1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6
12
14
11 12
14
18 18
15
0
400
800
1200
1600
2000
2400
2800
3200
3600
4000
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
18.0
20.0
UV70C/IJ37(3:1)
Acematt3600/IJ37
(3:1)
70C/OK607(3:1)
OK607/IJ37(3:1)
70C/Syloid620(3:1)
SyloidC812/IJ37(3:1)
SyloidED80/IJ37
(3:1)
70C/Syloid622
Viscosity,cps
StainRe
sistan
ce,G
loss
EffectofSilicaonGloss,StainResistanceandViscosity
StainResistance
60Gloss
Viscosity
25
• AwidevarietyofUVcurableresinswereevaluatedascandidatesforcoatingsonLVT.
• Ingeneral,highfunctionalityUrethaneAcrylatesworkbest,butneedtobecombinedwithalowerfunctionalitytoughresin.
• Polyesteracrylateresinsworkwell,butdonothavequitetheperformanceofUAresins.
• Epoxyacrylateresinshaveeithergoodstainresistanceandhighviscosityorreasonableviscosityandpoorerstainresistance
• StainresistancewasnotimprovedbyusingincreasedPIoranaminoacrylate toreduceO2 inhibition
Conclusions
26
• AllnexUSA:- JoshuaHollett- Hwei-LingYau
Acknowledgements
Thankyou!JonathanShawAllnex,USA
770-280-8370
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