TW201920585A - Cationic polymerization curing-type ink jet resin composition for sealing organic el element - Google Patents
Cationic polymerization curing-type ink jet resin composition for sealing organic el element Download PDFInfo
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- TW201920585A TW201920585A TW107121811A TW107121811A TW201920585A TW 201920585 A TW201920585 A TW 201920585A TW 107121811 A TW107121811 A TW 107121811A TW 107121811 A TW107121811 A TW 107121811A TW 201920585 A TW201920585 A TW 201920585A
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- Prior art keywords
- organic
- layer
- sealing
- resin composition
- cationic polymerization
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- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- 238000007789 sealing Methods 0.000 title claims abstract description 35
- 238000010538 cationic polymerization reaction Methods 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 107
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 52
- -1 polysiloxane Polymers 0.000 claims description 48
- 230000004888 barrier function Effects 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 239000012044 organic layer Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 23
- 229920001296 polysiloxane Polymers 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 15
- 239000003505 polymerization initiator Substances 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 238000004040 coloring Methods 0.000 abstract description 9
- 239000012952 cationic photoinitiator Substances 0.000 abstract 2
- 239000004593 Epoxy Substances 0.000 description 41
- 239000010408 film Substances 0.000 description 34
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910010272 inorganic material Inorganic materials 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 2
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QKAIFCSOWIMRJG-UHFFFAOYSA-N (4-methylphenyl)-(4-propan-2-ylphenyl)iodanium Chemical compound C1=CC(C(C)C)=CC=C1[I+]C1=CC=C(C)C=C1 QKAIFCSOWIMRJG-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- DQNSRQYYCSXZDF-UHFFFAOYSA-N 1,4-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1CCC(COC=C)CC1 DQNSRQYYCSXZDF-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- LJWZDTGRJUXOCE-UHFFFAOYSA-N 2-(2-ethylhexyl)oxetane Chemical compound CCCCC(CC)CC1CCO1 LJWZDTGRJUXOCE-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- QYJOVSLBSPJZHH-UHFFFAOYSA-N 2-[12-(oxiran-2-ylmethoxy)dodecoxymethyl]oxirane Chemical compound C1OC1COCCCCCCCCCCCCOCC1CO1 QYJOVSLBSPJZHH-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- OKRCJGMWAZBSSR-UHFFFAOYSA-N 2-[9-(oxiran-2-ylmethoxy)nonoxymethyl]oxirane Chemical compound C1OC1COCCCCCCCCCOCC1CO1 OKRCJGMWAZBSSR-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- MEVBAGCIOOTPLF-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CO1 MEVBAGCIOOTPLF-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- PRWJZNITVOUZBU-UHFFFAOYSA-N 2-chloroxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(Cl)=CC=C3OC2=C1 PRWJZNITVOUZBU-UHFFFAOYSA-N 0.000 description 1
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- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
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- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
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- XUOHEKMIZPOOOI-UHFFFAOYSA-N 7-oxabicyclo[2.2.1]heptane-4-carboxylic acid Chemical compound C1CC2CCC1(C(=O)O)O2 XUOHEKMIZPOOOI-UHFFFAOYSA-N 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical group C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1525—Four-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
- Epoxy Resins (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
Description
本發明為關於有機EL元件之密封用陽離子聚合硬化型噴墨用樹脂組成物。This invention relates to the resin composition for cationic polymerization hardening type inkjet for sealing of an organic EL element.
近年，由於有機電致發光元件(以下亦稱為「有機EL元件」)的高輝度、低消耗電力，故被使用於次世代的照明或顯示器等的電子裝置中。若該有機EL元件與水或氧接觸時，會產生劣化、輝度降低、或是變得不發光之問題。因此，必須保護有機EL元件以免於入侵至電子裝置中的水或氧。為此採用了使用金屬板或玻璃板而成的密封構造，但該構造時則無法使裝置可撓性化。In recent years, organic electroluminescence elements (hereinafter also referred to as "organic EL elements") have been used in electronic devices such as next-generation lighting and displays due to their high brightness and low power consumption. When the organic EL element is brought into contact with water or oxygen, problems such as deterioration, decrease in luminance, or non-light emission occur. Therefore, the organic EL element must be protected from water or oxygen intruding into the electronic device. For this purpose, a sealing structure using a metal plate or a glass plate is used, but in this structure, the device cannot be made flexible.
作為能使裝置可撓性化之同時並能保護有機EL元件以免於水或氧之方法，有將複數的無機層及有機層交互地進行層合於有機EL元件上來形成阻障膜(barrier film)，以密封有機EL元件之方法。依據該方法，藉由阻障膜而延長了水及氧的穿透路徑，將可保護有機EL元件以免於入侵至電子裝置中的水或氧。作為該阻障膜的無機層之形成方法係以ALD、CVD及濺鍍來進行。作為有機層之形成方法，如專利文獻1係揭示著藉由蒸鍍之方法。然而，藉由蒸鍍來形成有機層之方法時，所使用的組成物的損失(loss)為多之同時，亦具有反應室(chamber)會被污染之類的問題。As a method capable of making the device flexible and protecting the organic EL element from water or oxygen, there is a method in which a plurality of inorganic layers and organic layers are alternately laminated on the organic EL element to form a barrier film. ) To seal the organic EL element. According to this method, the penetration path of water and oxygen is extended by the barrier film, and the organic EL element can be protected from water or oxygen invading into the electronic device. The method for forming the inorganic layer as the barrier film is performed by ALD, CVD, and sputtering. As a method for forming the organic layer, Patent Document 1 discloses a method by vapor deposition. However, in the method for forming an organic layer by vapor deposition, there are many problems such as the loss of the composition used and the contamination of the chamber.
另一方面，作為塗佈組成物以形成有機層之一般的方法，如有噴墨法。藉由噴墨法係可解決蒸鍍法的上述問題點，但為了使從噴墨的噴嘴進行吐出，必須讓組成物成為低黏度。On the other hand, as a general method of applying a composition to form an organic layer, there is an inkjet method. The inkjet method can solve the above-mentioned problems of the vapor deposition method. However, in order to discharge the inkjet nozzle, the composition must have a low viscosity.
專利文獻2中揭示著一種作為噴墨塗佈用的組成物，其係使用於有機EL元件密封用阻障膜的有機層，藉由使用包含特定的聚矽氧化合物而成的硬化性樹脂，使組成物成為低黏度化。 [先前技術文獻] [專利文獻]Patent Document 2 discloses a composition for inkjet coating, which is used as an organic layer of a barrier film for sealing an organic EL element, and uses a curable resin containing a specific polysiloxane, Make the composition low in viscosity. [Prior Art Literature] [Patent Literature]
[專利文獻1] 日本特表2005-522891號公報 [專利文獻2] WO2016/167347號公報[Patent Document 1] Japanese Patent Publication No. 2005-522891 [Patent Document 2] WO2016 / 167347
[發明所欲解決之課題][Problems to be Solved by the Invention]
專利文獻2中所揭示的噴墨塗佈用的組成物，作為硬化性樹脂，除了特定的聚矽氧化合物以外亦包含黏度較高的樹脂，故組成物整體而言黏度仍為高，而難以在室溫下使用於噴墨。又，專利文獻2的噴墨塗佈用的組成物係以365nm的所謂的短波長來確認其硬化性，而被要求著即使是在可見光域亦可硬化的更優異的硬化性。 因此，本發明之課題係提供一種低黏度、且硬化性為優異、不具有著色的問題的有機EL元件之密封用樹脂組成物。 [解決課題之手段]The composition for inkjet coating disclosed in Patent Document 2 contains a resin having a high viscosity as a curable resin in addition to a specific polysiloxane, and therefore the composition has a high viscosity as a whole, which is difficult. Used for inkjet at room temperature. In addition, the composition for inkjet coating of Patent Document 2 confirms its curability at a so-called short wavelength of 365 nm, and is required to have more excellent curability even in the visible light region. Therefore, an object of the present invention is to provide a resin composition for sealing an organic EL device having a low viscosity, an excellent curability, and no coloring problem. [Means for solving problems]
本發明為具有下述之構成。 [1].一種有機EL元件之密封用陽離子聚合硬化型噴墨用樹脂組成物，其包含硬化性樹脂(A)及光陽離子聚合起始劑(B)， 前述硬化性樹脂(A)包含下述式(II)所表示之化合物， 前述光陽離子聚合起始劑(B)為碘鎓鹽(iodonium salt)。[2].如[1]所記載之有機EL元件之密封用陽離子聚合硬化型噴墨用樹脂組成物，其中，前述硬化性樹脂(A)進一步包含聚矽氧化合物。 [3].如[2]所記載之有機EL元件之密封用陽離子聚合硬化型噴墨用樹脂組成物，其中，前述聚矽氧化合物為具有陽離子硬化性官能基之化合物。 [4].如[2]或[3]所記載之有機EL元件之密封用陽離子聚合硬化型噴墨用組成物，其中，前述聚矽氧化合物包含選自由下述式(IV)、(V)及(IX)所表示之化合物所成之群中之至少1種。(式(IV)中，R1 係互相獨立為C1 ~C6 烷基，X1 係-R2 -R3 所表示之基，且R2 係互相獨立為單鍵或C1 ~C3 伸烷基，R3 係互相獨立為3,4-環氧環己基或3,4-環氧環戊基，m係0~3的整數，n係0~3的整數， 式(V)中，R4 係互相獨立為C1 ~C6 烷基，R5 係互相獨立為C1 ~C6 烷基或2-(3,4-環氧環己基)乙基， 式(IX)中，R10 、R11 、R12 係互相獨立為甲基、甲氧基或乙氧基，且R10 、R11 及R12 中的至少1個為甲氧基或乙氧基，R13 係下述式所表示之構造之任一者，a係1~4的整數) [5].如[1]~[4]中任一項所記載之有機EL元件之密封用陽離子聚合硬化型噴墨用組成物，其中，前述硬化性樹脂(A)進一步包含選自由下述式(I)、(III)及(VI)所表示之化合物所成之群中之至少1種。[6].如[1]~[5]中任一項所記載之有機EL元件之密封用陽離子聚合硬化型噴墨用樹脂組成物，其中，進一步包含噻吨酮(thioxanthone)系增感劑(C)。 [7].如[1]~[6]中任一項所記載之有機EL元件之密封用陽離子聚合硬化型噴墨用樹脂組成物，其中，25℃時的黏度為20mPa･s以下。 [8].一種有機EL元件，其具備有： 基板； 形成於前述基板上的由第1電極層及第2電極層以及前述第1電極層和第2電極層之間的有機電致發光層所構成的元件本體部； 形成於前述元件本體部上的使有機層與無機層交互層合而成的阻障膜， 前述阻障膜中的前述有機層為[1]~[7]中任一項所記載之有機EL元件之密封用陽離子聚合硬化型噴墨用樹脂組成物的硬化物。 [9].如[8]所記載之有機EL元件，其中，前述阻障膜中，以前述元件本體部側的第1層成為有機層之方式來使前述有機層與前述無機層交互層合。 [10].如[8]所記載之有機EL元件，其中，前述阻障膜中，以前述元件本體部側的第1層成為無機層之方式來使前述有機層與前述無機層交互層合。 [11].一種如[8]~[10]中任一項所記載之有機EL元件之製造方法，其係藉由下述步驟(i)與步驟(ii)來形成前述阻障膜中的有機層， 步驟(i)：藉由噴墨來塗佈[1]~[7]中任一項所記載之有機EL元件之密封用陽離子聚合硬化型噴墨用樹脂組成物； 步驟(ii)：將已塗佈的有機EL元件之密封用陽離子聚合硬化型噴墨用組成物以光照射及/或加熱來使其硬化。 [12].一種顯示體，其具有[8]~[10]中任一項所記載之有機EL元件。 [發明的效果]The present invention has the following constitution. [1]. A cationic polymerization hardening type inkjet resin composition for sealing an organic EL element, comprising a hardening resin (A) and a photocationic polymerization initiator (B), wherein the hardening resin (A) contains In the compound represented by the formula (II), the photocationic polymerization initiator (B) is an iodonium salt. [2]. The resin composition for cationic polymerization hardening type inkjet for sealing of the organic EL element according to [1], wherein the curable resin (A) further contains a polysiloxane. [3]. The cationic polymerization hardening type inkjet resin composition for sealing an organic EL element according to [2], wherein the polysiloxane compound is a compound having a cation-curable functional group. [4]. The cationic polymerization hardening type inkjet composition for sealing an organic EL element according to [2] or [3], wherein the polysiloxane compound contains a compound selected from the following formula (IV), (V ) And at least one of the groups formed by the compounds represented by (IX). (In formula (IV), R 1 is independently C 1 to C 6 alkyl, X 1 is a group represented by -R 2 to R 3 , and R 2 is independently a single bond or C 1 to C 3 Alkyl, R 3 is independently 3,4-epoxycyclohexyl or 3,4-epoxycyclopentyl, m is an integer of 0 to 3, n is an integer of 0 to 3, in formula (V) , R 4 is independently C 1 to C 6 alkyl, and R 5 is independently C 1 to C 6 alkyl or 2- (3,4-epoxycyclohexyl) ethyl. In formula (IX), R 10 , R 11 , and R 12 are each independently methyl, methoxy, or ethoxy, and at least one of R 10 , R 11, and R 12 is methoxy or ethoxy. R 13 is under Any one of the structures represented by the formula, a is an integer of 1 to 4) [5]. The cation polymerization hardening type inkjet composition for sealing an organic EL element according to any one of [1] to [4], wherein the curable resin ( A) It further contains at least 1 sort (s) chosen from the group which consists of the compound represented by following formula (I), (III), and (VI). [6]. The cationic polymerization hardening type inkjet resin composition for sealing the organic EL element according to any one of [1] to [5], further comprising a thioxanthone sensitizer (C). [7]. The cationic polymerization hardening type inkjet resin composition for sealing an organic EL element according to any one of [1] to [6], wherein the viscosity at 25 ° C is 20 mPams or less. [8] An organic EL element comprising: a substrate; and an organic electroluminescent layer formed on the substrate by a first electrode layer and a second electrode layer, and between the first electrode layer and the second electrode layer. A formed element body portion; a barrier film formed on the element body portion by laminating an organic layer and an inorganic layer alternately, the organic layer in the barrier film is any one of [1] to [7] The cured product of the resin composition for cationic polymerization hardening type inkjet for sealing of the organic EL element of one item. [9]. The organic EL device according to [8], wherein in the barrier film, the organic layer and the inorganic layer are alternately laminated such that the first layer on the element body side becomes an organic layer. . [10]. The organic EL device according to [8], wherein in the barrier film, the organic layer and the inorganic layer are alternately laminated so that the first layer on the element body side becomes an inorganic layer. . [11]. A method for manufacturing an organic EL device according to any one of [8] to [10], which comprises forming the barrier film in the foregoing barrier film by the following steps (i) and (ii). Organic layer, step (i): coating the resin composition for sealing cation polymerization hardening type inkjet of the organic EL element according to any one of [1] to [7] by inkjet; step (ii) : The coated cation polymerization hardening type inkjet composition for an organic EL element is hardened by light irradiation and / or heating. [12]. A display comprising the organic EL element according to any one of [8] to [10]. [Effect of the invention]
本發明之有機EL元件之密封用樹脂組成物為低黏度、且硬化性為優異、不具有著色的問題。The sealing resin composition of the organic EL element of the present invention has a low viscosity, is excellent in hardenability, and does not have a problem of coloring.
[實施發明之最佳形態][Best Mode for Implementing Invention]
1. 陽離子聚合硬化型噴墨用樹脂組成物 陽離子聚合硬化型噴墨用樹脂組成物(以下亦簡稱為「樹脂組成物」)，其係包含硬化性樹脂(A)及光陽離子聚合起始劑(B)的有機EL元件之密封用陽離子聚合硬化型噴墨用樹脂組成物，且前述硬化性樹脂(A)包含下述式(II)所表示之化合物、前述光陽離子聚合起始劑(B)為碘鎓鹽的有機EL元件之密封用陽離子聚合硬化型噴墨用樹脂組成物。於此，所謂的「陽離子聚合硬化型組成物」，係指以酸作為起始劑而進行聚合的硬化性組成物。1. Resin composition for cationic polymerization hardening type inkjet resin composition for cationic polymerization hardening type inkjet resin (hereinafter also referred to as "resin composition"), which contains a curable resin (A) and a photocationic polymerization initiator (B) A cationic polymerization-curable resin composition for sealing an organic EL element, wherein the curable resin (A) includes a compound represented by the following formula (II) and the photocationic polymerization initiator (B ) Is a resin composition for cation polymerization hardening type inkjet for sealing organic EL elements that are iodonium salts. Here, the "cationic hardening composition" refers to a hardening composition which is polymerized using an acid as an initiator.
(1)硬化性樹脂(A) 硬化性樹脂(A)為藉由光或熱而進行硬化的樹脂，較佳為藉由光而進行硬化的樹脂。 硬化性樹脂(A)包含上述式(II)所表示之化合物。 藉由使用上述式(II)所表示之化合物，可使表面張力及黏度之平衡為佳、適合於藉由噴墨之塗佈之同時，並可形成薄膜。(1) Curable resin (A) The curable resin (A) is a resin that is cured by light or heat, and is preferably a resin that is cured by light. The sclerosing | hardenable resin (A) contains the compound represented by the said Formula (II).使用 By using the compound represented by the above formula (II), the balance between surface tension and viscosity can be improved, it is suitable for coating by inkjet, and a thin film can be formed.
就硬化性為良好、可使表面張力成為對噴墨塗佈用而言為適切之值並可進一步成為低黏度之觀點而言，硬化性樹脂(A)中的上述式(II)所表示之化合物的比例，較佳為10~60質量%，又較佳為10~40質量%。The hardening resin (A) is represented by the above formula (II) from the viewpoint that the hardening property is good, the surface tension can be adjusted to a value suitable for inkjet coating, and the viscosity can be further reduced. The proportion of the compound is preferably 10 to 60% by mass, and more preferably 10 to 40% by mass.
硬化性樹脂(A)係較佳進一步包含聚矽氧化合物。聚矽氧化合物係可改善濕潤性。作為聚矽氧化合物，以具有陽離子硬化性官能基之聚矽氧化合物為又較佳。所謂的陽離子硬化性官能基，係指能藉由酸而進行聚合之官能基，可舉出含雜環基及具有電子供給基的電子密度高的乙烯基，更具體而言可舉出環氧基、氧雜環丁烷基(oxetanyl)、乙烯醚基(CH2 =CH-O-)等，特佳為環氧基。具有陽離子硬化性官能基之聚矽氧化合物之中，以脂環式環氧聚矽氧化合物為更佳。The curable resin (A) is preferably further containing a polysiloxane. Polysiloxanes improve wetting. The polysiloxane is preferably a polysiloxane having a cation-curable functional group. The cation-curable functional group refers to a functional group that can be polymerized by an acid, and examples include a vinyl group having a high electron density containing a heterocyclic group and an electron donating group, and more specifically, an epoxy group. Group, oxetanyl, vinyl ether group (CH 2 = CH-O-), and the like, particularly preferably an epoxy group. Among polysiloxanes having a cation-curable functional group, an alicyclic epoxy polysiloxane is more preferred.
作為具有陽離子硬化性官能基之聚矽氧化合物，較佳為選自由下述式(IV)、(V)及(IX)所成之群中之至少1種。(式(IV)中，R1 係互相獨立為C1 ~C6 烷基，X1 係-R2 -R3 所表示之基，且R2 係互相獨立為單鍵或C1 ~C3 伸烷基，R3 係互相獨立為3,4-環氧環己基或3,4-環氧環戊基，m係0~3的整數，n係0~3的整數， 式(V)中，R4 係互相獨立為C1 ~C6 烷基，R5 係互相獨立為C1 ~C6 烷基或2-(3,4-環氧環己基)乙基， 式(IX)中，R10 、R11 、R12 係互相獨立為甲基、甲氧基或乙氧基，且R10 、R11 及R12 中的至少1個為甲氧基或乙氧基，R13 係下述式所表示之構造之任一者，a係1~4的整數)。The polysiloxane compound having a cation-curable functional group is preferably at least one selected from the group consisting of the following formulae (IV), (V), and (IX). (In formula (IV), R 1 is independently C 1 to C 6 alkyl, X 1 is a group represented by -R 2 to R 3 , and R 2 is independently a single bond or C 1 to C 3 Alkyl, R 3 is independently 3,4-epoxycyclohexyl or 3,4-epoxycyclopentyl, m is an integer of 0 to 3, n is an integer of 0 to 3, in formula (V) , R 4 is independently C 1 to C 6 alkyl, and R 5 is independently C 1 to C 6 alkyl or 2- (3,4-epoxycyclohexyl) ethyl. In formula (IX), R 10 , R 11 , and R 12 are each independently methyl, methoxy, or ethoxy, and at least one of R 10 , R 11, and R 12 is methoxy or ethoxy. R 13 is under Any one of the structures represented by the formula, a is an integer from 1 to 4).
於此，上述烷基可任意為直鏈狀或支鏈狀，可舉出甲基、乙基、丙基、i-丙基、n-丁基、ｔ-丁基、n-戊基、n-己基等。Here, the alkyl group may be arbitrarily linear or branched, and examples thereof include methyl, ethyl, propyl, i-propyl, n-butyl, t-butyl, n-pentyl, and n -Hexy etc.
式(IV)中，R1 係較佳為相同的甲基或乙基。R2 係較佳為相同的C2 ~C3 伸烷基。R3 係較佳為相同的3,4-環氧環己基。 式(V)中，R4 係較佳為相同的甲基或乙基，R5 係較佳為相同的甲基、乙基或2-(3,4-環氧己基)乙基。In formula (IV), R 1 is preferably the same methyl or ethyl group. R 2 is preferably the same C 2 to C 3 alkylene. The R 3 system is preferably the same 3,4-epoxycyclohexyl group. In formula (V), R 4 is preferably the same methyl or ethyl group, and R 5 is preferably the same methyl, ethyl or 2- (3,4-epoxyhexyl) ethyl group.
作為式(IX)所表示之化合物，可舉出：該等係以作為Shinetsu silicone股份有限公司的KBM-403、KBM-402、KBE-403、KBE-402、KBM-303而被市售著。Examples of the compound represented by the formula (IX) include: These are commercially available as KBM-403, KBM-402, KBE-403, KBE-402, KBM-303 as Shinetsu silicone Co., Ltd.
式(IX)中，R10 、R11 及R12 係以互相獨立為甲氧基或乙氧基為較佳，R13 較佳為下述式所表示之構造。 In formula (IX), R 10 , R 11, and R 12 are each preferably a methoxy group or an ethoxy group, and R 13 is preferably a structure represented by the following formula.
作為式(IV)所表示之化合物，特佳為以下之化合物。作為式(V)所表示之化合物，特佳為以下之化合物。作為式(IX)所表示之化合物，特佳為以下之化合物。 As the compound represented by formula (IV), the following compounds are particularly preferred. As the compound represented by formula (V), the following compounds are particularly preferred. As the compound represented by formula (IX), the following compounds are particularly preferred.
式(IV)所表示之化合物、式(V)所表示之化合物及式(IX)所表示之化合物係可為單獨或可為2種以上之組合。式(IV)所表示之化合物、式(V)所表示之化合物及式(IX)所表示之化合物之中，較佳為選自由式(V)所表示之化合物及式(IX)所表示之化合物所成之群中之至少1種的化合物。 上述式(IV)、(V)及(IX)所表示之化合物係可提高硬化性，又，分子量大幅地為低黏度，故可降低揮發性。The compound represented by the formula (IV), the compound represented by the formula (V), and the compound represented by the formula (IX) may be used alone or in a combination of two or more. Among the compound represented by formula (IV), the compound represented by formula (V), and the compound represented by formula (IX), it is preferably selected from the compound represented by formula (V) and the compound represented by formula (IX) At least one compound in a group of compounds.化合物 The compounds represented by the above formulae (IV), (V), and (IX) can improve the hardenability, and the molecular weight is substantially low, so the volatility can be reduced.
若包含上述式(IV)、(V)及(IX)所表示之化合物之情形時，就硬化性為良好、可使成為低黏度之觀點而言，硬化性樹脂(A)中的上述式(IV)所表示之化合物的比例，較佳為10~80質量%，又較佳為10~40質量%，更佳為10~30質量%，硬化性樹脂(A)中的上述式(V)所表示之化合物的比例，較佳為10~50質量%，又較佳為10~40質量%，硬化性樹脂(A)中的上述式(IX)所表示之化合物的比例，較佳為10~60質量%，又較佳為20~50質量%。When the compounds represented by the above formulae (IV), (V), and (IX) are included, the above formula (in the curable resin (A)) is from the viewpoint of good curability and low viscosity. The proportion of the compound represented by IV) is preferably 10 to 80% by mass, more preferably 10 to 40% by mass, and even more preferably 10 to 30% by mass. The above formula (V) in the curable resin (A) The proportion of the compound represented is preferably 10 to 50% by mass, and more preferably 10 to 40% by mass. The proportion of the compound represented by the formula (IX) in the curable resin (A) is preferably 10 ~ 60% by mass, and more preferably 20 ~ 50% by mass.
硬化性樹脂(A)係以進一步包含選自由下述式(I)、(III)及(VI)所表示之化合物所成之群中之至少1種又較佳為。 The curable resin (A) preferably further contains at least one selected from the group consisting of compounds represented by the following formulae (I), (III), and (VI).
若包含上述式(I)、(III)及(VI)所表示之化合物之情形時，就硬化性為良好、可使成為低黏度之觀點而言，硬化性樹脂(A)中的上述式(I)所表示之化合物的比例，較佳為10~50質量%，又較佳為10~40質量%，硬化性樹脂(A)中的上述式(III)所表示之化合物的比例，較佳為10~40質量%，又較佳為10~30質量%，硬化性樹脂(A)中的上述式(VI)所表示之化合物的比例，較佳為5~40質量%，又較佳為5~30質量%。In the case where the compounds represented by the formulae (I), (III), and (VI) are included, the formula (I) in the curable resin (A) is in terms of good curability and low viscosity. The proportion of the compound represented by I) is preferably from 10 to 50% by mass, and more preferably from 10 to 40% by mass. The proportion of the compound represented by the formula (III) in the curable resin (A) is more preferred. It is 10 to 40% by mass, and more preferably 10 to 30% by mass. The proportion of the compound represented by the formula (VI) in the curable resin (A) is preferably 5 to 40% by mass, and more preferably 5 to 30% by mass.
硬化性樹脂(A)，除了上述化合物以外，亦可包含以下的硬化性樹脂。 作為其他的硬化性樹脂，只要是分子中具有至少1個的陽離子聚合性官能基即可，未特別限定，可舉例如分子內具有至少1個的環氧基、氧雜環丁烷基、乙烯醚基(CH2 =CH-O-)等之化合物等。The curable resin (A) may include the following curable resins in addition to the compounds described above. The other curable resin is not particularly limited as long as it has at least one cationically polymerizable functional group in the molecule, and examples thereof include epoxy, oxetanyl, and ethylene having at least one in the molecule. Ether group (CH 2 = CH-O-) and the like.
作為分子內具有環氧基之化合物，可舉出芳香族環氧化合物、脂肪族環氧化合物、脂環式環氧化合物及其他的環氧樹脂。由於陽離子聚合性為更高、且可有效地進行光硬化，故較佳為脂環式環氧化合物。Examples of the compound having an epoxy group in the molecule include an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, and other epoxy resins. An alicyclic epoxy compound is preferable because it has higher cationic polymerizability and can effectively perform light curing.
作為芳香族環氧化合物，除了如苯基縮水甘油醚般的化合物以外，可舉出雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚AD型環氧化合物、雙酚S型環氧化合物等的雙酚型環氧化合物；萘型環氧化合物；苯酚酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物等的酚醛清漆型環氧化合物；氫化雙酚A型環氧化合物等的醇型環氧化合物；溴化環氧化合物等的鹵化環氧化合物；多官能型環氧化合物，作為該具體例，可舉出DIC公司製的EPICLON850、850-S、EXA-850CPR等的雙酚A型環氧化合物；DIC公司製的EPICLON830-S、EXA-830LVP等的雙酚F型環氧化合物；DIC公司製的EPICLON之HP-4032D、HP-7200H等的萘型環氧化合物；DIC公司製的EPICLON N-740、N-770等的苯酚酚醛清漆型環氧化合物；DIC公司製的EPICLON N-660、N-670、N-655-EXP-S等的甲酚酚醛清漆型環氧化合物；四(羥基苯基)烷烴的縮水甘油醚、四羥基二苯基酮的縮水甘油醚、環氧化聚乙烯酚等的多官能環氧化合物。Examples of the aromatic epoxy compound include compounds such as phenyl glycidyl ether, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol AD type epoxy compounds, and bisphenol S type Bisphenol epoxy compounds such as epoxy compounds; naphthalene epoxy compounds; novolac epoxy compounds such as phenol novolac epoxy compounds, cresol novolac epoxy compounds; hydrogenated bisphenol A epoxy Alcohol-type epoxy compounds such as compounds; halogenated epoxy compounds such as brominated epoxy compounds; polyfunctional epoxy compounds. Specific examples thereof include EPICLON850, 850-S, and EXA-850CPR manufactured by DIC Corporation. Bisphenol A epoxy compounds; bisphenol F epoxy compounds such as EPICLON830-S, EXA-830LVP manufactured by DIC; naphthalene epoxy compounds such as HP-4032D and HP-7200H of EPICLON manufactured by DIC ; Phenol novolac type epoxy compounds such as EPICLON N-740, N-770 manufactured by DIC; cresol novolac types such as EPICLON N-660, N-670, N-655-EXP-S manufactured by DIC Epoxy compound; glycidyl ether of tetra (hydroxyphenyl) alkane, tetra Polyfunctional epoxy compounds such as glycidyl ether of hydroxydiphenyl ketone, epoxidized polyvinyl phenol and the like.
作為脂肪族環氧化合物，可舉出多元醇或其環氧烷烴加成物的聚縮水甘油醚，作為該具體例，可舉出乙二醇二縮水甘油醚、二乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、1,4-丁二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、1,9-壬二醇二縮水甘油醚、1,12-十二烷二醇二縮水甘油醚、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚(共榮社化學公司製的Epolite 100MF)、聚乙二醇二縮水甘油醚等。Examples of the aliphatic epoxy compound include polyglycidyl ether of a polyhydric alcohol or an alkylene oxide adduct thereof, and specific examples thereof include ethylene glycol diglycidyl ether and diethylene glycol diglycidyl ether , Propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether Ether, 1,12-dodecanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether (Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), polyethylene glycol diglycidyl Ether, etc.
作為脂環式環氧化合物，可舉出前述芳香族環氧化合物的氫化物、環己烷系、環己基甲基酯系、環己基甲基醚系、螺環系及三環癸烷系環氧化合物，作為該具體例，可舉出ADEKA公司製的KRM-2408、JER公司製的YX-8034等的氫化雙酚A型環氧化合物；3’,4’-環氧環己基甲基 3,4-環氧環己烷羧酸酯、1,2：8,9-二環氧檸檬烯、1,2-環氧基-4-乙烯基環己烷、2,2-雙(羥基甲基)-1-丁醇的1,2-環氧基-4-(2-環氧乙烷基)環己烷加成物(Daicel公司製的EHPE3150)等的脂環型環氧化合物。Examples of the alicyclic epoxy compound include a hydride of the aforementioned aromatic epoxy compound, a cyclohexane system, a cyclohexyl methyl ester system, a cyclohexyl methyl ether system, a spiro ring system, and a tricyclodecane system ring. Examples of the oxygen compound include hydrogenated bisphenol A type epoxy compounds such as KRM-2408 manufactured by ADEKA Corporation and YX-8034 manufactured by JER Corporation; 3 ', 4'-epoxycyclohexylmethyl 3 1,4-epoxycyclohexane carboxylic acid ester, 1, 2: 8,9-diepoxy limonene, 1,2-epoxy-4-vinylcyclohexane, 2,2-bis (hydroxymethyl An alicyclic epoxy compound such as 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol (EHPE3150 manufactured by Daicel).
作為其他的分子內具有環氧基之化合物，可舉出雜環狀型環氧化合物、縮水甘油醚型環氧化合物、縮水甘油酯型環氧化合物、縮水甘油胺型環氧化合物、橡膠改質環氧化合物、胺基甲酸酯改質環氧化合物、環氧化聚丁二烯、環氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物、含環氧基的聚酯化合物、含環氧基的聚胺基甲酸酯化合物、含環氧基的丙烯酸化合物等。Examples of other compounds having an epoxy group in the molecule include a heterocyclic epoxy compound, a glycidyl ether epoxy compound, a glycidyl ester epoxy compound, a glycidylamine epoxy compound, and rubber modification. Epoxy compound, urethane modified epoxy compound, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene block copolymer, epoxy-containing polyester compound, epoxy-containing Based polyurethane compounds, epoxy-containing acrylic compounds, and the like.
作為分子內具有氧雜環丁烷基之化合物之具體例，可舉出3-乙基-3-羥基甲基氧雜環丁烷(氧雜環丁烷醇)(例如，東亞合成公司製OXT-101)、2-乙基己基氧雜環丁烷(例如，東亞合成公司製OXT-212)、亞二甲苯基雙氧雜環丁烷(XDO/例如，東亞合成公司製OXT-121)、3-乙基-3{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷(例如，東亞合成公司製OXT-221)、氧雜環丁烷基矽倍半氧烷(例如，東亞合成公司製OXT-191)、苯酚酚醛清漆氧雜環丁烷(例如，東亞合成公司製PHOX)及3-乙基-3-苯氧基甲基氧雜環丁烷(POX：例如，東亞合成公司製OXT-211)。Specific examples of the compound having an oxetanyl group in the molecule include 3-ethyl-3-hydroxymethyloxetane (oxetanol) (for example, OXT manufactured by Toa Synthesis Corporation) -101), 2-ethylhexyloxetane (e.g., OXT-212 manufactured by Toa Synthesis), xylylene dioxetane (XDO / e.g., OXT-121 manufactured by Toa Synthesis), 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (for example, OXT-221 manufactured by Toa Synthetic Corporation), oxetan Butylsilsesquioxane (e.g., OXT-191 manufactured by Toa Synthesis), phenol novolac oxetane (e.g., PHOX manufactured by Toa Synthesis) and 3-ethyl-3-phenoxymethyl Oxetane (POX: For example, OXT-211 manufactured by Toa Synthesis Corporation).
作為分子內具有乙烯醚基之化合物之具體例，可舉出羥基丁基乙烯基醚(例如，Nippon Carbide工業公司製HBVE)、1,4-環己烷二甲醇的乙烯基醚(例如，Nippon Carbide工業公司製CHVE)、三乙二醇二乙烯基醚(例如，ISP公司製DVE-3)、十二烷基乙烯基醚(例如，Nippon Carbide工業公司製DVE)、及環己基乙烯基醚(例如，Nippon Carbide工業公司製CVE)。Specific examples of the compound having a vinyl ether group in the molecule include hydroxybutyl vinyl ether (for example, HBVE manufactured by Nippon Carbide Industries), and vinyl ether of 1,4-cyclohexanedimethanol (for example, Nippon Carveide Industries (CHVE), triethylene glycol divinyl ether (for example, DVE-3 manufactured by ISP), dodecyl vinyl ether (for example, DVE manufactured by Nippon Carbide Industries), and cyclohexyl vinyl ether (For example, CVE manufactured by Nippon Carbide Industries).
以上的化合物，在與上述式(I)~(VI)及(IX)所表示之化合物組合之際，以黏度、表面張力等為適合於噴墨之塗佈之方式來進行選擇，又，來決定調配量。因此，硬化性樹脂(A)中，上述式(I)~(VI)及(IX)所表示之化合物以外的硬化性樹脂較佳為未滿10質量%，又較佳為5質量%以下，更佳為不包含上述式(I)~(VI)及(IX)所表示之化合物以外的硬化性樹脂。When the above compounds are combined with the compounds represented by the formulae (I) to (VI) and (IX), the viscosity and surface tension are selected in a manner suitable for inkjet coating. Decide how much to deploy. Therefore, in the curable resin (A), the curable resin other than the compounds represented by the formulae (I) to (VI) and (IX) is preferably less than 10% by mass, and more preferably 5% by mass or less. It is more preferable that curable resins other than the compounds represented by the formulae (I) to (VI) and (IX) are not included.
(2)光陽離子聚合起始劑(B) 光陽離子聚合起始劑(B)為碘鎓鹽。由於碘鎓鹽係以少量來使用即可獲得優異的硬化性，故不具有著色等的問題。 作為碘鎓鹽，可舉出下述式(VII)所表示之化合物。式(VII)中，Ar1 及Ar2 係獨立為取代或非取代的芳基，X- 係陰離子。(2) Photocationic polymerization initiator (B) The photocationic polymerization initiator (B) is an iodonium salt. Since an iodonium salt can be used in a small amount to obtain excellent curability, it does not have problems such as coloring. Examples of the iodonium salt include compounds represented by the following formula (VII). In formula (VII), Ar 1 and Ar 2 are independently a substituted or unsubstituted aryl group, and an X - based anion.
於此，式(VII)中的「芳基」係意味著碳數6~18的芳香族烴基，較佳為苯基或萘基。芳基可為非取代，亦可被1個以上的任意取代基所取代，作為如此般的取代基，可舉出碳數1~18的直鏈或支鏈狀的烷基、碳數1~18的直鏈或支鏈狀的烷氧基、碳數2~18的直鏈或支鏈狀的烷氧基羰基、碳數2~18的直鏈或支鏈狀的醯氧基、鹵素原子、氰基、硝基、羥基等。Here, the "aryl group" in the formula (VII) means an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is preferably a phenyl group or a naphthyl group. The aryl group may be unsubstituted or substituted with one or more optional substituents. Examples of such a substituent include a linear or branched alkyl group having 1 to 18 carbon atoms and a carbon number of 1 to 18 Straight or branched alkoxy group of 18, straight or branched alkoxycarbonyl group of 2 to 18 carbon atoms, straight or branched alkoxy group of 2 to 18 carbon atoms, halogen atom , Cyano, nitro, hydroxyl, etc.
作為式(VII)中的陰離子部分X- ，可舉出C1- 、Br- 、SbF6 - 、PF6 - 、BF4 - 、下述式(VIII)所表示之陰離子部分、PF4 (CF3 CF2 )2 - 、PF5 (CF3 CF2 )- 、(C6 F5 )4 B- 、((CF3 )2 C6 H3 )4 B- 、(C6 F5 )4 Ga- 、((CF3 )2 C6 H3 )4 Ga- 等，較佳為下述式(VIII)所表示之陰離子部分或(C6 F5 )4 B- ，又較佳為下述式(VIII)所表示之陰離子部分。式(VIII)中，n係3~5的整數，p係1~3的整數。 式(VIII)中，由於6-n為1以上，故陰離子具有氟化碳鏈，而可作為相對較強的酸來產生作用。因此，陽離子聚合性能會變高，使得UV硬化性變得更好。 作為式(VIII)所表示之陰離子部，較佳為[P(C2 F5 )3 F3 ]- 。 作為碘鎓鹽，較佳為氟代烷基氟磷酸鎓碘鎓鹽，特別是以上述式(VII)中的Ar1 為4-甲基苯基、Ar2 為4-異丙基苯基、X- 為[P(C2 F5 )3 F3 ]- 的化合物為較佳。 作為光陽離子聚合起始劑(B)之市售品，可舉出IK-1(San-apro公司製)。The anionic portion X of the formula (VII) -, include C1 -, Br -, SbF 6 -, PF 6 -, BF 4 -, by the following formula (VIII) represented by the anion portion, PF 4 (CF 3 CF 2) 2 -, PF 5 (CF 3 CF 2) -, (C 6 F 5) 4 B -, ((CF 3) 2 C 6 H 3) 4 B -, (C 6 F 5) 4 Ga - , ((CF 3) 2 C 6 H 3) 4 Ga - like, preferably by the following formula (VIII) or of the anionic portion represented by (C 6 F 5) 4 B -, and is preferably represented by the following formula ( VIII). In formula (VIII), n is an integer of 3 to 5, and p is an integer of 1 to 3. In formula (VIII), since 6-n is 1 or more, the anion has a fluorinated carbon chain and can act as a relatively strong acid. Therefore, the cationic polymerization performance becomes higher, and the UV curability becomes better. As the anion moiety of formula (VIII) represented by the, preferably [P (C 2 F 5) 3 F 3] -. As the iodonium salt, a fluoroalkylfluorophosphonium iodonium salt is preferred, and in particular, Ar 1 in the formula (VII) is 4-methylphenyl, Ar 2 is 4-isopropylphenyl, X - is [P (C 2 F 5) 3 F 3] - compounds are preferred. As a commercial item of a photocationic polymerization initiator (B), IK-1 (made by San-apro company) is mentioned.
(3)噻吨酮系增感劑(C) 上述光陽離子聚合起始劑(B)，較佳為與噻吨酮系增感劑(C)一起使用。 作為噻吨酮系增感劑，可舉出異丙基噻吨酮、2,4-二乙基噻吨酮、2-氯噻吨酮、2,4-二乙基噻吨酮、2-氯噻吨酮、噻吨酮銨鹽等，該等之中較佳為2,4-二乙基噻吨酮。(3) Thiotanone-type sensitizer (C) The photocationic polymerization initiator (B) is preferably used together with thioxanthone-type sensitizer (C). Examples of the thioxanthone-based sensitizer include isopropylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2- Chloroxanthones, thioxanthone ammonium salts, and the like, among these, 2,4-diethylthioxanthone is preferred.
(4)其他的成分 在可發揮本發明之效果之範圍內，樹脂組成物可包含進一步的成分。作為進一步的成分，可舉出保存穩定劑、抗氧化劑、可塑劑、黏彈性調整劑、界面活性調整劑(潤濕劑或消泡劑)及填充劑。樹脂組成物中的其他的成分，較佳為未滿10質量%，又較佳為未滿3質量%。 作為保存穩定劑，可使用受阻酚系抗氧化劑，可使用例如Irganox 1010、Irganox 565、Irganox 1035FF(均為BASF公司製)。(4) Other components 树脂 As long as the effects of the present invention can be exhibited, the resin composition may contain further components. Examples of the further components include a storage stabilizer, an antioxidant, a plasticizer, a viscoelasticity adjusting agent, an interfacial activity adjusting agent (wetting agent or antifoaming agent), and a filler. The other components in the resin composition are preferably less than 10% by mass, and more preferably less than 3% by mass. As the storage stabilizer, a hindered phenol-based antioxidant can be used, and for example, Irganox 1010, Irganox 565, and Irganox 1035FF (all manufactured by BASF) can be used.
(5)樹脂組成物 樹脂組成物係被使用於藉由噴墨之塗佈。 為了使適合於從噴墨的噴嘴來進行吐出，樹脂組成物的黏度，在25℃時較佳為20mPa･s以下，又較佳為5~20mPa･s。黏度的測定為依據實施例所記載之方法。有機EL元件密封用途之組成物，較佳為未加溫下即為低黏度化，如此般之黏度時，以未加溫則可將樹脂組成物適合於藉由噴墨來進行塗佈。(5) Resin composition The resin composition is used for coating by inkjet. In order to discharge from a nozzle suitable for inkjet, the viscosity of the resin composition at 25 ° C is preferably 20 mPa ･ s or less, and more preferably 5 to 20 mPa ･ s. The viscosity was measured according to the method described in the examples. The composition for sealing the organic EL element is preferably reduced in viscosity without heating. With such a viscosity, the resin composition is suitable for coating by inkjet without heating.
樹脂組成物較佳為不包含有機溶劑。為了使組成物低黏度化，通常會使用有機溶劑，但如果有機EL元件密封用途之組成物中含有有機溶劑的話，有機溶劑會滲入至層合體的有機EL元件之各界面並氣化，而成為界面剝離之原因，或因為殘留的有機溶劑使得電子及電洞的載體被淬滅(quench)，而成為妨礙有機EL元件機能之原因，因而不宜將組成物以有機溶劑稀釋來予以低黏度化。於此，所謂的不包含有機溶劑，係指不包含對於組成物的黏度或有機EL元件之機能會造成影響的量的有機溶劑之意思，但並未排除對於該等而言為不會造成影響的極微量的有機溶劑。作為有機溶劑，可舉出25℃時的黏度為未滿1mPa･s的有機化合物，特別是25℃時的黏度為未滿1mPa･s的醇類、醚類、內酯類。由於會對有機EL元件造成影響，故樹脂組成物較佳為不包含水來作為溶劑，但並未排除大氣中的水分之混入。 樹脂組成物係被使用於有機EL元件之密封用。The resin composition preferably does not contain an organic solvent. In order to reduce the viscosity of the composition, an organic solvent is generally used. However, if an organic solvent is contained in the composition for sealing the organic EL element, the organic solvent will penetrate into the interfaces of the organic EL element of the laminate and vaporize, thereby becoming The reason for interfacial peeling or because the remaining organic solvents cause the carriers of electrons and holes to be quenched and become a cause of hindering the function of the organic EL element, it is not appropriate to dilute the composition with an organic solvent to reduce the viscosity. Here, the term “does not include organic solvents” means that organic solvents are not included in an amount that affects the viscosity of the composition or the function of the organic EL element, but it does not exclude that it will not affect them. A very small amount of organic solvents. Examples of the organic solvent include organic compounds having a viscosity of less than 1 mPa ･ s at 25 ° C, and particularly alcohols, ethers, and lactones having a viscosity of less than 1 mPa ･ s at 25 ° C. Since it affects the organic EL element, it is preferable that the resin composition does not include water as a solvent, but the inclusion of moisture in the atmosphere is not excluded. Resin compositions are used for sealing organic EL devices.
相對於樹脂組成物中的硬化性樹脂(A)100質量份，光陽離子聚合起始劑(B)的比例較佳為0.5~2質量份，又較佳為0.5~1質量份；噻吨酮系增感劑(C)的比例較佳為0.01~1質量份，又較佳為0.01~0.05質量份。以如此般之範圍時，可充分發揮硬化性之同時，不會產生著色。保存穩定劑(包含作為保存穩定劑所使用的抗氧化劑)的比例，相對於樹脂組成物中的硬化性樹脂(A)100質量份，較佳為0.01~1.0質量份，又較佳為0.01~0.50質量份。 可藉由包含將上述各成分進行混合的步驟之方法來製造樹脂組成物。The ratio of the photocationic polymerization initiator (B) to 100 parts by mass of the curable resin (A) in the resin composition is preferably 0.5 to 2 parts by mass, and more preferably 0.5 to 1 part by mass; thioxanthone The ratio of the system sensitizer (C) is preferably 0.01 to 1 part by mass, and more preferably 0.01 to 0.05 part by mass. In such a range, the hardening properties can be fully exhibited without coloring. The proportion of the storage stabilizer (including the antioxidant used as the storage stabilizer) is preferably 0.01 to 1.0 parts by mass, and more preferably 0.01 to 100 parts by mass of the curable resin (A) in the resin composition. 0.50 parts by mass.树脂 A resin composition can be produced by a method including a step of mixing the aforementioned components.
2. 有機EL元件及其製造方法 有機EL元件為具備有基板、元件本體部與阻障膜，該元件本體部係形成於前述基板上的由第1電極層及第2電極層以及前述第1電極層和第2電極層之間的有機電致發光層所構成者，該阻障膜係形成於前述元件本體部上的使有機層與無機層交互層合而成者。2. Organic EL element and manufacturing method thereof The organic EL element includes a substrate, an element body portion, and a barrier film. The element body portion is formed on the substrate by a first electrode layer and a second electrode layer, and the first electrode layer. The barrier film is formed of an organic electroluminescence layer between an electrode layer and a second electrode layer. The barrier film is formed on the element body, and an organic layer and an inorganic layer are alternately laminated.
有機EL元件，在元件本體部、與阻障膜之間可進一步具有氟化鋰等的離子性無機化合物的蒸鍍膜、或由聚對二甲苯(parylene)等的有機物等所成的保護膜・機能膜。 作為基板未特別限制，可舉出：玻璃基板；以聚二甲基矽氧烷、二苯基矽氧烷等的聚矽氧烷系聚合物、聚矽氧樹脂/聚矽氧橡膠、聚(甲基)丙烯酸酯、聚對苯二甲酸乙二醇酯、聚甲基丙烯酸甲酯A、聚碳酸酯、聚乙烯、聚丙烯等的聚烯烴、聚胺基甲酸酯、聚苯乙烯、氟化聚合物(PTFE(聚四氟乙烯)、PVdF(聚偏二氟乙烯)等)、聚氯乙烯、聚甲基氫矽氧烷、及二甲基矽氧烷與甲基氫矽氧烷單位的共聚合物等所形成的基板；有機或者無機的發光體元件；以及有機或者無機的半導體基板，較佳為透明、可撓性之材料，又較佳為高分子材料。The organic EL device may further include a vapor-deposited film of an ionic inorganic compound such as lithium fluoride, or a protective film made of an organic substance such as parylene between the element body and the barrier film. Functional film. The substrate is not particularly limited, and examples thereof include glass substrates, polysiloxane polymers such as polydimethylsiloxane and diphenylsiloxane, polysiloxane resin / polysiloxane rubber, and poly (siloxane). (Meth) acrylate, polyethylene terephthalate, polymethyl methacrylate A, polycarbonate, polyethylene, polypropylene, etc. polyolefin, polyurethane, polystyrene, fluorine Polymers (PTFE (polytetrafluoroethylene), PVdF (polyvinylidene fluoride), etc.), polyvinyl chloride, polymethylhydrosiloxane, and dimethylsiloxane and methylhydrosiloxane units A substrate formed of a copolymer or the like; an organic or inorganic light-emitting element; and an organic or inorganic semiconductor substrate, preferably a transparent and flexible material, and more preferably a polymer material.
作為第1及第2電極未特別限制，可舉出ITO、ZnO或IZO等的鋅氧化物、錫氧化物、鋅鋁氧化物、鉭氧化物、金屬薄膜(例如，厚度10~20nm的Ag、MgAg等的金屬膜)等的周知的透明電極材料。 作為有機電致發光層，通常而言為將由電洞注入層、電洞輸送層、發光層、電子輸送層及電子注入層所構成的層合構造設定為基本，但亦可為省略該等層中的幾個層而構成的構造。作為各層的材料，可從周知的材料中予以適當地選擇使用。The first and second electrodes are not particularly limited, and examples include zinc oxide, tin oxide, zinc aluminum oxide, tantalum oxide, and metal thin films (such as Ag with a thickness of 10 to 20 nm, ITO, ZnO, or IZO). A well-known transparent electrode material such as a metal film such as MgAg. As the organic electroluminescent layer, a layered structure composed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is generally set as a basic structure, but these layers may be omitted. A few layers in the structure. As a material of each layer, a well-known material can be suitably selected and used.
阻障膜係將元件本體部的與基板接觸之面為相反側之面進行包覆者，因應所需，亦可將元件本體部的側面及元件本體部的周邊的基板進行包覆。又，除了上述以外，亦可於元件本體部與基板之間進一步設置阻障膜。 阻障膜中的有機層與無機層，可以元件本體部側的第1層成為有機層之方式來交互地進行層合，或亦可以本體部側的第1層成為無機層之方式來交互地進行層合，但較佳為以元件本體部側的第1層成為有機層之方式來交互地進行層合。此係由於，可使有機EL元件之彎折變強之同時，可使阻障膜變得平坦，進一步亦可將元件本體上的異物進行包埋。The barrier film covers a surface of the element main body portion that is in contact with the substrate on the opposite side, and the side surface of the element main body portion and the substrate around the element main body portion may be covered as required. In addition to the above, a barrier film may be further provided between the element body and the substrate. The organic layer and the inorganic layer in the barrier film can be alternately laminated in such a manner that the first layer on the element body side becomes an organic layer, or the first layer in the body portion side can be interactively laminated. The lamination is performed, but the lamination is preferably performed alternately such that the first layer on the element body portion side becomes an organic layer. This is because at the same time that the bending of the organic EL element can be strengthened, the barrier film can be flattened, and further, foreign matter on the element body can be embedded.
阻障膜中所包含的有機層為前述陽離子聚合硬化型噴墨用樹脂組成物的硬化物，可藉由下述步驟(i)與步驟(ii)來形成，步驟(i)：藉由噴墨來塗佈前述陽離子聚合硬化型噴墨用樹脂組成物；步驟(ii)：將已塗佈的陽離子聚合硬化型噴墨用樹脂組成物以光照射及/或加熱來使其硬化。相較於藉由蒸鍍法來形成有機層之情形，藉由使用噴墨來形成有機層時的樹脂組成物的損失較少，故可減少樹脂組成物的使用量之同時，亦不會污染反應室。The organic layer included in the barrier film is a cured product of the aforementioned cationic polymerization-curable resin composition for inkjet, and can be formed by the following steps (i) and (ii). Step (i): by spraying The above-mentioned resin composition for cation polymerization-curable inkjet is coated with ink; step (ii): the applied cation polymerization-curable resin composition for inkjet is cured by light irradiation and / or heating. Compared with the case where the organic layer is formed by the vapor deposition method, the resin composition is less lost when the organic layer is formed by using inkjet, so the amount of the resin composition can be reduced while not contaminating. Reaction chamber.
(步驟i) 作為噴墨裝置，可使用周知的裝置。 作為藉由噴墨來進行塗佈中的塗佈方式，可舉出壓電噴墨方式、感熱噴墨方式、閥噴墨方式、連續式噴墨等，但作為有機EL元件之密封用，以未加溫者為較佳，故較佳為壓電噴墨方式、閥噴墨方式。 作為噴墨裝置中的上述樹脂組成物的吐出溫度，較佳為23~55℃，又較佳為23~50℃。上述樹脂組成物，即使是未加溫亦可進行吐出，且有機EL元件之製造係以未加溫來進行吐出為期望，故特佳為23~27℃。(Step i) As the inkjet device, a known device can be used. Examples of the coating method in coating by inkjet include a piezoelectric inkjet method, a thermal inkjet method, a valve inkjet method, and a continuous inkjet method. However, as a method of sealing an organic EL element, The unheated one is preferable, so the piezoelectric inkjet method and the valve inkjet method are preferable. The discharge temperature of the resin composition in the inkjet device is preferably 23 to 55 ° C, and more preferably 23 to 50 ° C. The above resin composition can be discharged without being heated, and the production of the organic EL element is desirably carried out without being heated, so it is particularly preferably 23 to 27 ° C.
(步驟ii) 作為步驟ii中的光源，只要是能量線即可，未特別限定，可舉出可見光線、紫外線、X線、電子線等的活性能量線。作為能量線之光源，可舉例如金屬鹵素燈、超高壓水銀燈、高壓水銀燈、低壓水銀燈、氙氣燈、水銀氙氣燈、鹵素燈、脈衝氙氣燈、LED等。能量線之照射，可以能量線之累積光量成為100~15,000mJ/cm2 之方式來進行照射。累積光量係較佳為500~10,000mJ/cm2 ，又較佳為1,000~6,000mJ/cm2 。 上述樹脂組成物，從上述光源所照射的光線之波長，就硬化性之觀點而言，係以自可見光區域至更短波長為止之波長為合適，就防止有機EL元件之損壞之觀點而言，係以自可見光區域至更長波長為止之波長為合適，故就兼具硬化性及防止有機EL元件之損壞之觀點而言，以可見光區域波長為更合適。具體而言，LED的波峰波長可舉出365nm、405nm、375nm、385nm、395nm及405nm等，較佳為395nm及405nm。(Step ii) The light source in step ii is not particularly limited as long as it is an energy ray, and examples thereof include active energy rays such as visible rays, ultraviolet rays, X-rays, and electron rays. Examples of the light source of the energy line include metal halogen lamps, ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, mercury-xenon lamps, halogen lamps, pulsed xenon lamps, and LEDs. Irradiation of energy rays can be performed in such a manner that the accumulated light amount of the energy rays becomes 100 to 15,000 mJ / cm 2 . The cumulative light amount is preferably 500 to 10,000 mJ / cm 2 , and more preferably 1,000 to 6,000 mJ / cm 2 . The resin composition has a wavelength from the visible light region to a shorter wavelength from the viewpoint of the curability of the wavelength of the light irradiated by the light source. From the viewpoint of preventing damage to the organic EL element, Since the wavelength from the visible light region to a longer wavelength is suitable, the wavelength in the visible light region is more suitable in terms of both the hardening property and the prevention of damage to the organic EL element. Specifically, the peak wavelength of the LED includes 365 nm, 405 nm, 375 nm, 385 nm, 395 nm, and 405 nm, and is preferably 395 nm and 405 nm.
阻障膜中所包含的無機層，可藉由ALD、CVD、濺鍍等來形成。作為所使用的無機材料，可舉出氮化金屬化合物、氧化金屬化合物、鹵化金屬化合物等，但不限定於該等。The inorganic layer included in the barrier film can be formed by ALD, CVD, sputtering, or the like. Examples of the inorganic material used include, but are not limited to, metal nitride compounds, metal oxide compounds, and metal halide compounds.
當元件本體部上存在著有機層與無機層為交互進行層合而成的阻障膜時，可延長水及氧的穿透路徑，並可保護元件本體部以免於入侵至電子裝置中的水或氧。 有機EL元件可具有進一步的層。作為進一步的層，可舉出有機材料、無機材料及其組合之膜，較佳為無機材料膜。作為有機材料，可舉例如在基材的材料中所舉出的有機材料。作為無機材料，可舉例如A12 O3 、SiO2 、TiO2 、ZrO2 、ITO等的金屬氧化物、Cu、Au、Mg、Ag等的金屬、BN、Si3 N4 、GaN、TiN等的金屬氮化物等。形成進一步的層之方法未特別限定，方法並未特別限定若為無機材料膜之情形時，可舉出濺鍍法或電子迴旋共振電漿CVD法等。進一步的層之厚度未特別限制，較佳為0.01~1,000μm，又較佳為0.1~0.2μm。When a barrier film formed by laminating an organic layer and an inorganic layer alternately on the element body portion, the penetration path of water and oxygen can be extended, and the element body portion can be protected from water invading into the electronic device. Or oxygen. The organic EL element may have further layers. Examples of further layers include films of organic materials, inorganic materials, and combinations thereof, and inorganic material films are preferred. As an organic material, the organic material mentioned in the material of a base material is mentioned, for example. Examples of the inorganic material include metal oxides such as A1 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , and ITO, metals such as Cu, Au, Mg, and Ag, BN, Si 3 N 4 , GaN, and TiN. Metal nitride and so on. The method for forming a further layer is not particularly limited, and in the case of an inorganic material film, the method is not particularly limited, and examples thereof include a sputtering method and an electron cyclotron resonance plasma CVD method. The thickness of the further layer is not particularly limited, but is preferably 0.01 to 1,000 μm, and more preferably 0.1 to 0.2 μm.
較佳的有機EL元件之製造方法，如下述的有機EL元件之製造方法，其包含下述步驟(1)與步驟(2)， 步驟(1)：將元件本體部形成於基板上； 步驟(2)：將有機層與無機層交互地層合於前述元件本體部上來形成阻障膜， 前述步驟(2)中的有機層為藉由下述步驟(i)與步驟(ii)來形成， 步驟(i)：藉由噴墨來塗佈前述陽離子聚合硬化型噴墨用樹脂組成物； 步驟(ii)：將已塗佈的噴墨用組成物以光照射及/或加熱來使其硬化。 [實施例]A preferred method for manufacturing an organic EL element is as follows: a method for manufacturing an organic EL element, which includes the following steps (1) and (2), (1): forming the element body on the substrate; (1) step ( 2): An organic layer and an inorganic layer are alternately laminated on the element body to form a barrier film. The organic layer in the step (2) is formed by the following steps (i) and (ii). ， Step (i): coating the aforementioned cationic polymerization-curable inkjet resin composition by inkjet; (ii) step (ii): curing the coated inkjet composition by light irradiation and / or heating. [Example]
將實施例及比較例之各組成物，使用以下之原材料來進行製造。 式(I)：上述式(I)所表示之化合物 式(II)：上述式(II)所表示之化合物 式(III)：上述式(III)所表示之化合物 式(IV)：作為上述式(IV)所表示之化合物之一種的下述的化合物式(V)：作為上述式(V)所表示之化合物之一種的下述的化合物式(VI)：上述式(VI)所表示之化合物 式(IX)：作為上述式(IX)所表示之化合物之一種的下述的化合物AL-OX：EX-141：苯基縮水甘油醚(Nagase chemtex股份有限公司製) POX：苯基氧雜環丁烷(東亞合成公司製)。具有以下之構造。IK-1：4-甲基苯基-4-(1-甲基乙基)苯基碘鎓・三(五氟乙基)三氟磷酸鹽(San-apro公司製) DETXs：2,4-二乙基噻吨酮(日本化藥公司製) CPI-410S：San-apro公司製 鋶型光酸產生劑 SI助劑：4-羥基苯基二甲基鋶甲基亞硫酸酯(三新工業公司製) 保存穩定劑 Irganox 1010：作為保存穩定劑所使用的受阻酚系抗氧化劑(BASF公司製)Each composition of the Example and the comparative example was manufactured using the following raw materials. Formula (I): The compound represented by the above formula (I) Formula (II): The compound represented by the above formula (II) Formula (III): The compound represented by the above formula (III) Formula (IV): As the above formula (IV) One of the following compounds Formula (V): The following compound is one of the compounds represented by the formula (V). Formula (VI): The compound represented by the above formula (VI) Formula (IX): The following compound as one of the compounds represented by the above formula (IX) AL-OX: EX-141: Phenyl glycidyl ether (manufactured by Nagase chemtex Co., Ltd.) POX: phenyloxetane (manufactured by Toa Synthetic Corporation). It has the following structure. IK-1: 4-methylphenyl-4- (1-methylethyl) phenyliodonium tris (pentafluoroethyl) trifluorophosphate (manufactured by San-apro) DETXs: 2,4- Diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) CPI-410S: 鋶 -type photoacid generator manufactured by San-apro Co. SI auxiliary: 4-hydroxyphenyldimethyl sulfonium methyl sulfite (Sanshin Industries (Production company) Storage stabilizer Irganox 1010: Hindered phenolic antioxidant (manufactured by BASF) used as a storage stabilizer
＜測定方法及評估基準＞ (黏度) 使用黏度計(東機產業製RC-215)，以25℃、No.1°34’×R24轉子、100rpm之條件下來進行測定。<Measurement method and evaluation criteria> (Viscosity) Measured at 25 ° C, No. 1 ° 34 '× R24 rotor, and 100 rpm using a viscometer (RC-215 manufactured by Toki Sangyo).
(薄膜硬化性) 將實施例及比較例之各樹脂組成物，利用旋轉塗佈法以10μm的厚度來塗佈至玻璃基板上，對於塗膜分別進行： (1)以100mW/cm2 、10秒鐘(1000mJ/cm2 )來照射395nm的LED之情形； (2)以100mW/cm2 、30秒鐘(3000mJ/cm2 )來照射395nm的LED之情形； (3)使通過金屬鹵素燈(MHL)2次以照射3000mJ/cm2 之情形； ，利用手指觸碰並依據以下之基準來評估光照射後立即的硬化狀態。 ○：膜的表面為乾燥，故判斷硬化為充分結束。 △：在膜上殘留部分的沾黏性，故判斷隨著時間的繼續經過而硬化會持續進行，但於上述照射後當下的硬化為不足。 ×：膜整體性並未乾燥，故判斷硬化性為不足。(Film hardenability) Each resin composition of the examples and comparative examples was applied on a glass substrate by a spin coating method to a thickness of 10 μm, and the coating films were each performed: (1) at 100 mW / cm 2 , 10 seconds (1000mJ / cm 2) to illuminate an LED 395nm case; (2) at 100mW / cm 2, 30 seconds (3000mJ / cm 2) to illuminate an LED 395nm situation; (3) passing through the metal halide lamp (the MHL) is irradiated 2 times to 3000mJ / cm 2 of the case; by finger touch and evaluated according to the following basis of a hardened state immediately after the light irradiation. ：: The surface of the film is dry, so it is judged that the curing is sufficiently completed. (Triangle | delta): The stickiness of the residual part on a film, it is judged that hardening will continue as time progresses, but the current hardening after the said irradiation is insufficient. ×: The integrity of the film was not dried, so the hardenability was judged to be insufficient.
(著色) 使實施例及比較例之各樹脂組成物成為厚度100μm之方式利用載玻片來予以夾住，以100mW/cm2 、10秒鐘(1000mJ/cm2 )來照射395nm的LED，利用目視對於光照射後立即的著色狀態來進行外觀觀察，並依以下之基準來進行評估。 ○：幾乎為無色 ×：帶有黃色(Coloring) Each resin composition of the Examples and Comparative Examples was sandwiched by a glass slide so that the thickness was 100 μm, and 395 nm LEDs were irradiated at 100 mW / cm 2 for 10 seconds (1000 mJ / cm 2 ), The appearance of the coloring state immediately after light irradiation was visually observed, and evaluated based on the following criteria. ○: almost colorless ×: with yellow
[實施例1~8、比較例1~5] 依據表1所記載之調配，將各成分放入容量160m1的NANKO容器中，在室溫(25℃)下利用Three-one-motor(新東科學公司製)來進行攪拌，而得到約50g的樹脂組成物。 [Examples 1 to 8, Comparative Examples 1 to 5] According to the preparations described in Table 1, each component was placed in a NANKO container with a capacity of 160 m1, and a three-one-motor (Shinto) was used at room temperature (25 ° C). (Manufactured by Scientific Corporation), and about 50 g of a resin composition was obtained.
將實施例1~3與比較例1及2進行比較時可得知，若使用其他的氧雜環丁烷化合物的AL-OX來替代上述式(II)所表示之化合物的話，硬化性為差。將實施例1~3與比較例3進行比較時可得知，若大量地使用縮水甘油基化合物的EX-141來替代上述式(II)所表示之化合物的話，硬化性為差。由實施例4~8可得知，上述式(II)所表示之化合物即使是不與上述式(I)之化合物組合，亦可展現出良好的硬化性、且無著色。將實施例與比較例4及5進行比較時可得知，作為光聚合起始劑，若使用鋶鹽的CPI-410S來替代碘鎓鹽的話，量較少之情形時則硬化性為差，而量較多之情形時雖然硬化性為些許不佳之程度，但產生了著色的問題。 [產業利用性]When comparing Examples 1 to 3 and Comparative Examples 1 and 2, it can be seen that if AL-OX of another oxetane compound is used instead of the compound represented by the formula (II), the hardenability is poor. . When comparing Examples 1 to 3 and Comparative Example 3, it was found that if a large amount of EX-141 of a glycidyl compound is used instead of the compound represented by the formula (II), the hardenability is poor. It can be seen from Examples 4 to 8 that the compound represented by the above formula (II) can exhibit good hardenability without coloring even if it is not combined with the compound of the above formula (I). When comparing the Examples with Comparative Examples 4 and 5, it can be seen that, as a photopolymerization initiator, if CPI-410S of a sulfonium salt is used instead of the iodonium salt, the curability is poor when the amount is small. On the other hand, when the amount is large, although the hardenability is somewhat poor, coloring problems occur. [Industrial availability]
本發明之樹脂組成物係可適合使用於有機EL元件之密封。The resin composition of the present invention can be suitably used for sealing an organic EL device.
本專利申請案係主張於2017年6月30日所提出專利申請的日本專利申請案特願2017-129703的優先權，並參考特願2017-129703的全部揭示內容而予以援用在本說明書中。This patent application claims the priority of Japanese Patent Application No. 2017-129703 for a patent application filed on June 30, 2017, and refers to the entire disclosure of Japanese Patent Application No. 2017-129703 for reference in this specification.
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| JP3162634B2 (en) * | 1995-10-02 | 2001-05-08 | 関西ペイント株式会社 | UV-curable can coating composition |
| US8808457B2 (en) | 2002-04-15 | 2014-08-19 | Samsung Display Co., Ltd. | Apparatus for depositing a multilayer coating on discrete sheets |
| US8030401B1 (en) * | 2006-08-03 | 2011-10-04 | Henkel Corporation | Photoinitiated cationic epoxy compositions |
| CN101631832A (en) * | 2007-03-14 | 2010-01-20 | 亨斯迈先进材料（瑞士）有限公司 | Photocurable compositions for preparing ABS-like articles |
| KR20110134407A (en) * | 2009-02-20 | 2011-12-14 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for dye-sensitized solar cell and dye-sensitized solar cell |
| JP6200203B2 (en) * | 2013-05-16 | 2017-09-20 | 積水化学工業株式会社 | Sealant for organic electroluminescence display element and method for producing organic electroluminescence display element |
| CN107109190B (en) * | 2015-04-17 | 2020-06-23 | 积水化学工业株式会社 | Sealing agent for electronic device and method for manufacturing electronic device |
| CN104892549A (en) * | 2015-04-20 | 2015-09-09 | 南昌大学 | Synthesis method of allyl oxetane compound for ultraviolet light curing |
| JP6410158B2 (en) * | 2016-10-07 | 2018-10-24 | パナソニックＩｐマネジメント株式会社 | Ultraviolet curable resin composition, organic EL light emitting device manufacturing method, and organic EL light emitting device |
-
2018
- 2018-06-19 JP JP2018550006A patent/JP6464409B1/en active Active
- 2018-06-19 CN CN201880030035.6A patent/CN110603276B/en active Active
- 2018-06-19 KR KR1020197035383A patent/KR102337035B1/en active IP Right Grant
- 2018-06-19 WO PCT/JP2018/023181 patent/WO2019003991A1/en active Application Filing
- 2018-06-26 TW TW107121811A patent/TWI742294B/en active
Also Published As
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| CN110603276A (en) | 2019-12-20 |
| JPWO2019003991A1 (en) | 2019-06-27 |
| KR102337035B1 (en) | 2021-12-08 |
| JP6464409B1 (en) | 2019-02-06 |
| CN110603276B (en) | 2020-07-17 |
| WO2019003991A1 (en) | 2019-01-03 |
| KR20200024768A (en) | 2020-03-09 |
| TWI742294B (en) | 2021-10-11 |
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