JPWO2015029689A1 - Light post-curing resin composition - Google Patents
Light post-curing resin composition Download PDFInfo
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- JPWO2015029689A1 JPWO2015029689A1 JP2014539172A JP2014539172A JPWO2015029689A1 JP WO2015029689 A1 JPWO2015029689 A1 JP WO2015029689A1 JP 2014539172 A JP2014539172 A JP 2014539172A JP 2014539172 A JP2014539172 A JP 2014539172A JP WO2015029689 A1 JPWO2015029689 A1 JP WO2015029689A1
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- resin composition
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- 239000011342 resin composition Substances 0.000 title claims abstract description 48
- 238000011417 postcuring Methods 0.000 title claims abstract description 34
- 125000000524 functional group Chemical group 0.000 claims abstract description 35
- 125000003277 amino group Chemical group 0.000 claims abstract description 33
- 125000002091 cationic group Chemical group 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 16
- 239000003822 epoxy resin Substances 0.000 claims description 25
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- 238000000016 photochemical curing Methods 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000001302 tertiary amino group Chemical group 0.000 claims description 5
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 6
- -1 3,4-epoxycyclohexyl Chemical group 0.000 description 39
- 239000000758 substrate Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 11
- 239000006087 Silane Coupling Agent Substances 0.000 description 11
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 11
- 229920001187 thermosetting polymer Polymers 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910010272 inorganic material Inorganic materials 0.000 description 7
- 239000011147 inorganic material Substances 0.000 description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 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 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010943 off-gassing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- UCBQKJQXUPVHFJ-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-yl-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C1C=CC=C1 UCBQKJQXUPVHFJ-UHFFFAOYSA-N 0.000 description 4
- PFHLXMMCWCWAMA-UHFFFAOYSA-N [4-(4-diphenylsulfoniophenyl)sulfanylphenyl]-diphenylsulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC(C=C1)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 PFHLXMMCWCWAMA-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 102100033806 Alpha-protein kinase 3 Human genes 0.000 description 2
- 101710082399 Alpha-protein kinase 3 Proteins 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 125000003566 oxetanyl group Chemical group 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003553 thiiranes Chemical group 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- VLTYTTRXESKBKI-UHFFFAOYSA-N (2,4-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 VLTYTTRXESKBKI-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- 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
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- QLGYTJLZFZUDFL-UHFFFAOYSA-N 1,3-bis[1-(1h-imidazol-2-yl)propyl]urea Chemical compound N=1C=CNC=1C(CC)NC(=O)NC(CC)C1=NC=CN1 QLGYTJLZFZUDFL-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VSHKLLPSERFSRJ-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)pyridin-1-ium-2-carbonitrile Chemical compound N#CC1=CC=CC=[N+]1CC1=CC=CC2=CC=CC=C12 VSHKLLPSERFSRJ-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- VDAIJDKQXDCJSI-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethylurea Chemical compound CC1=NC=CN1CCNC(N)=O VDAIJDKQXDCJSI-UHFFFAOYSA-N 0.000 description 1
- HTJPMGZZCKEJNA-UHFFFAOYSA-N 2-[3-[4-[4-[2,3-bis(2-hydroxyethoxy)phenyl]sulfanylphenyl]sulfanylphenyl]sulfanyl-2-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(SC=2C=CC(SC=3C=CC(SC=4C(=C(OCCO)C=CC=4)OCCO)=CC=3)=CC=2)=C1OCCO HTJPMGZZCKEJNA-UHFFFAOYSA-N 0.000 description 1
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 1
- OLKHRYQRCJLWLL-UHFFFAOYSA-N 2-cyclohex-3-en-1-yloxirane Chemical compound C1OC1C1CC=CCC1 OLKHRYQRCJLWLL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JIRSPRISVBOKLX-UHFFFAOYSA-N 6-[(3-methyl-7-oxabicyclo[4.1.0]heptan-2-yl)methoxy]-6-oxohexanoic acid Chemical compound OC(=O)CCCCC(=O)OCC1C(C)CCC2OC21 JIRSPRISVBOKLX-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
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- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical compound N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
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- AENNXXRRACDJAY-UHFFFAOYSA-N bis(2-dodecylphenyl)iodanium Chemical compound CCCCCCCCCCCCC1=CC=CC=C1[I+]C1=CC=CC=C1CCCCCCCCCCCC AENNXXRRACDJAY-UHFFFAOYSA-N 0.000 description 1
- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 1
- OWZDULOODZHVCQ-UHFFFAOYSA-N diphenyl-(4-phenylsulfanylphenyl)sulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC1=CC=CC=C1 OWZDULOODZHVCQ-UHFFFAOYSA-N 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- QCGKUFZYSPBMAY-UHFFFAOYSA-N methyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1C(C(=O)OC)CCC2OC21 QCGKUFZYSPBMAY-UHFFFAOYSA-N 0.000 description 1
- BLGWXSOTAXXXDE-UHFFFAOYSA-N n'-[1-(1h-imidazol-2-yl)propyl]hexanediamide Chemical compound NC(=O)CCCCC(=O)NC(CC)C1=NC=CN1 BLGWXSOTAXXXDE-UHFFFAOYSA-N 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G59/20—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 epoxy compounds used
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
- C08G2650/24—Polymeric initiators
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Electroluminescent Light Sources (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本発明は、アウトガスの発生を抑制することができ、透明性及び信頼性に優れる光後硬化性樹脂組成物を提供することを目的とする。本発明は、カチオン硬化性樹脂、光カチオン重合開始剤、及び、アミノ基とカチオン重合性官能基とを有する化合物を含有する光後硬化性樹脂組成物である。An object of the present invention is to provide an optical post-curing resin composition that can suppress the generation of outgas and is excellent in transparency and reliability. The present invention is a photo post-curing resin composition comprising a cationic curable resin, a photo cationic polymerization initiator, and a compound having an amino group and a cationic polymerizable functional group.
Description
本発明は、アウトガスの発生を抑制することができ、透明性及び信頼性に優れる光後硬化性樹脂組成物に関する。 The present invention relates to a light post-curing resin composition that can suppress generation of outgas and is excellent in transparency and reliability.
近年、有機エレクトロルミネッセンス(有機EL)表示素子や有機薄膜太陽電池素子等の有機薄膜素子を用いた有機光デバイスの研究が進められている。有機薄膜素子は真空蒸着や溶液塗布等により簡便に作製できるため、生産性にも優れる。 In recent years, research on organic optical devices using organic thin film elements such as organic electroluminescence (organic EL) display elements and organic thin film solar cell elements has been advanced. The organic thin film element can be easily produced by vacuum deposition, solution coating, or the like, and thus has excellent productivity.
有機EL表示素子は、互いに対向する一対の電極間に有機発光材料層が挟持された薄膜構造体を有する。この有機発光材料層に一方の電極から電子が注入されるとともに他方の電極から正孔が注入されることにより有機発光材料層内で電子と正孔とが結合して自己発光を行う。バックライトを必要とする液晶表示素子等と比較して視認性がよく、より薄型化が可能であり、かつ、直流低電圧駆動が可能であるという利点を有する。 The organic EL display element has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. When electrons are injected from one electrode into the organic light emitting material layer and holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to perform self-light emission. Compared with a liquid crystal display element or the like that requires a backlight, the visibility is better, the thickness can be reduced, and direct current low voltage driving is possible.
ところが、このような有機EL表示素子は、有機発光材料層や電極が外気に曝されるとその発光特性が急激に劣化し寿命が短くなるという問題があった。従って、有機EL表示素子の安定性及び耐久性を高めることを目的として、有機EL表示素子においては、有機発光材料層や電極を大気中の水分や酸素から遮断する封止技術が不可欠となっている。 However, such an organic EL display element has a problem that when the organic light emitting material layer and the electrode are exposed to the outside air, the light emission characteristics thereof are rapidly deteriorated and the life is shortened. Therefore, for the purpose of improving the stability and durability of the organic EL display element, in the organic EL display element, a sealing technique for shielding the organic light emitting material layer and the electrode from moisture and oxygen in the atmosphere is indispensable. Yes.
特許文献1には、上面発光型有機EL表示素子等において、有機EL表示素子基板の間に光硬化性接着剤を満たし、光を照射して封止する方法が開示されている。しかしながら、このように光硬化性接着剤を用いた場合には、光照射時にアウトガスが発生して素子内に充満し、素子の劣化を促進することがあるという問題があった。 Patent Document 1 discloses a method of filling a photocurable adhesive between organic EL display element substrates in a top emission organic EL display element or the like, and irradiating light to seal. However, when the photocurable adhesive is used in this way, there is a problem that outgas is generated during light irradiation and fills the element, thereby promoting deterioration of the element.
本発明は、アウトガスの発生を抑制することができ、透明性及び信頼性に優れる光後硬化性樹脂組成物を提供することを目的とする。 An object of the present invention is to provide an optical post-curing resin composition that can suppress the generation of outgas and is excellent in transparency and reliability.
本発明は、カチオン硬化性樹脂、光カチオン重合開始剤、及び、アミノ基とカチオン重合性官能基とを有する化合物を含有する光後硬化性樹脂組成物である。
以下に本発明を詳述する。The present invention is a photo post-curing resin composition comprising a cationic curable resin, a photo cationic polymerization initiator, and a compound having an amino group and a cationic polymerizable functional group.
The present invention is described in detail below.
本発明者らは、有機EL表示素子等の封止に光硬化性接着剤を用いた場合にアウトガスが発生する原因が、特に光後硬化性接着剤に通常配合されているクラウンエーテル等のエーテル結合を有する化合物からなる硬化遅延剤にあると考えた。即ち、該硬化遅延剤が光照射時に酸等により分解することにより、ジオキサン等がアウトガスとして発生していると考えた。
そこで本発明者らは、このような硬化遅延剤に代えて、アミノ基とカチオン重合性官能基とを有する化合物を用いることにより、アミノ基が硬化遅延効果を発揮しつつ、カチオン重合性官能基により硬化物に取り込まれることでアウトガスの発生を抑制することができることを見出し、本発明を完成させるに至った。The inventors of the present invention are the cause of outgassing when a photocurable adhesive is used for sealing an organic EL display element or the like, and particularly ethers such as crown ethers that are usually blended in a photopostcurable adhesive. It was thought that it exists in the hardening retarder which consists of a compound which has a coupling | bonding. That is, it was considered that dioxane or the like was generated as outgas by decomposition of the curing retarder with an acid or the like during light irradiation.
Therefore, the present inventors have used a compound having an amino group and a cationically polymerizable functional group in place of such a curing retarder, whereby the amino group exhibits a curing retardation effect, and the cationically polymerizable functional group. As a result, it was found that outgassing can be suppressed by being taken into the cured product, and the present invention has been completed.
本発明の光後硬化性樹脂組成物は、アミノ基とカチオン重合性官能基とを有する化合物を含有する。上記アミノ基とカチオン重合性官能基とを有する化合物は、アミノ基が硬化遅延効果を発揮しつつ、カチオン重合性官能基により硬化物に取り込まれることでアウトガスの発生を抑制することができる。
なお、上記アミノ基とカチオン重合性官能基とを有する化合物は、カチオン重合性官能基を有するが、アミノ基を有するためカチオン重合性が極めて低い。The photo post-curing resin composition of the present invention contains a compound having an amino group and a cationic polymerizable functional group. The compound having an amino group and a cationically polymerizable functional group can suppress the generation of outgas by being taken into the cured product by the cationically polymerizable functional group while the amino group exhibits a curing retardation effect.
In addition, although the compound which has the said amino group and a cation polymerizable functional group has a cation polymerizable functional group, since it has an amino group, cation polymerizability is very low.
上記アミノ基としては、第一級アミノ基、第二級アミノ基、第三級アミノ基が挙げられる。上記アミノ基として第二級アミノ基又は第三級アミノ基を有する場合、少なくとも1つのアミノ基の窒素原子がカチオン重合性官能基と直接又はアルキレン基を介して結合していることが好ましい。
上記アミノ基は、適度な効果遅延効果を発揮する観点から、第三級アミノ基であることが好ましい。Examples of the amino group include a primary amino group, a secondary amino group, and a tertiary amino group. When the amino group has a secondary amino group or a tertiary amino group, it is preferable that the nitrogen atom of at least one amino group is bonded to the cationically polymerizable functional group directly or via an alkylene group.
The amino group is preferably a tertiary amino group from the viewpoint of exhibiting an appropriate effect delaying effect.
上記カチオン重合性官能基としては、例えば、エポキシ基、オキセタン基、水酸基、ビニルエーテル基、エピスルフィド基、エチレンイミン基等が挙げられる。なかでも、硬化物に取り込まれやすくする観点から、エポキシ基が好ましい。
また、上記アミノ基とカチオン重合性官能基とを有する化合物は、硬化物に取り込まれやすくする観点から、1分子中に上記カチオン重合性官能基を2個以上有することが好ましい。Examples of the cationic polymerizable functional group include an epoxy group, an oxetane group, a hydroxyl group, a vinyl ether group, an episulfide group, and an ethyleneimine group. Of these, an epoxy group is preferred from the viewpoint of easy incorporation into a cured product.
Moreover, it is preferable that the compound which has the said amino group and a cation polymerizable functional group has 2 or more of the said cation polymerizable functional groups in 1 molecule from a viewpoint made easy to be taken in into hardened | cured material.
上記アミノ基とカチオン重合性官能基とを有する化合物は、硬化遅延効果と硬化物に取り込まれアウトガスを抑制する効果との両立性に特に優れるため、下記式(1)〜(7)で表される化合物からなる群より選択される少なくとも1種であることが好ましい。 The compound having an amino group and a cationically polymerizable functional group is particularly excellent in compatibility between the curing retardation effect and the effect of being taken into the cured product and suppressing outgas, and is therefore represented by the following formulas (1) to (7). It is preferably at least one selected from the group consisting of the following compounds.
式(1)中、R1は、炭素数1〜3のアルキレン基を表す。各R1は、同一であってもよいし、異なっていてもよい。In formula (1), R 1 represents an alkylene group having 1 to 3 carbon atoms. Each R 1 may be the same or different.
式(2)中、R2は、炭素数1〜3のアルキレン基を表す。各R2は、同一であってもよいし、異なっていてもよい。In formula (2), R 2 represents an alkylene group having 1 to 3 carbon atoms. Each R 2 may be the same or different.
式(3)中、R3は、炭素数1〜3のアルキレン基を表す。各R3は、同一であってもよいし、異なっていてもよい。In formula (3), R 3 represents an alkylene group having 1 to 3 carbon atoms. Each R 3 may be the same or different.
式(4)中、R4は、炭素数1〜3のアルキレン基を表す。各R4は、同一であってもよいし、異なっていてもよい。R5は、メチル基、エチル基、エチレン基、プロピル基のいずれかである。In formula (4), R 4 represents an alkylene group having 1 to 3 carbon atoms. Each R 4 may be the same or different. R 5 is any one of a methyl group, an ethyl group, an ethylene group, and a propyl group.
式(5)中、R6は、炭素数1〜3のアルキレン基を表す。各R6は、同一であってもよいし、異なっていてもよい。R7は、メチル基、エチル基、エチレン基、プロピル基のいずれかであり、各R7は、同一であってもよいし、異なっていてもよい。In formula (5), R 6 represents an alkylene group having 1 to 3 carbon atoms. Each R 6 may be the same or different. R 7 is any one of a methyl group, an ethyl group, an ethylene group, and a propyl group, and each R 7 may be the same or different.
式(6)中、R8は、炭素数1〜3のアルキレン基を表す。各R8は、同一であってもよいし、異なっていてもよい。In Formula (6), R 8 represents an alkylene group having 1 to 3 carbon atoms. Each R 8 may be the same or different.
式(7)中、R9は、炭素数1〜3のアルキレン基を表す。各R9は、同一であってもよいし、異なっていてもよい。In Formula (7), R 9 represents an alkylene group having 1 to 3 carbon atoms. Each R 9 may be the same or different.
上記式(1)中、R1は、メチレン基であることが好ましく、上記式(2)中、R2は、メチレン基であることが好ましく、上記式(3)中、R3は、メチレン基であることが好ましく、上記式(4)中、R4は、メチレン基であることが好ましく、R5は、プロピル基であることが好ましく、上記式(5)中、R6は、メチレン基であることが好ましく、R7は、プロピル基であることが好ましく、上記式(6)中、R8は、メチレン基であることが好ましく、上記式(7)中、R9は、メチレン基であることが好ましい。In the formula (1), R 1 is preferably a methylene group. In the formula (2), R 2 is preferably a methylene group. In the formula (3), R 3 is methylene. In the formula (4), R 4 is preferably a methylene group, R 5 is preferably a propyl group, and in the formula (5), R 6 is methylene. R 7 is preferably a propyl group. In the above formula (6), R 8 is preferably a methylene group. In the above formula (7), R 9 is methylene. It is preferably a group.
上記アミノ基とカチオン重合性官能基とを有する化合物の重量平均分子量の好ましい下限は200、好ましい上限は1000である。上記アミノ基とカチオン重合性官能基とを有する化合物の重量平均分子量が200未満であると、硬化物に取り込まれずに残った上記アミノ基とカチオン重合性官能基とを有する化合物がアウトガス発生の原因となることがある。上記アミノ基とカチオン重合性官能基とを有する化合物の重量平均分子量が1000を超えると、得られる光後硬化性樹脂組成物の粘度が高くなりすぎ、塗工性等が悪化することがある。上記アミノ基とカチオン重合性官能基とを有する化合物の重量平均分子量のより好ましい下限は300、より好ましい上限は800である。
なお、本明細書において、上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定を行い、ポリスチレン換算により求められる値である。GPCによってポリスチレン換算による重量平均分子量を測定する際のカラムとしては、例えば、Shodex LF−804(昭和電工社製)等が挙げられる。The preferable lower limit of the weight average molecular weight of the compound having an amino group and a cationically polymerizable functional group is 200, and the preferable upper limit is 1000. If the compound having the amino group and the cationic polymerizable functional group has a weight average molecular weight of less than 200, the compound having the amino group and the cationic polymerizable functional group remaining without being incorporated into the cured product is a cause of outgassing. It may become. When the weight average molecular weight of the compound having an amino group and a cationic polymerizable functional group exceeds 1000, the viscosity of the resulting photo-curing resin composition becomes too high, and the coatability and the like may be deteriorated. The more preferable lower limit of the weight average molecular weight of the compound having an amino group and a cationic polymerizable functional group is 300, and the more preferable upper limit is 800.
In addition, in this specification, the said weight average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
上記アミノ基とカチオン重合性官能基とを有する化合物のうち市販されているものとしては、例えば、TEPIC(日産化学社製)、jER604、jER630(いずれも三菱化学社製)等が挙げられる。 Examples of commercially available compounds having the amino group and the cationic polymerizable functional group include TEPIC (manufactured by Nissan Chemical Industries), jER604, jER630 (all manufactured by Mitsubishi Chemical Corporation), and the like.
上記アミノ基とカチオン重合性官能基とを有する化合物の含有量は、カチオン硬化性樹脂100重量部に対して、好ましい下限が0.01重量部、好ましい上限が20重量部である。上記アミノ基とカチオン重合性官能基とを有する化合物の含有量が0.01重量部未満であると、硬化遅延効果が充分に発揮されないことがある。上記アミノ基とカチオン重合性官能基とを有する化合物の含有量が20重量部を超えると、得られる光後硬化性樹脂組成物が硬化性に劣るものとなることがある。上記アミノ基とカチオン重合性官能基とを有する化合物の含有量のより好ましい下限は0.05重量部、より好ましい上限は15重量部、更に好ましい下限は0.1重量部、更に好ましい上限は10重量部である。 The content of the compound having an amino group and a cationic polymerizable functional group is preferably 0.01 parts by weight and preferably 20 parts by weight with respect to 100 parts by weight of the cationic curable resin. When the content of the compound having an amino group and a cationic polymerizable functional group is less than 0.01 parts by weight, the curing retardation effect may not be sufficiently exhibited. When the content of the compound having an amino group and a cationically polymerizable functional group exceeds 20 parts by weight, the resulting photo-curable resin composition may be inferior in curability. The more preferred lower limit of the content of the compound having an amino group and a cationically polymerizable functional group is 0.05 parts by weight, the more preferred upper limit is 15 parts by weight, the still more preferred lower limit is 0.1 parts by weight, and the still more preferred upper limit is 10 parts. Parts by weight.
本発明の光後硬化性樹脂組成物は、カチオン硬化性樹脂を含有する。
上記カチオン硬化性樹脂としては、分子内に少なくとも1個のカチオン重合性官能基を有し、かつ、カチオン重合性に富む化合物であれば特に限定されない。
上記カチオン重合性官能基としては、例えば、エポキシ基、オキセタン基、水酸基、ビニルエーテル基、エピスルフィド基、エチレンイミン基等が挙げられる。なかでも、上記カチオン硬化性樹脂は、硬化後に高い接着性と耐久性とを発現することから、エポキシ樹脂を含有することが好ましい。The photo post-curing resin composition of the present invention contains a cationic curable resin.
The cationic curable resin is not particularly limited as long as it is a compound having at least one cationic polymerizable functional group in the molecule and rich in cationic polymerizable properties.
Examples of the cationic polymerizable functional group include an epoxy group, an oxetane group, a hydroxyl group, a vinyl ether group, an episulfide group, and an ethyleneimine group. Especially, since the said cationic curable resin expresses high adhesiveness and durability after hardening, it is preferable to contain an epoxy resin.
上記エポキシ樹脂としては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、レゾルシノール型エポキシ樹脂等の芳香族環を有するエポキシ樹脂や、水添ビスフェノールA型エポキシ樹脂、水添ビスフェノールF型エポキシ樹脂等の脂肪族環を有するエポキシ樹脂や、脂環式エポキシ樹脂等が挙げられる。なかでも、アウトガス発生を抑制する観点から、脂環式エポキシ樹脂を含有することが好ましい。これらのエポキシ樹脂は、単独で用いられてもよいし、2種以上が併用されてもよい。 Examples of the epoxy resin include aromatics such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, resorcinol type epoxy resin, and the like. Examples thereof include epoxy resins having a ring, epoxy resins having an aliphatic ring such as hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, and alicyclic epoxy resins. Especially, it is preferable to contain an alicyclic epoxy resin from a viewpoint of suppressing outgas generation | occurrence | production. These epoxy resins may be used independently and 2 or more types may be used together.
上記脂環式エポキシ樹脂としては、例えば、1,2:8,9−ジエポキシリモネン、4−ビニルシクロヘキセンモノオキサイド、ビニルシクロヘキセンジオキサイド、メチル化ビニルシクロヘキセンジオキサイド、(3,4−エポキシシクロヘキシル)メチル−3,4−エポキシシクロヘキシルカルボキシレート、ビス−(3,4−エポキシシクロヘキシル)アジペート、ビス−(3,4−エポキシシクロヘキシルメチレン)アジペート、ビス−(2,3−エポキシシクロペンチル)エーテル、(2,3−エポキシ−6−メチルシクロヘキシルメチル)アジペート、ジシクロペンタジエンジオキサイド等が挙げられる。なかでも、(3,4−エポキシシクロヘキシル)メチル−3,4−エポキシシクロヘキシルカルボキシレートが好ましい。これらの脂環式エポキシ樹脂は、単独で用いられてもよいし、2種以上が併用されてもよい。 Examples of the alicyclic epoxy resin include 1,2: 8,9-diepoxy limonene, 4-vinylcyclohexene monooxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, and (3,4-epoxycyclohexyl). Methyl-3,4-epoxycyclohexylcarboxylate, bis- (3,4-epoxycyclohexyl) adipate, bis- (3,4-epoxycyclohexylmethylene) adipate, bis- (2,3-epoxycyclopentyl) ether, (2 , 3-epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentadiene dioxide and the like. Of these, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate is preferable. These alicyclic epoxy resins may be used alone or in combination of two or more.
本発明の光後硬化性樹脂組成物は、光カチオン重合開始剤を含有する。
上記光カチオン重合開始剤は、光照射によりプロトン酸又はルイス酸を発生するものであれば特に限定されず、イオン性光酸発生型であってもよいし、非イオン性光酸発生型であってもよい。The photo post-curing resin composition of the present invention contains a photo cationic polymerization initiator.
The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generating type or a nonionic photoacid generating type. May be.
上記イオン性光酸発生型の光カチオン重合開始剤としては、例えば、カチオン部分が芳香族スルホニウム、芳香族ヨードニウム、芳香族ジアゾニウム、芳香族アンモニウム、又は、(2,4−シクロペンタジエン−1−イル)((1−メチルエチル)ベンゼン)−Feカチオンであり、アニオン部分がBF4−、PF6−、SbF6−、又は、(BX4)−(但し、Xは、少なくとも2つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基を表す)で構成されるオニウム塩等が挙げられる。Examples of the ionic photoacid-generating photocationic polymerization initiator include a cation moiety that is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, or (2,4-cyclopentadien-1-yl). ) ((1-methylethyl) benzene) -Fe cation, and the anion portion is BF 4− , PF 6− , SbF 6− , or (BX 4 ) − (where X is at least two or more fluorine atoms) Or an onium salt composed of a phenyl group substituted with a trifluoromethyl group).
上記芳香族スルホニウム塩としては、例えば、ビス(4−(ジフェニルスルホニオ)フェニル)スルフィドビスヘキサフルオロホスフェート、ビス(4−(ジフェニルスルホニオ)フェニル)スルフィドビスヘキサフルオロアンチモネート、ビス(4−(ジフェニルスルホニオ)フェニル)スルフィドビステトラフルオロボレート、ビス(4−(ジフェニルスルホニオ)フェニル)スルフィドテトラキス(ペンタフルオロフェニル)ボレート、ジフェニル−4−(フェニルチオ)フェニルスルホニウムヘキサフルオロホスフェート、ジフェニル−4−(フェニルチオ)フェニルスルホニウムヘキサフルオロアンチモネート、ジフェニル−4−(フェニルチオ)フェニルスルホニウムテトラフルオロボレート、ジフェニル−4−(フェニルチオ)フェニルスルホニウムテトラキス(ペンタフルオロフェニル)ボレート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムテトラキス(ペンタフルオロフェニル)ボレート、ビス(4−(ジ(4−(2−ヒドロキシエトキシ))フェニルスルホニオ)フェニル)スルフィドビスヘキサフルオロホスフェート、ビス(4−(ジ(4−(2−ヒドロキシエトキシ))フェニルスルホニオ)フェニル)スルフィドビスヘキサフルオロアンチモネート、ビス(4−(ジ(4−(2−ヒドロキシエトキシ))フェニルスルホニオ)フェニル)スルフィドビステトラフルオロボレート、ビス(4−(ジ(4−(2−ヒドロキシエトキシ))フェニルスルホニオ)フェニル)スルフィドテトラキス(ペンタフルオロフェニル)ボレート等が挙げられる。 Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) Phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (di ( 4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluoroantimonate, Bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (di ( - (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, and the like.
上記芳香族ヨードニウム塩としては、例えば、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムテトラキス(ペンタフルオロフェニル)ボレート、ビス(ドデシルフェニル)ヨードニウムヘキサフルオロホスフェート、ビス(ドデシルフェニル)ヨードニウムヘキサフルオロアンチモネート、ビス(ドデシルフェニル)ヨードニウムテトラフルオロボレート、ビス(ドデシルフェニル)ヨードニウムテトラキス(ペンタフルオロフェニル)ボレート、4−メチルフェニル−4−(1−メチルエチル)フェニルヨードニウムヘキサフルオロホスフェート、4−メチルフェニル−4−(1−メチルエチル)フェニルヨードニウムヘキサフルオロアンチモネート、4−メチルフェニル−4−(1−メチルエチル)フェニルヨードニウムテトラフルオロボレート、4−メチルフェニル−4−(1−メチルエチル)フェニルヨードニウムテトラキス(ペンタフルオロフェニル)ボレート等が挙げられる。 Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (Dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) Such as phenyl iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Can be mentioned.
上記芳香族ジアゾニウム塩としては、例えば、フェニルジアゾニウムヘキサフルオロホスフェート、フェニルジアゾニウムヘキサフルオロアンチモネート、フェニルジアゾニウムテトラフルオロボレート、フェニルジアゾニウムテトラキス(ペンタフルオロフェニル)ボレート等が挙げられる。 Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
上記芳香族アンモニウム塩としては、例えば、1−ベンジル−2−シアノピリジニウムヘキサフルオロホスフェート、1−ベンジル−2−シアノピリジニウムヘキサフルオロアンチモネート、1−ベンジル−2−シアノピリジニウムテトラフルオロボレート、1−ベンジル−2−シアノピリジニウムテトラキス(ペンタフルオロフェニル)ボレート、1−(ナフチルメチル)−2−シアノピリジニウムヘキサフルオロホスフェート、1−(ナフチルメチル)−2−シアノピリジニウムヘキサフルオロアンチモネート、1−(ナフチルメチル)−2−シアノピリジニウムテトラフルオロボレート、1−(ナフチルメチル)−2−シアノピリジニウムテトラキス(ペンタフルオロフェニル)ボレート等が挙げられる。 Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, and 1-benzyl. 2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) Examples include 2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
上記(2,4−シクロペンタジエン−1−イル)((1−メチルエチル)ベンゼン)−Fe塩としては、例えば、(2,4−シクロペンタジエン−1−イル)((1−メチルエチル)ベンゼン)−Fe(II)ヘキサフルオロホスフェート、(2,4−シクロペンタジエン−1−イル)((1−メチルエチル)ベンゼン)−Fe(II)ヘキサフルオロアンチモネート、(2,4−シクロペンタジエン−1−イル)((1−メチルエチル)ベンゼン)−Fe(II)テトラフルオロボレート、(2,4−シクロペンタジエン−1−イル)((1−メチルエチル)ベンゼン)−Fe(II)テトラキス(ペンタフルオロフェニル)ボレート等が挙げられる。 Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene. ) -Fe (II) hexafluorophosphate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -Yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (penta Fluorophenyl) borate and the like.
上記非イオン性光酸発生型の光カチオン重合開始剤としては、例えば、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、N−ヒドロキシイミドスホナート等が挙げられる。 Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate and the like.
上記光カチオン重合開始剤のうち市販されているものとしては、例えば、DTS−200(みどり化学社製)、UVI6990、UVI6974(いずれもユニオンカーバイド社製)、SP−150、SP−170(いずれもADEKA社製)、FC−508、FC−512(いずれも3M社製)、イルガキュア261(BASF Japan社製)、PI2074(ローディア社製)等が挙げられる。 Examples of commercially available photocationic polymerization initiators include, for example, DTS-200 (manufactured by Midori Chemical Co., Ltd.), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all ADEKA), FC-508, FC-512 (all from 3M), Irgacure 261 (BASF Japan), PI 2074 (Rhodia) and the like.
上記光カチオン重合開始剤の含有量は、上記カチオン硬化性樹脂100重量部に対して、好ましい下限が0.1重量部、好ましい上限が10重量部である。上記光カチオン重合開始剤の含有量が0.1重量部未満であると、カチオン重合が充分に進行しなかったり、硬化反応が遅くなりすぎたりすることがある。上記光カチオン重合開始剤の含有量が10重量部を超えると、得られる光後硬化性樹脂組成物の硬化反応が速くなりすぎて、作業性が低下したり、得られる光後硬化性樹脂組成物の硬化物が不均一となったりすることがある。上記光カチオン重合開始剤の含有量のより好ましい下限は0.5重量部、より好ましい上限は5重量部である。 The content of the photo cationic polymerization initiator is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the cationic curable resin. If the content of the photocationic polymerization initiator is less than 0.1 parts by weight, the cationic polymerization may not proceed sufficiently or the curing reaction may become too slow. When the content of the photocationic polymerization initiator is more than 10 parts by weight, the curing reaction of the resulting photo-curing resin composition becomes too fast, and the workability is lowered, or the resulting photo-curing resin composition is obtained. The cured product may be non-uniform. The minimum with more preferable content of the said photocationic polymerization initiator is 0.5 weight part, and a more preferable upper limit is 5 weight part.
本発明の光後硬化性樹脂組成物は、増感剤を含有してもよい。上記増感剤は、上記カチオン重合開始剤の重合開始効率をより向上させて、本発明の光後硬化性樹脂組成物の硬化反応をより促進させる役割を有する。 The photo post-curing resin composition of the present invention may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the cationic polymerization initiator and further promoting the curing reaction of the photo post-curing resin composition of the present invention.
上記増感剤としては、例えば、2,4−ジエチルチオキサントン等のチオキサントン系化合物や、2,2−ジメトキシ−1,2−ジフェニルエタン−1−オン、ベンゾフェノン、2,4−ジクロロベンゾフェノン、o−ベンゾイル安息香酸メチル、4,4’−ビス(ジメチルアミノ)ベンゾフェノン、4−ベンゾイル−4’メチルジフェニルサルファイド等が挙げられる。 Examples of the sensitizer include thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, o- Examples include methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4-benzoyl-4′methyldiphenyl sulfide.
上記増感剤の含有量は、上記カチオン硬化性樹脂100重量部に対して、好ましい下限は0.05重量部、好ましい上限は3重量部である。上記増感剤の含有量が0.05重量部未満であると、増感効果が充分に得られないことがある。上記増感剤の含有量が3重量部を超えると、吸収が大きくなりすぎて深部まで光が伝わらないことがある。上記増感剤の含有量のより好ましい下限は0.1重量部、より好ましい上限は1重量部である。 The content of the sensitizer is preferably 0.05 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the cationic curable resin. When the content of the sensitizer is less than 0.05 parts by weight, the sensitizing effect may not be sufficiently obtained. When the content of the sensitizer exceeds 3 parts by weight, absorption may be excessively increased and light may not be transmitted to the deep part. The minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
本発明の光後硬化性樹脂組成物は、シランカップリング剤を含有してもよい。上記シランカップリング剤は、本発明の光後硬化性樹脂組成物と基板等との接着性を向上させる役割を有する。 The photo post-curing resin composition of the present invention may contain a silane coupling agent. The said silane coupling agent has a role which improves the adhesiveness of the post-photocurable resin composition of this invention, a board | substrate, etc.
上記シランカップリング剤としては、例えば、γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−イソシアネートプロピルトリメトキシシラン等が挙げられる。これらのシランカップリング剤は、単独で用いられてもよいし、2種以上が併用されてもよい。 Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-isocyanatopropyltrimethoxysilane. These silane coupling agents may be used independently and 2 or more types may be used together.
上記シランカップリング剤の含有量は、上記カチオン硬化性樹脂100重量部に対して、好ましい下限が0.1重量部、好ましい上限が10重量部である。上記シランカップリング剤の含有量が0.1重量部未満であると、得られる光後硬化性樹脂組成物の接着性を向上させる効果が充分に発揮されないことがある。上記シランカップリング剤の含有量が10重量部を超えると、余剰のシランカップリング剤がブリードアウトすることがある。上記シランカップリング剤の含有量のより好ましい下限は0.5重量部、より好ましい上限は5重量部である。 The content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the cation curable resin. When the content of the silane coupling agent is less than 0.1 parts by weight, the effect of improving the adhesiveness of the obtained photo post-curing resin composition may not be sufficiently exhibited. When content of the said silane coupling agent exceeds 10 weight part, an excess silane coupling agent may bleed out. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.
本発明の光後硬化性樹脂組成物は、更に、本発明の目的を阻害しない範囲において、熱硬化剤を含有してもよい。上記熱硬化剤を含有することで、本発明の光後硬化性樹脂組成物に熱硬化性を付与することができる。 The photo post-curing resin composition of the present invention may further contain a thermosetting agent as long as the object of the present invention is not impaired. By containing the said thermosetting agent, thermosetting property can be provided to the post-photocurable resin composition of this invention.
上記熱硬化剤は特に限定されず、例えば、ヒドラジド化合物、イミダゾール誘導体、酸無水物、ジシアンジアミド、グアニジン誘導体、変性脂肪族ポリアミン、各種アミンとエポキシ樹脂との付加生成物等が挙げられる。
上記ヒドラジド化合物としては、例えば、1,3−ビス(ヒドラジノカルボノエチル−5−イソプロピルヒダントイン)等が挙げられる。
上記イミダゾール誘導体としては、例えば、1−シアノエチル−2−フェニルイミダゾール、N−(2−(2−メチル−1−イミダゾリル)エチル)尿素、2,4−ジアミノ−6−(2’−メチルイミダゾリル−(1’))−エチル−s−トリアジン、N,N’−ビス(2−メチル−1−イミダゾリルエチル)尿素、N,N’−(2−メチル−1−イミダゾリルエチル)−アジポアミド、2−フェニル−4−メチル−5−ヒドロキシメチルイミダゾール、2−フェニル−4,5−ジヒドロキシメチルイミダゾール等が挙げられる。
上記酸無水物としては、例えば、テトラヒドロ無水フタル酸、エチレングリコールービス(アンヒドロトリメリテート)等が挙げられる。
これらの熱硬化剤は、単独で用いられてもよいし、2種類以上が併用されてもよい。The thermosetting agent is not particularly limited, and examples thereof include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products of various amines and epoxy resins, and the like.
Examples of the hydrazide compound include 1,3-bis (hydrazinocarbonoethyl-5-isopropylhydantoin).
Examples of the imidazole derivatives include 1-cyanoethyl-2-phenylimidazole, N- (2- (2-methyl-1-imidazolyl) ethyl) urea, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, N, N′-bis (2-methyl-1-imidazolylethyl) urea, N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
Examples of the acid anhydride include tetrahydrophthalic anhydride, ethylene glycol bis (anhydro trimellitate), and the like.
These thermosetting agents may be used alone or in combination of two or more.
上記熱硬化剤の含有量は、上記カチオン硬化性樹脂100重量部に対して、好ましい下限が0.5重量部、好ましい上限が30重量部である。上記熱硬化剤の含有量が0.5重量部未満であると、得られる光後硬化性樹脂組成物に充分な熱硬化性を付与できないことがある。上記熱硬化剤の含有量が30重量部を超えると、得られる光後硬化性樹脂組成物の保存安定性が不充分となったり、得られる光後硬化性樹脂組成物の硬化物の耐湿性が悪くなったりすることがある。上記熱硬化剤の含有量のより好ましい下限は1重量部、より好ましい上限は15重量部である。 The content of the thermosetting agent is preferably 0.5 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the cationic curable resin. If the content of the thermosetting agent is less than 0.5 parts by weight, sufficient thermosetting property may not be imparted to the obtained photo-curing resin composition. When the content of the thermosetting agent exceeds 30 parts by weight, the storage stability of the obtained photo post-curing resin composition becomes insufficient, or the moisture resistance of the cured product of the photo post-curing resin composition obtained. May get worse. The minimum with more preferable content of the said thermosetting agent is 1 weight part, and a more preferable upper limit is 15 weight part.
本発明の光後硬化性樹脂組成物は、本発明の目的を阻害しない範囲において、表面改質剤を含有してもよい。上記表面改質剤を含有することにより、本発明の光後硬化性樹脂組成物に塗膜の平坦性を付与することができる。
上記表面改質剤としては、例えば、界面活性剤やレベリング剤等が挙げられる。The photo post-curing resin composition of the present invention may contain a surface modifier as long as the object of the present invention is not impaired. By containing the surface modifier, the flatness of the coating film can be imparted to the photo post-curing resin composition of the present invention.
Examples of the surface modifier include surfactants and leveling agents.
上記界面活性剤や上記レベリング剤としては、例えば、シリコン系、アクリル系、フッ素系等のものが挙げられる。
上記界面活性剤や上記レベリング剤のうち市販されているものとしては、例えば、BYK−345(ビックケミー・ジャパン社製)、BYK−340(ビックケミー・ジャパン社製)、サーフロンS−611(AGCセイミケミカル社製)等が挙げられる。Examples of the surfactant and the leveling agent include silicon-based, acrylic-based, and fluorine-based ones.
Examples of commercially available surfactants and leveling agents include BYK-345 (manufactured by BYK Japan), BYK-340 (manufactured by BYK Japan), Surflon S-611 (AGC Seimi Chemical). Etc.).
本発明の光後硬化性樹脂組成物は、硬化物の透明性を阻害しない範囲で、素子電極の耐久性を向上させるために、光後硬化性樹脂組成物中に発生した酸と反応する化合物又はイオン交換樹脂を含有してもよい。 The photo-post-curing resin composition of the present invention is a compound that reacts with an acid generated in the photo-post-curing resin composition in order to improve the durability of the element electrode within a range that does not impair the transparency of the cured product. Or you may contain an ion exchange resin.
上記発生した酸と反応する化合物としては、酸と中和する物質、例えば、アルカリ金属の炭酸塩若しくは炭酸水素塩、又は、アルカリ土類金属の炭酸塩若しくは炭酸水素塩等が挙げられる。具体的には例えば、炭酸カルシウム、炭酸水素カルシウム、炭酸ナトリウム、炭酸水素ナトリウム等が用いられる。 Examples of the compound that reacts with the generated acid include substances that neutralize the acid, for example, alkali metal carbonates or bicarbonates, or alkaline earth metal carbonates or bicarbonates. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like are used.
上記イオン交換樹脂としては、陽イオン交換型、陰イオン交換型、両イオン交換型のいずれも使用することができるが、特に塩化物イオンを吸着することのできる陽イオン交換型又は両イオン交換型が好適である。 As the ion exchange resin, any of a cation exchange type, an anion exchange type, and a both ion exchange type can be used, and in particular, a cation exchange type or a both ion exchange type capable of adsorbing chloride ions. Is preferred.
また、本発明の光後硬化性樹脂組成物は、必要に応じて、補強剤、軟化剤、可塑剤、粘度調整剤、紫外線吸収剤、酸化防止剤等の公知の各種添加剤を含有してもよい。 Further, the photo post-curing resin composition of the present invention contains various known additives such as a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, an ultraviolet absorber, and an antioxidant as necessary. Also good.
本発明の光後硬化性樹脂組成物を製造する方法としては、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、3本ロール等の混合機を用いて、カチオン硬化性樹脂と、光カチオン重合開始剤と、アミノ基とカチオン重合性官能基とを有する化合物と、必要に応じて添加するシランカップリング剤等の添加剤とを混合する方法等が挙げられる。 As a method for producing the photo post-curing resin composition of the present invention, for example, using a mixer such as a homodisper, homomixer, universal mixer, planetary mixer, kneader, three rolls, And a method of mixing a photocationic polymerization initiator, a compound having an amino group and a cationically polymerizable functional group, and an additive such as a silane coupling agent to be added as necessary.
本発明によれば、アウトガスの発生を抑制することができ、透明性及び信頼性に優れる光後硬化性樹脂組成物を提供することができる。 According to this invention, generation | occurrence | production of outgas can be suppressed and the optical post-curing resin composition excellent in transparency and reliability can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
(実施例1)
カチオン硬化性樹脂として、ビスフェノールF型エポキシ樹脂(DIC社製、「EPICLON EXA−830LVP」)50重量部、水添ビスフェノールA型エポキシ樹脂(三菱化学社製、「jER YL8034」)25重量部、及び、水添ビスフェノールF型エポキシ樹脂(三菱化学社製、「jER YL6753」)25重量部と、光カチオン重合開始剤として芳香族スルホニウム塩(みどり化学社製、「DTS−200」)1.0重量部と、第三級アミノ基とカチオン重合性官能基とを有する化合物としてトリグリシジルイソシアヌラート(日産化学社製、「TEPIC」)5重量部と、増感剤として2,4−ジエチルチオキサントン(日本化薬社製、「DETX−S」)0.01重量部と、シランカップリング剤としてγ−グリシドキシプロピルトリメトキシシラン(信越シリコーン社製、「KBM−403」)1重量部と、フッ素系レベリング剤(AGCセイミケミカル社製、「サーフロンS−611」)1重量部とを混合し、80℃に加熱した後、ホモディスパー型撹拌混合機(プライミクス社製、「ホモディスパーL型」)を用い、撹拌速度3000rpmで均一に撹拌混合して、光後硬化性樹脂組成物を作製した。Example 1
As a cationic curable resin, 50 parts by weight of bisphenol F type epoxy resin (manufactured by DIC, “EPICLON EXA-830LVP”), 25 parts by weight of hydrogenated bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “jER YL8034”), and , 25 parts by weight of hydrogenated bisphenol F type epoxy resin (Mitsubishi Chemical Co., Ltd., “jER YL6753”) and 1.0 weight of aromatic sulfonium salt (Midori Chemical Co., Ltd., “DTS-200”) as a photocationic polymerization initiator Part, 5 parts by weight of triglycidyl isocyanurate (manufactured by Nissan Chemical Co., “TEPIC”) as a compound having a tertiary amino group and a cationic polymerizable functional group, and 2,4-diethylthioxanthone ( Nippon Kayaku Co., Ltd. “DETX-S”) 0.01 parts by weight and γ-glycy as a silane coupling agent 1 part by weight of xylpropyltrimethoxysilane (manufactured by Shin-Etsu Silicone, “KBM-403”) and 1 part by weight of a fluorine leveling agent (manufactured by AGC Seimi Chemical Co., “Surflon S-611”) are mixed at 80 ° C. Then, the mixture was uniformly stirred and mixed at a stirring speed of 3000 rpm by using a homodisper type stirring mixer (“Homodisper L type” manufactured by PRIMIX Co., Ltd.) to prepare a photo post-curing resin composition.
(実施例2〜6、比較例1〜3)
表1に記載された各材料を、表1に記載された配合比に従い、実施例1と同様にして撹拌混合して、光後硬化性樹脂組成物を作製した。(Examples 2-6, Comparative Examples 1-3)
Each material described in Table 1 was stirred and mixed in the same manner as in Example 1 in accordance with the blending ratio described in Table 1 to prepare a photo post-curing resin composition.
<評価>
実施例及び比較例で得られた各光後硬化性樹脂組成物について以下の評価を行った。結果を表1に示した。<Evaluation>
The following evaluation was performed about each light post-curing resin composition obtained by the Example and the comparative example. The results are shown in Table 1.
(1)粘度
実施例及び比較例で得られた各光後硬化性樹脂組成物について、E型粘度計(東機産業社製、「VISCOMETER TV−22」)を用いて、25℃、100rpmの条件における粘度を測定した。(1) Viscosity
About each optical post-curing resin composition obtained by the Example and the comparative example, the viscosity in the conditions of 25 degreeC and 100 rpm was used for E type viscometer (the Toki Sangyo company make, "VISCOMETER TV-22"). It was measured.
(2)硬化遅延性
実施例及び比較例で得られた各光後硬化性樹脂組成物の試験片に紫外線照射装置(オーク社製、「JL−4300−3S」)を用いて紫外線を1500mJ/cm2照射した。10分後硬化性を確認し、更にその後100℃のオーブンで15分加熱を行い、硬化性を確認した。その結果、UV照射10分後未硬化、かつ、100℃加熱後硬化した場合を「○」、UV照射10分後増粘しており、かつ、100℃加熱後硬化した場合を「△」、UV照射10分以内に硬化した場合、又は、100℃加熱後も未硬化だった場合を「×」として硬化遅延性を評価した。(2) Curing retardance UV rays were applied to test pieces of each photo-curing resin composition obtained in Examples and Comparative Examples using an ultraviolet irradiation device (“JL-4300-3S” manufactured by Oak Co., Ltd.) at 1500 mJ / Irradiated cm 2 . After 10 minutes, the curability was confirmed, and further heated for 15 minutes in an oven at 100 ° C. to confirm the curability. As a result, the case where it is uncured after 10 minutes of UV irradiation and cured after heating at 100 ° C. is “O”, the viscosity is increased after 10 minutes of UV irradiation and is cured after heating at 100 ° C. Curing retardancy was evaluated as “x” when cured within 10 minutes of UV irradiation or when uncured after heating at 100 ° C.
(3)硬化物の透明性
実施例及び比較例で得られた各光後硬化性樹脂組成物をそれぞれ75mm×25mm×1mmのガラス板2枚の間に10μmの厚みに形成し、真空環境下で高圧水銀灯を用いて波長365nmの紫外線を照射量が3000mJ/cm2となるように照射することにより硬化させて硬化物を得た。得られた硬化物について、分光光度計(日立ハイテクノロジーズ社製、「U−2900」)を用いて全光線透過率を測定した。その結果、透過率が95以上であった場合を「○」、90以上95未満であった場合を「△」、90未満であった場合を「×」として硬化物の透明性を評価した。(3) Transparency of cured product Each post-light-curing resin composition obtained in Examples and Comparative Examples was formed to a thickness of 10 μm between two 75 mm × 25 mm × 1 mm glass plates, and in a vacuum environment Then, using a high-pressure mercury lamp, ultraviolet rays having a wavelength of 365 nm were irradiated so that the irradiation amount was 3000 mJ / cm 2 to be cured to obtain a cured product. About the obtained hardened | cured material, the total light transmittance was measured using the spectrophotometer (The Hitachi High-Technologies company make, "U-2900"). As a result, the transparency of the cured product was evaluated as “◯” when the transmittance was 95 or more, “Δ” when it was 90 or more and less than 95, and “X” when it was less than 90.
(4)アウトガス防止性
実施例及び比較例で得られた各光後硬化性樹脂組成物を、バイアル瓶中に300mg計量して封入した後、紫外線照射装置(オーク社製、「JL−4300−3S」)を用いて紫外線を1500mJ/cm2照射し、その後100℃で15分間加熱を行うことで樹脂を硬化させた。更にこのバイアル瓶を85℃の恒温オーブンで100時間加熱し、バイアル瓶中の気化成分をガスクロマトグラフ質量分析計(日本電子社製、「JMS−k9」)を用いて測定した。
気化成分量が10ppm未満であった場合を「◎」、10ppm以上50ppm未満であった場合を「〇」、50ppm以上100ppm未満であった場合を「△」、100ppm以上であった場合を「×」としてアウトガス防止性を評価した。(4) Outgassing prevention After each photo-curing resin composition obtained in Examples and Comparative Examples was weighed and sealed in a vial, 300 mg, and then irradiated with an ultraviolet irradiation device (Oak, “JL-4300- 3S ") was irradiated with ultraviolet rays at 1500 mJ / cm 2 and then heated at 100 ° C for 15 minutes to cure the resin. Furthermore, this vial was heated in a constant temperature oven at 85 ° C. for 100 hours, and the vaporized components in the vial were measured using a gas chromatograph mass spectrometer (“JMS-k9” manufactured by JEOL Ltd.).
The case where the amount of vaporized component was less than 10 ppm was “◎”, the case where it was 10 ppm or more and less than 50 ppm was “◯”, the case where it was 50 ppm or more but less than 100 ppm was “Δ”, and the case where it was 100 ppm or more was “×”. The outgassing prevention property was evaluated.
(5)有機EL表示素子の信頼性
(有機発光材料層を有する積層体が配置された基板の作製)
ガラス基板(長さ25mm、幅25mm、厚さ0.7mm)にITO電極を1000Åの厚さで成膜したものを基板とした。上記基板をアセトン、アルカリ水溶液、イオン交換水、イソプロピルアルコールにてそれぞれ15分間超音波洗浄した後、煮沸させたイソプロピルアルコールにて10分間洗浄し、更に、UV−オゾンクリーナ(日本レーザー電子社製、「NL−UV253」)にて直前処理を行った。
次に、この基板を真空蒸着装置の基板フォルダに固定し、素焼きの坩堝にN,N’−ジ(1−ナフチル)−N,N’−ジフェニルベンジジン(α−NPD)を200mg、他の異なる素焼き坩堝にトリス(8−ヒドロキシキノリラ)アルミニウム(Alq3)を200mg入れ、真空チャンバー内を、1×10−4Paまで減圧した。その後、α−NPDの入った坩堝を加熱し、α−NPDを蒸着速度15Å/sで基板に堆積させ、膜厚600Åの正孔輸送層を成膜した。次いで、Alq3の入った坩堝を加熱し、15Å/sの蒸着速度で膜厚600Åの有機発光材料層を成膜した。その後、正孔輸送層及び有機発光材料層が形成された基板を別の真空蒸着装置に移し、この真空蒸着装置内のタングステン製抵抗加熱ボートにフッ化リチウム200mgを、別のタングステン製ボートにアルミニウム線1.0gを入れた。その後、真空蒸着装置の蒸着器内を2×10−4Paまで減圧してフッ化リチウムを0.2Å/sの蒸着速度で5Å成膜した後、アルミニウムを20Å/sの速度で1000Å成膜した。窒素により蒸着器内を常圧に戻し、10mm×10mmの有機発光材料層を有する積層体が配置された基板を取り出した。(5) Reliability of organic EL display element (production of a substrate on which a laminate having an organic light emitting material layer is disposed)
A glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm) on which an ITO electrode was formed to a thickness of 1000 mm was used as the substrate. The substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes each, then washed with boiled isopropyl alcohol for 10 minutes, and further UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd., The last treatment was performed with “NL-UV253”).
Next, this substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is put into an unglazed crucible in other different ways. 200 mg of tris (8-hydroxyquinola) aluminum (Alq 3 ) was put in an unglazed crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 −4 Pa. Thereafter, the crucible containing α-NPD was heated and α-NPD was deposited on the substrate at a deposition rate of 15 Å / s to form a 600 正 孔 hole transport layer. Next, the crucible containing Alq 3 was heated to form an organic light emitting material layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and aluminum is added to another tungsten boat. 1.0 g of wire was added. Then, after reducing the pressure in the vapor deposition unit of the vacuum vapor deposition apparatus to 2 × 10 −4 Pa and depositing 5 μm of lithium fluoride at a deposition rate of 0.2 kg / s, deposit 1000 μm of aluminum at a rate of 20 kg / s. did. The inside of the vapor deposition unit was returned to normal pressure with nitrogen, and the substrate on which the laminate having the organic light emitting material layer of 10 mm × 10 mm was arranged was taken out.
(無機材料膜Aによる被覆)
得られた積層体が配置された基板の、該積層体全体を覆うように、13mm×13mmの開口部を有するマスクを設置し、プラズマCVD法にて無機材料膜Aを形成した。
プラズマCVD法は、原料ガスとしてSiH4ガス及び窒素ガスを用い、各々の流量を10sccm及び200sccmとし、RFパワーを10W(周波数2.45GHz)、チャンバー内温度を100℃、チャンバー内圧力を0.9Torrとする条件で行った。
形成された無機材料膜Aの厚さは、約1μmであった。(Coating with inorganic material film A)
A mask having an opening of 13 mm × 13 mm was placed so as to cover the entire laminated body of the substrate on which the obtained laminated body was arranged, and an inorganic material film A was formed by a plasma CVD method.
In the plasma CVD method, SiH 4 gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, RF power is 10 W (frequency: 2.45 GHz), chamber temperature is 100 ° C., and chamber pressure is 0. The test was performed at 9 Torr.
The formed inorganic material film A had a thickness of about 1 μm.
(樹脂保護膜の形成)
真空装置内に、無機材料膜Aで被覆された積層体が配置された基板を設置し、真空装置の中に設置された加熱ボートに実施例及び比較例で得られた各光後硬化性樹脂組成物を0.5g入れ、10Paに減圧して、積層体を含む11mm×11mmの四角形の部分に、光後硬化性樹脂組成物を200℃にて加熱し、厚さが0.5μmになるように真空蒸着を行った。その後、真空環境下で高圧水銀灯を用いて波長365nmの紫外線を照射量が3000mJ/cm2となるように照射して、光後硬化性樹脂組成物を硬化させて樹脂保護膜を形成した。(Formation of resin protective film)
In the vacuum apparatus, a substrate on which a laminate coated with the inorganic material film A is arranged, and each light post-curing resin obtained in the examples and comparative examples is placed on a heating boat installed in the vacuum apparatus. 0.5 g of the composition is put, the pressure is reduced to 10 Pa, and the photo-post-curing resin composition is heated at 200 ° C. to a 11 mm × 11 mm square portion including the laminate, resulting in a thickness of 0.5 μm. As described above, vacuum deposition was performed. Thereafter, ultraviolet light having a wavelength of 365 nm was irradiated using a high pressure mercury lamp in a vacuum environment so that the irradiation amount was 3000 mJ / cm 2 to cure the photo-curable resin composition, thereby forming a resin protective film.
(無機材料膜Bによる被覆)
樹脂保護膜を形成した後、該樹脂保護膜の全体を覆うように、12mm×12mmの開口部を有するマスクを設置し、プラズマCVD法にて無機材料膜Bを形成して有機EL表示素子を得た。
プラズマCVD法は、原料ガスとしてSiH4ガス及び窒素ガスを用い、各々の流量をSiH4ガス10sccm、窒素ガス200sccmとし、RFパワーを10W(周波数2.45GHz)、チャンバー内温度を100℃、チャンバー内圧力を0.9Torrとする条件で行った。
形成された無機材料膜Bの厚さは、約1μmであった。(Coating with inorganic material film B)
After forming the resin protective film, a mask having an opening of 12 mm × 12 mm is installed so as to cover the entire resin protective film, and the inorganic material film B is formed by plasma CVD to form an organic EL display element. Obtained.
In the plasma CVD method, SiH 4 gas and nitrogen gas are used as source gases, the flow rates of each are SiH 4 gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The formed inorganic material film B had a thickness of about 1 μm.
(有機EL表示素子の発光状態の観察)
得られた有機EL表示素子を、温度85℃、湿度85%の環境下で100時間暴露した後、3Vの電圧を印加し、有機EL表示素子の発光状態(ダークスポット及び画素周辺消光の有無)を目視で観察した。ダークスポットや周辺消光が無く均一に発光した場合を「○」、僅かでもダークスポットや周辺消光が認められた場合を「×」として有機EL表示素子の信頼性を評価した。(Observation of light emission state of organic EL display element)
The obtained organic EL display element is exposed for 100 hours in an environment of a temperature of 85 ° C. and a humidity of 85%, and then a voltage of 3 V is applied, and the light emission state of the organic EL display element (whether dark spots and pixel periphery quenching) Was visually observed. The reliability of the organic EL display element was evaluated with “◯” when the light was emitted uniformly without dark spots or peripheral quenching, and “X” when the dark spot or peripheral quenching was observed even slightly.
本発明によれば、アウトガスの発生を抑制することができ、透明性及び信頼性に優れる光後硬化性樹脂組成物を提供することができる。 According to this invention, generation | occurrence | production of outgas can be suppressed and the optical post-curing resin composition excellent in transparency and reliability can be provided.
本発明は、カチオン硬化性樹脂、光カチオン重合開始剤、及び、アミノ基とカチオン重合性官能基とを有する化合物を含有し、前記アミノ基とカチオン重合性官能基とを有する化合物の含有量が、カチオン硬化性樹脂100重量部に対して、0.01〜20重量部である光後硬化性樹脂組成物である。
以下に本発明を詳述する。
The present invention contains a cationic curable resin, a photocationic polymerization initiator, and a compound having an amino group and a cationic polymerizable functional group, and the content of the compound having the amino group and the cationic polymerizable functional group is The photo-curable resin composition is 0.01 to 20 parts by weight with respect to 100 parts by weight of the cationic curable resin .
The present invention is described in detail below.
Claims (7)
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CN112955488A (en) * | 2018-11-28 | 2021-06-11 | 积水化学工业株式会社 | Curable resin composition, cured product, and organic EL display element |
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