TheEffectofMercuryvsLEDLight SourcesonTackFreeCuring UVLED2015 MikeIdacavage,NeilCramer,Ma;hewSchreiber,andAmeliaDavenport ColoradoPhotopolymerSoluHons October28,2015 OxygenInhibi?on Unpolymerized“tacky” Layer FactorsAffecHngOxygenDiffusion O2 O2O2 O2O O O2O O2 O O2 O2 O2 2 2 O2 2 O2 2 Viscosity PolymerizedLayer GelPoint Substrate CrosslinkingDensity/Tg OxygenSolubility 2 OxygenInhibi?on I • IniHaHon I•+M I•+O2 IM•+O2• IM•+M • PropagaHon IMM•+M IMMM•+M UVEnergy 2I• IM• I+O2• M-O-O• IMM• IMMM• IMMMM• I=IniHatorM=Monomer(oranyacrylate)P=Polymerchain 3 OvercomingOxygenInhibi?on TotalRateofOxygen ConsumpHonwithinthe Sample FluxofOxygenintothe Sample - OxygenSolubility - Viscosity IfFO2>RI--OxygeninhibiHonwill notbeovercome IfFO2<RI--OxygeninhibiHon willbeovercome,resulHngintack freesurfaces,providedexposure Hmesarelongenough AsformulaHonpolymerizes, viscosityincreasesandthe fluxofoxygenintothe sampledecreases 4 OvercomingOxygenInhibi?on ParametersAffecHngOxygenInhibiHon IrradiaHonIntensity PhotoiniHatorConcentraHon PhotoiniHator/IrradiaHonSourceEfficiency/Overlap AffectsRI Viscosity FuncHonality/Crosslinking AffectsFO2 ExposureTime OvercomesoxygeninhibiHonifRI>FO2 5 CuringSetup 300W/inchHeraeusF300HBulb 25WHeraeus385nmLED XXXfpm BeltSpeed/ExposureLength=ExposureTime(Dose) 6 Irgacure 184 Absorption Spectrum 7 TPOAbsorp?onSpectrum 8 UVlampoutput 9 MatchingPIandUVBulb 10 SurfaceCureUsingUV-LED 11 SurfaceCureUsingUV-LED 12 OxygenInhibi?onMercuryBulb PhotoiniHatoris1-hydroxy-cyclohexyl-phenyl-ketone(184)orTPO FormulaHonswerespreadontoglasssubstrateswitha128umdrawdownbar SamplesareirradiatedonaconveyorsystemwithanF300HeraeusHBulb 13 OxygenInhibi?onMercuryBulb PhotoiniHatoris1-hydroxy-cyclohexyl-phenyl-ketone(184)orTPO FormulaHonswerespreadontoglasssubstrateswitha128umdrawdownbar SamplesareirradiatedonaconveyorsystemwithanF300HeraeusHBulb 14 OxygenInhibi?onMercuryBulb PhotoiniHatoris1-hydroxy-cyclohexyl-phenyl-ketone(184)orTPO FormulaHonswerespreadontoglasssubstrateswitha128umdrawdownbar SamplesareirradiatedonaconveyorsystemwithanF300HeraeusHBulb 15 OxygenInhibi?on–Viscosity&Thiols 16 DiluentEffectonMaterialProper?es 17 OxygenInhibi?on–UVvsUV-Vis PhotoiniHatoris1-hydroxy-cyclohexyl-phenyl-ketone(184)orTPO FormulaHonswerespreadontoglasssubstrateswitha128umdrawdownbar SamplesareirradiatedonaconveyorsystemwithanF300HeraeusHBulb 18 UVvsUV-VisIni?ator–Viscosity&Thiols 19 Tradi?onalvsThiol-BasedFormula?ons 20 MercuryvsLED-Acrylates HBulb–300W/inch385nmLED–25W ~2inchheight6mm(.24inch)height 21 MercuryvsLED-Acrylates 22 MercuryvsLED-Thiols 23 Summary–O2Inhibi?on ! ScaleswithphotoiniHatorconcentraHoninallcases(UV, UV-Vis,andLED). ! Scalesnon-linearlywithphotoiniHatorconcentraHon ! Isaffectedbyviscosity ! IsaffectedbytheaddiHonofthiolmonomer ! WasrelaHvelyunaffectedbydifferenttypesofacrylates ! Mercury:UVvsUV-Vis ! Veryli;leeffect 24 Summary–MercuryvsLED ! Achievingtack-freecuringwithLEDismoredifficult ! Mercuryappearstobebe;erthanLEDfortackfreecuring ! Thismaybeduetothebroaderwavelength(most likelythelowwavelengths) ! TheLEDlightwasmuchlowerpower,sothismayalso playasignificantrole ! Thiol-basedsystemsandhigherphotoiniHator concentraHonscanresultincomparaHvebeltspeedsto classicMercuryLampcuring 25 Acknowledgments MiwonSpecialtyChemicalCo.,Ltd CPSTechnicalTeam 26 ThankYou ContactinformaHon: Dr.MikeJ.Idacavage VPBusinessDevelopment ColoradoPhotopolymerSoluHons 1880S.FlaHronCt Boulder,CO80301 303-551-3213 mike.idacavage@cpspolymers.com www.cpspolymers.com 27
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