WO2017170888A1 - Resin composition - Google Patents
Resin composition Download PDFInfo
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- WO2017170888A1 WO2017170888A1 PCT/JP2017/013301 JP2017013301W WO2017170888A1 WO 2017170888 A1 WO2017170888 A1 WO 2017170888A1 JP 2017013301 W JP2017013301 W JP 2017013301W WO 2017170888 A1 WO2017170888 A1 WO 2017170888A1
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- group
- resin composition
- compound
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- 239000011342 resin composition Substances 0.000 title claims abstract description 146
- 150000001875 compounds Chemical class 0.000 claims abstract description 158
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 125000006239 protecting group Chemical group 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000005647 linker group Chemical group 0.000 claims description 16
- 125000002252 acyl group Chemical group 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 238000005401 electroluminescence Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 9
- 239000000565 sealant Substances 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000001188 haloalkyl group Chemical group 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 38
- 239000000463 material Substances 0.000 abstract description 35
- 238000000034 method Methods 0.000 abstract description 27
- 230000035699 permeability Effects 0.000 abstract description 16
- 238000010943 off-gassing Methods 0.000 abstract description 11
- 238000007789 sealing Methods 0.000 abstract description 10
- 230000008719 thickening Effects 0.000 abstract description 4
- 238000005538 encapsulation Methods 0.000 abstract 1
- -1 Phenyl sulfide compound Chemical class 0.000 description 41
- 239000000047 product Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 15
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 11
- 230000001678 irradiating effect Effects 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 230000003111 delayed effect Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 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 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 5
- 238000012663 cationic photopolymerization Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WQUQHXQTTKKFGY-UHFFFAOYSA-N 1-ethenylsulfanyl-4-(4-ethenylsulfanylphenyl)sulfanylbenzene Chemical class C1=CC(SC=C)=CC=C1SC1=CC=C(SC=C)C=C1 WQUQHXQTTKKFGY-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GHBQLFWTMLRYKN-UHFFFAOYSA-N 9-prop-2-enylcarbazole Chemical compound C1=CC=C2N(CC=C)C3=CC=CC=C3C2=C1 GHBQLFWTMLRYKN-UHFFFAOYSA-N 0.000 description 3
- LPQBQAXHOAEOAX-UHFFFAOYSA-N C=1C=C(C=2C=CC=CC=2)C=CC=1SC(C=C1)=CC=C1SC(C=C1)=CC=C1C1=CC=CC=C1C1=CC=CC=C1 Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1SC(C=C1)=CC=C1SC(C=C1)=CC=C1C1=CC=CC=C1C1=CC=CC=C1 LPQBQAXHOAEOAX-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002596 lactones Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000006585 (C6-C10) arylene group Chemical group 0.000 description 2
- 0 *C(*[n]1c2ccccc2c2c1cccc2)=C Chemical compound *C(*[n]1c2ccccc2c2c1cccc2)=C 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- OIERSKAUJNRYCS-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-phenylbenzene Chemical compound C=COCCOC1=CC=CC=C1C1=CC=CC=C1 OIERSKAUJNRYCS-UHFFFAOYSA-N 0.000 description 2
- WKYLNWXULYGAST-UHFFFAOYSA-N 1-(9h-carbazol-1-yl)prop-2-en-1-one Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2C(=O)C=C WKYLNWXULYGAST-UHFFFAOYSA-N 0.000 description 2
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 description 2
- LMPIWGZJJUJACB-UHFFFAOYSA-N 9-(1-phenylprop-2-enyl)carbazole Chemical compound C(=C)C(C1=CC=CC=C1)N1C2=CC=CC=C2C=2C=CC=CC1=2 LMPIWGZJJUJACB-UHFFFAOYSA-N 0.000 description 2
- JLLMOYPIVVKFHY-UHFFFAOYSA-N Benzenethiol, 4,4'-thiobis- Chemical compound C1=CC(S)=CC=C1SC1=CC=C(S)C=C1 JLLMOYPIVVKFHY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 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 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000003566 oxetanyl group Chemical group 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 125000005654 1,2-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([*:2])C([H])([*:1])C1([H])[H] 0.000 description 1
- 125000005837 1,2-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([*:2])C1([H])[H] 0.000 description 1
- 125000005838 1,3-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:2])C([H])([H])C1([H])[*:1] 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 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
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 description 1
- DNVXWIINBUTFEP-UHFFFAOYSA-N 2-[(2-phenylphenoxy)methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C1=CC=CC=C1 DNVXWIINBUTFEP-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 102100033806 Alpha-protein kinase 3 Human genes 0.000 description 1
- 101710082399 Alpha-protein kinase 3 Proteins 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- DMHQOZIJKIQYLE-UHFFFAOYSA-N C(C=C1)=CC=C1C(C=C1)=CC=C1SC(C=CC=C1)=C1SC(C=C1)=CC=C1C(C=CC=C1)=C1C1=CC=CC=C1 Chemical compound C(C=C1)=CC=C1C(C=C1)=CC=C1SC(C=CC=C1)=C1SC(C=C1)=CC=C1C(C=CC=C1)=C1C1=CC=CC=C1 DMHQOZIJKIQYLE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000005098 aryl alkoxy carbonyl group Chemical group 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QKQFIIOUCQZCFT-UHFFFAOYSA-O benzyl-(4-hydroxyphenyl)-methylsulfanium Chemical compound C=1C=C(O)C=CC=1[S+](C)CC1=CC=CC=C1 QKQFIIOUCQZCFT-UHFFFAOYSA-O 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001976 hemiacetal group Chemical group 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/30—Sulfides having the sulfur atom of at least one thio group bound to two carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- 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
-
- 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
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
-
- 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
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1458—Monomers containing nitrogen
-
- 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
- C08F228/00—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 a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—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 a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
- C08F228/04—Thioethers
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Definitions
- the present invention relates to a resin composition that can be used as a fill material when an organic electroluminescence element is sealed by a dam and fill method.
- This application claims the priority of Japanese Patent Application No. 2016-074517 for which it applied to Japan on April 1, 2016, and uses the content here.
- organic EL device including an organic electroluminescence (hereinafter sometimes referred to as “organic EL”) element is used as a full-color flat panel display or an LED because of high impact resistance, high visibility, and a variety of emission colors. Expected to replace.
- organic EL devices There are two types of organic EL devices, a top emission type and a bottom emission type, due to differences in light extraction methods.
- organic EL elements are more susceptible to moisture than other electronic components, and moisture that penetrates into the organic EL elements can cause electrode oxidation or organic modification, resulting in a significant decrease in light emission characteristics.
- Met As a method for solving this problem, a method of sealing (or covering) the periphery of the organic EL element with a low moisture-permeable resin is known.
- a method for sealing with the resin As a method for sealing with the resin, a method of sealing by filling the periphery of the organic EL element formed on the substrate with a resin composition that is cured by ultraviolet irradiation, and then curing the resin composition (1) And a method (2) in which a resin composition is applied to a lid (lid) and irradiated with ultraviolet rays, and then bonded to a substrate on which an organic EL element is formed and sealed (2).
- the method (1) has a problem in that the light emission characteristics are deteriorated by directly exposing the organic EL element to ultraviolet rays.
- the problem is that the resin composition is difficult to cure because the color filter blocks ultraviolet rays. It was.
- Patent Document 1 discloses that a resin composition containing an epoxy compound, a cationic photopolymerization initiator, and a crown ether or a polyether as a curing retarder gradually progresses after the ultraviolet irradiation, It is described that when the composition is used in the method (2), the organic EL device can be sealed without being directly exposed to ultraviolet rays.
- crown ethers and polyethers are decomposed by an acid generated from a photocationic polymerization initiator to generate outgas, and the organic EL element is deteriorated by the outgas.
- the cured product of the resin composition is required to have a high refractive index in order to make it difficult for light to be reflected at the interface with the organic EL element.
- a resin for forming a cured product having a high refractive index a bis (4-vinylthiophenyl) sulfide derivative is known (Patent Document 2).
- the bis (4-vinylthiophenyl) sulfide derivative has a low viscosity, and when the resin composition containing the bis (4-vinylthiophenyl) sulfide derivative is used as a fill material when sealing an organic EL device by, for example, a dam and fill method, the above method (2 ) Is likely to flow out of the dam when bonded to the substrate.
- a polymer compound for example, petroleum resin
- a resin composition containing an acetone-insoluble polymer compound is used in a liquid dispensing device such as a dispenser or an inkjet coating device.
- the viscosity is increased to such an extent that it can be prevented from flowing out of the dam, it may be difficult to discharge using the device, etc., good dischargeability from the device, etc., cleanability inside the device, etc. It was very difficult to combine the prevention of spillage from the dam.
- an object of the present invention is a resin composition that can be used as a fill material when sealing an organic EL element by a dam and fill method, and is excellent in applicability and acetone solubility, and has a timing of thickening and curing. It is an object to provide a resin composition capable of forming a cured product having a high refractive index, a low moisture permeability, and a low outgassing property. Another object of the present invention is to provide an organic EL device having a configuration in which an organic EL element is sealed with a cured product of the resin composition.
- Phenyl sulfide compound (A) having two reactive functional groups in a molecule, a specific compound (B) having one polymerizable unsaturated group in one molecule, a photocationic polymerization initiator (C 1) is low in viscosity, excellent in coatability and excellent in acetone solubility.
- the resin composition is irradiated with ultraviolet rays, the (A) exhibits curing retardation, and at the same time, the (B) exhibits curing properties, so that the curing reaction of the resin composition is moderately thickened.
- the curing reaction once stopped can be resumed by applying heat treatment, and thereafter a cured product can be formed quickly.
- the obtained cured product has high refractive index, low moisture permeability, and low outgassing properties.
- the present invention has been completed based on these findings.
- this invention provides the resin composition containing the following compound (A), the following compound (B), and a photocationic polymerization initiator (C).
- a hydroxyalkyl group an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protecting group;
- An acyl group which may be protected R c represents a single bond or a linking group, m represents an integer of 0 to 4, n represents an integer of 0 to 10.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a hydrocarbon group
- t represents an integer of 0 or more
- t represents an integer of 2 or more
- a plurality of R 2 are the same.
- a plurality of R 2 may be bonded to each other to form a ring together with the carbon atoms constituting the aromatic ring in the formula.
- the present invention also provides the above resin composition, wherein R a in the formula (a) is a vinyl group or an allyl group.
- the compound represented by the formula (b-2) is represented by the following formula (b-2-1): (Wherein R 1 represents a hydrogen atom or a methyl group, and L represents a linking group)
- the resin composition is a compound represented by:
- the content ratio of the compound (A) to the compound (B) is 60:40 to 95: 5, and the compound (A) and the compound (B) Provided is the above resin composition having a total content of 50% by weight or more of the total amount of the curable compound contained in the resin composition.
- the present invention also provides the above resin composition having a viscosity at 25 ° C. of 10 mPa ⁇ s or more and less than 30 mPa ⁇ s.
- the present invention also provides the resin composition as described above, which is an organic electroluminescence device sealant.
- the present invention also provides a method for producing an organic electroluminescent device, wherein the organic electroluminescent element is sealed through the following steps 1 and 2.
- Step 1 UV irradiation is performed on the coating film made of the resin composition.
- Step 2 The UV-irradiated coating film obtained through Step 1 is bonded to the element mounting surface of the substrate on which the organic electroluminescence element is mounted. Heat treatment
- the present invention also provides an organic electroluminescence device having a structure in which an element is sealed with a cured product of the resin composition.
- the present invention relates to the following.
- At least one selected from the compound (A) represented by the formula (a), the compound represented by the formula (b-1), and the compound represented by the following formula (b-2) The resin composition containing a compound (B) and a photocationic polymerization initiator (C).
- R a in the formula (a) is a cationically polymerizable group.
- R a in the formula (a) is a group selected from a vinyl group, an allyl group, an epoxy group, a glycidyl group, and an oxetanyl group.
- Y in formula (b-1) is a divalent hydrocarbon group (preferably a C 1-18 alkylene group, a C 2-8 alkenylene group, a C 6-10 arylene group, and a single bond thereof.
- [1] to [9] which are groups selected from a group selected from a group linked via a carbonyl group, an ether bond, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these groups are linked.
- At least one compound in which the compound represented by the formula (b-1) is selected from N-vinylcarbazole, N-allylcarbazole, N- (meth) acryloylcarbazole, and N- (vinylbenzyl) carbazole The resin composition according to any one of [1] to [11].
- L in the formula (b-2) is a divalent hydrocarbon group (preferably a C 1-18 alkylene group, a C 2-8 alkenylene group, a C 6-10 arylene group, or a single bond thereof) A group selected from a group linked through a carbonyl group, an ether bond, a thioether bond, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these are linked, [1] -The resin composition as described in any one of [12]. [14] In any one of [1] to [13], the molecular weight of the compound represented by the formula (b-2) is 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). The resin composition as described.
- the content of the compound other than the compound (A), the compound (B), and the photocationic polymerization initiator (C) is 40% by weight or less (preferably 20% by weight or less, particularly preferably 10% by weight) of the total amount of the resin composition. % Or less), the resin composition according to any one of [1] to [15].
- the total content of the compound (A), the compound (B) and the photocationic polymerization initiator (C) is 60% by weight or more (preferably 80% by weight or more, particularly preferably 90% by weight or more) of the total amount of the resin composition.
- the content of the polymer compound having a weight average molecular weight of more than 1000 is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight or less).
- the content of a compound having a solubility parameter (SP value at 25 ° C .; a value calculated by the formula of Fedors) of 8.5 or more is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight)
- the content ratio of the compound (A) to the compound (B) is 60:40 to 95: 5 (preferably 65:35 to 90:10, particularly preferably 70: 30 to 85:15), and the total content of the compound (A) and the compound (B) is 50% by weight or more (preferably 60% by weight or more, more preferably, the total amount of the curable compound contained in the resin composition).
- the content of the compound (A) is 45 to 95% (preferably 60 to 95% by weight, more preferably 65 to 90% by weight) of the total amount (100% by weight) of the curable compound contained in the resin composition.
- the content of the compound (B) is 5 to 40% by weight (preferably 10 to 35% by weight, particularly preferably 15 to 30% by weight) of the total amount (100% by weight) of the curable compound contained in the resin composition.
- the content of the photocationic polymerization initiator (C) is 0.01 to 15 parts by weight (preferably 0.01 to 10 parts by weight, particularly preferably 100 parts by weight of the curable compound contained in the resin composition). Is 0.05 to 5 parts by weight, and most preferably 0.1 to 3 parts by weight).
- the resin composition according to any one of [1] to [23].
- the viscosity according to any one of [1] to [24], in which the viscosity at 25 ° C. when not irradiated with ultraviolet rays is 10 mPa ⁇ s or more and less than 30 mPa ⁇ s (preferably 15 to 25 mPa ⁇ s). Resin composition.
- the degree of increase in viscosity during 30 minutes after ultraviolet irradiation is 1.30 or less (preferably 1.20 or less).
- Step 1 UV coating is applied to the coating film made of the resin composition according to any one of [1] to [29]
- Step 2 is applied to the element mounting surface of the substrate on which the organic electroluminescence element is mounted.
- the device was sealed with a cured product of the resin composition as described in any one of [1] to [29], after the ultraviolet-irradiated coating film obtained through the above was pasted and heat-treated An organic electroluminescence device having a configuration.
- the moisture permeability (g / m 2 ⁇ day ⁇ atm) of the cured product having a thickness of 100 ⁇ m is 100 or less (preferably 50 or less, particularly preferably 35 or less, most preferably 25 or less).
- Organic electroluminescence device is
- the resin composition of the present invention Since the resin composition of the present invention has the above-described configuration, it is low in viscosity and excellent in fluidity until it is irradiated with ultraviolet rays, and can be discharged satisfactorily using a liquid dispensing apparatus or the like. Moreover, since the solubility which was excellent with respect to acetone used as an industrial cleaning agent is shown, the inside of the said apparatus etc. can be easily wash
- the progress of the curing reaction can be stopped in the semi-cured state until the heat treatment is performed even after irradiation with ultraviolet rays, and the timing for restarting the curing reaction can be arbitrarily set by adjusting the timing for performing the heat treatment. can do.
- it can harden
- the resin composition of the present invention includes, in particular, a sealant (in particular, a fill material) for a top emission type organic EL device, a light extraction layer material for a bottom emission type organic EL device, a solar cell material, and a lens material. Etc. can be preferably used.
- a sealant in particular, a fill material
- Etc. can be preferably used.
- an organic EL device having excellent light extraction efficiency, high efficiency, high luminance, and long life can be obtained.
- the resin composition of the present invention is used as a lens material, a lens having a high refractive index can be obtained, and the lens can be made thinner and lighter, and the design of an electronic device including the lens can be improved. Can do.
- the compound (A) in the present invention is a compound (curable compound) represented by the above formula (a).
- Two R a in the above formula (a) represent a reactive functional group (polymerizable functional group).
- the two R a may be respectively identical or different.
- the reactive functional group include a cationic polymerizable group such as a vinyl group, an allyl group, an epoxy group, a glycidyl group, and an oxetanyl group.
- a vinyl group or an allyl group is preferable.
- a plurality of R b in the formula (a) may be the same or different and may be protected with a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, or a protecting group.
- Examples of the halogen atom for R b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Examples of the alkyl group in R b include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, hexyl group, heptyl group, octyl group, and nonyl group.
- a C 1-10 (preferably C 1-5 ) alkyl group such as a decyl group.
- haloalkyl group for R b examples include C 1-10 (preferably C 1-5 ) haloalkyl groups such as a chloromethyl group, a trifluoromethyl group, a trifluoroethyl group, and a pentafluoroethyl group. it can.
- aryl group for R b examples include a phenyl group and a naphthyl group.
- the aromatic ring of the aryl group includes, for example, a halogen atom such as a fluorine atom, a C 1-4 alkyl group such as a methyl group, a C 1-5 haloalkyl group such as a trifluoromethyl group, a hydroxyl group, and a methoxy group.
- a halogen atom such as a fluorine atom
- a C 1-4 alkyl group such as a methyl group
- a C 1-5 haloalkyl group such as a trifluoromethyl group
- a hydroxyl group and a methoxy group.
- C 1-4 alkoxy group an amino group, a dialkylamino group, a carboxyl group, C 1-4 alkoxycarbonyl group such as methoxycarbonyl group, a nitro group, a cyano group
- an acyl group such as an acetyl group (in particular, C 1-6 aliphatic Group (s
- hydroxyalkyl group for R b examples include C 1-10 (preferably C 1-5 ) in which at least one hydrogen atom of the C 1-10 alkyl group such as hydroxymethyl group is substituted with a hydroxyl group.
- a hydroxyalkyl group etc. can be mentioned.
- a protecting group commonly used in the field of organic synthesis for example, alkyl group (for example, C 1-4 alkyl such as methyl group, t-butyl group, etc.) Alkenyl group (eg, allyl group); cycloalkyl group (eg, cyclohexyl group); aryl group (eg, 2,4-dinitrophenyl group); aralkyl group (eg, benzyl group); A substituted methyl group (eg, methoxymethyl group, methylthiomethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl group, etc.), tetrahydropyrani Hydroxyl groups, tetrahydrofuranyl groups, 1-hydroxyalkyl groups (for example, 1-hydroxyethyl)
- Examples of the protecting group for the amino group in R b include protecting groups commonly used in the field of organic synthesis (eg, alkyl groups, aralkyl groups, acyl groups, alkoxycarbonyl groups and the like exemplified as the protecting groups for the hydroxyl group). Can do.
- Examples of the protecting group for carboxyl group and sulfo group for R b include protecting groups commonly used in the field of organic synthesis [eg, alkoxy groups (eg, C 1-6 alkoxy such as methoxy group, ethoxy group, butoxy group, etc.). Group, etc.), cycloalkyloxy group, aryloxy group, aralkyloxy group, trialkylsilyloxy group, optionally substituted amino group, hydrazino group, alkoxycarbonylhydrazino group, aralkylcarbonylhydrazino group, etc. ] Can be mentioned.
- alkoxy groups eg, C 1-6 alkoxy such as methoxy group, ethoxy group, butoxy group, etc.
- Group, etc. cycloalkyloxy group, aryloxy group, aralkyloxy group, trialkylsilyloxy group, optionally substituted amino group, hydrazino group, alkoxycarbonylhydrazino group
- Examples of the acyl group in R b include C 1-6 aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, and pivaloyl group; aromatic acyl groups such as acetoacetyl group; Groups and the like.
- As the protecting group for the acyl group a protecting group commonly used in the field of organic synthesis can be used. Examples of the form in which the acyl group is protected include acetal (including hemiacetal).
- a plurality of R b bonds to one aromatic ring in the formula (a) that is, when m in the formula (a) is 2 to 4
- two or more selected from the plurality of R b Are bonded together to form a ring together with carbon atoms constituting an aromatic ring (for example, a 5-membered alicyclic carbocyclic ring, a 6-membered alicyclic carbocyclic ring, two or more alicyclic carbocyclic rings (monocyclic)).
- a alicyclic carbocyclic ring such as a condensed ring of the above; a lactone ring such as a 5-membered lactone ring or a 6-membered lactone ring).
- R c in the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms).
- the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond ( -CONH-), carbonate bond (-OCOO-), and a group in which a plurality of these are linked.
- the linking group may have a substituent such as a hydroxyl group or a carboxyl group, and examples of such a linking group include a divalent hydrocarbon group having one or more hydroxyl groups.
- Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups.
- Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
- Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group.
- the molecular weight of the compound (A) is not particularly limited, but is preferably 1000 or less, particularly preferably 700 or less, and most preferably 500 or less in terms of compatibility with the compound (B).
- the lower limit of the molecular weight is 302.
- a plurality of m are the same or different and represent an integer of 0 to 4.
- N (the number of repeating structural units in parentheses to which n is attached) represents an integer of 0 to 10.
- n is preferably 0 to 3 and particularly preferably 0 in that the viscosity of the resin composition can be adjusted in a wide range. That is, as the compound (A), a compound represented by the following formula (a ′) is particularly preferable. (Wherein R a , R b and m are the same as above)
- Examples of the compound (A) include compounds represented by the following formulas (a′-1) to (a′-12).
- Compound (A) can be produced by a known or conventional method. For example, a method in which 4,4′-thiobisbenzenethiol or the like is used as a raw material and reacted with vinyl halide, allyl halide, halide of (meth) acrylic acid, epihalohydrin, etc. in the presence of a base. Can do.
- a compound in which R a in formula (a) is a vinyl group can also be produced by a method of reacting 4,4′-thiobisbenzenethiol and dihaloethane, followed by dehydrohalogenation. .
- Compound (A) has low viscosity and excellent acetone solubility. Moreover, the curing delay property is exhibited by trapping the acid generated from the photocationic polymerization initiator (C) by ultraviolet irradiation. When heat treatment is performed after irradiation with ultraviolet rays, the compound (A) releases the trapped acid and quickly cures to form a cured product having a high refractive index, low moisture permeability, and low outgassing properties. .
- the compound (B) in the present invention includes at least one compound selected from the compound (b-1) and the compound (b-2).
- the compound (b-1) in the present invention is a compound (cation and radical polymerizable compound) represented by the following formula (b-1).
- the compound (b-1) undergoes a rapid polymerization reaction by the acid generated from the photocationic polymerization initiator (C). Therefore, the polymerization reaction can be allowed to proceed in a short time until the compound (A) traps the acid generated from the photocationic polymerization initiator (C). Further, when the photocationic polymerization initiator (C) is irradiated with ultraviolet rays, the photocationic polymerization initiator (C) absorbs the ultraviolet rays and decomposes to form a radical body, and the radical body extracts hydrogen to remove the acid.
- the compound (b-1) can also react with the radical body to cause a polymerization reaction to proceed. Therefore, the polymerization reaction can proceed to some extent even in the presence of the compound (A) having an action of trapping an acid generated from the photocationic polymerization initiator (C), and the resin composition of the present invention is semi-cured. Can lead to a state. (Wherein Y represents a single bond or a linking group, and R 1 represents a hydrogen atom or a methyl group)
- Y represents a single bond or a linking group.
- the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond (—CONH—), a carbonate bond ( -OCOO-) and a group in which a plurality of these are linked.
- divalent hydrocarbon group examples include, for example, a linear or branched alkylene group having 1 to 18 carbon atoms; vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group A straight or branched alkenylene group having 2 to 8 carbon atoms such as a hexenylene group, a heptenylene group or an octenylene group; a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms; Valent aromatic hydrocarbon group (for example, phenylene group, etc.) and a group in which these are linked through a single bond.
- a linear or branched alkylene group having 1 to 18 carbon atoms vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group A straight or branched alkenylene group having 2 to 8 carbon atoms such as
- the molecular weight (or weight average molecular weight) of the compound (b-1) is, for example, about 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). It is preferable at the point which can provide the property.
- the weight average molecular weight is a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).
- Examples of the compound (b-1) include N-vinylcarbazole, N-allylcarbazole, N- (meth) acryloylcarbazole, N- (vinylbenzyl) carbazole and the like. These can be used alone or in combination of two or more.
- the compound (b-2) in the present invention is a compound (radical polymerizable compound) represented by the following formula (b-2).
- the photocationic polymerization initiator (C) absorbs the ultraviolet rays and decomposes to form radicals, which generate acids by extracting hydrogen.
- the compound (b-2) undergoes a curing reaction by reacting with the radical body, leading to the semi-cured state of the resin composition of the present invention.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a hydrocarbon group
- t represents an integer of 0 or more, and when t is an integer of 2 or more, the plurality of R 2 may be the same or different.
- L represents a linking group.
- the hydrocarbon group in R 2 includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded.
- Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a decyl group, and a dodecyl group.
- An alkyl group having about 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 3 carbon atoms) such as vinyl group, allyl group, 1-butenyl group, etc.
- an alkenyl group having about 2 to 3 More preferred is an alkenyl group having about 2 to 3); an alkynyl group having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as an ethynyl group and a propynyl group.
- Examples of the alicyclic hydrocarbon group include 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.
- a cycloalkenyl group of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as a cyclopentenyl group and a cyclohexenyl group; a perhydronaphthalen-1-yl group , Norbornyl group, adamantyl group, tetracyclo [4.4.0.1 2,5 .
- a bridged cyclic hydrocarbon group such as a 1,7,10 ] dodecan-3-yl group.
- aromatic hydrocarbon group examples include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as a phenyl group and a naphthyl group.
- examples of the ring that may be bonded together to form a carbon atom that constitutes the aromatic ring in the formula include 3 to 20
- examples include a non-aromatic carbocycle having 3 members and a non-aromatic heterocycle having 3 to 20 members.
- the hydrocarbon group may have one or more substituents.
- substituents include a halogen atom such as a fluorine atom, a C 1-5 haloalkyl group such as a trifluoromethyl group, a hydroxyl group, an amino group, a dialkylamino group, a carboxyl group, a nitro group, and a cyano group.
- a halogen atom such as a fluorine atom
- a C 1-5 haloalkyl group such as a trifluoromethyl group
- a hydroxyl group such as an amino group, a dialkylamino group, a carboxyl group, a nitro group, and a cyano group.
- R 2 in the formula (b-2) is preferably an aromatic hydrocarbon group.
- T in the formula (b-2) represents an integer of 0 or more.
- t is, for example, an integer of 0 to 3, and is preferably an integer of 1 or more (eg, an integer of 1 to 3).
- L represents a linking group.
- the linking group is a divalent group having one or more atoms.
- a divalent hydrocarbon group a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), Examples thereof include an ester bond (—COO—), an amide bond (—CONH—), a carbonate bond (—OCOO—), and a group in which a plurality of these are linked.
- Examples of the divalent hydrocarbon group include the same examples as those in Y in the above formula (b-1).
- the molecular weight (or weight average molecular weight) of the compound (b-2) is, for example, about 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). It is preferable at the point which can provide the property.
- the weight average molecular weight is a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).
- the compound (b-2) is excellent in compatibility with the above-described compound (A), and can form a cured product having a high refractive index, low moisture permeability, and low outgassing property.
- a compound represented by formula (b-2-1) is preferred. In the following formulae, R 1 and L are the same as described above.
- the resin composition of the present invention contains at least one compound selected from the compound (b-1) and the compound (b-2) as the compound (B) together with the compound (A).
- the compound (A) traps an acid generated from the photocationic polymerization initiator (C) and exhibits curing retardation, while the compound (B) Since the curing reaction proceeds to some extent, a combination of these actions results in a semi-cured state.
- Compound (B) in the present invention has low viscosity and excellent acetone solubility. Moreover, the hardened
- the cationic photopolymerization initiator is a compound that decomposes by irradiation with ultraviolet rays to form a radical body, and the radical body extracts hydrogen to generate an acid to initiate a curing reaction of the curable compound.
- the cationic photopolymerization initiator is composed of a cation moiety that absorbs light and an anion moiety that is a source of acid generation.
- Examples of the photocationic polymerization initiator of the present invention include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salts. And the like, and the like.
- a sulfonium salt compound is preferable in that a cured product having excellent curability can be formed.
- the cation moiety of the sulfonium salt compound include aryls such as (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and tri-p-tolylsulfonium ion.
- aryls such as (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and tri-p-tolylsulfonium ion.
- examples include sulfonium ions (particularly triarylsulfonium ions).
- anion part of the cationic photopolymerization initiator examples include BF 4 ⁇ , B (C 6 F 5 ) 4 ⁇ , PF 6 ⁇ , [(Rf) k PF 6 ⁇ k ] ⁇ (Rf: 80% of hydrogen atoms)
- the above is an alkyl group substituted with a fluorine atom, k: an integer of 1 to 5), AsF 6 ⁇ , SbF 6 ⁇ , SbF 5 OH ⁇ and the like.
- Examples of the photocationic polymerization initiator of the present invention include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (penta Fluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4- (4-biphenylylthio) phenyl-4 -Biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, trade names “Syracure UVI-6970”, “S
- the resin composition of the present invention may further include, for example, a curable compound (excluding compounds (A) and (B)), a filler, a silane coupling agent, a polymerization inhibitor, an antioxidant, and a light stabilizer, as necessary.
- a curable compound excluding compounds (A) and (B)
- Conventional additives such as an agent, a plasticizer, a leveling agent, an antifoaming agent, a pigment, an organic solvent, an ultraviolet absorber, an ion adsorbent, a phosphor, a release agent, and a rheology control agent may be contained.
- the content thereof is, for example, 40% by weight or less, preferably 20% by weight or less, particularly preferably 10% by weight or less, based on the total amount of the resin composition.
- the resin composition of the present invention is a polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5000, particularly preferably more than 10,000) and / or a solubility parameter (SP value at 25 ° C .; Fedors formula) May contain a compound having a value of 8.5 or more, but the content thereof is, for example, 5% by weight or less, preferably 3% by weight or less, particularly preferably 1% by weight or less. If the content of the polymer compound exceeds the above range, the acetone solubility is lowered, and it is difficult to wash the inside of the liquid quantitative discharge device or the like with acetone.
- the resin composition of the present invention may contain a polymerization initiator other than the photocationic polymerization initiator (C) (for example, a radical photopolymerization initiator), but is included in the resin composition of the present invention.
- the proportion of the photocationic polymerization initiator (C) in the total amount of the polymerization initiator is, for example, 60% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more.
- the upper limit is 100% by weight.
- the content of the photo radical polymerization initiator in the resin composition of the present invention is, for example, 10% by weight or less (in particular, 5% by weight or less, particularly 1% by weight) of the total amount of the polymerization initiator contained in the resin composition of the present invention. Or less), and most preferably not substantially contained.
- the content of the photo radical polymerization initiator exceeds the above range, the viscosity after ultraviolet irradiation becomes too high, and it tends to be difficult to maintain adhesiveness.
- the resin composition of the present invention can be produced by uniformly mixing the above-described compound (A), compound (B), photocationic polymerization initiator (C), and other components as necessary.
- a compound (A), a compound (B), and a photocationic polymerization initiator (C) can each be used individually by 1 type or in combination of 2 or more types.
- each component is made as uniform as possible by using generally known mixing equipment such as a revolving and stirring agitation / deaerator, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. It is desirable to perform stirring, dissolution, mixing, dispersion, and the like. Each component may be mixed simultaneously or sequentially.
- the content of the compound (A) in the resin composition of the present invention is, for example, 45 to 95% by weight, preferably 60 to 95% by weight, more preferably the total amount (100% by weight) of the curable compound contained in the resin composition. Is 65 to 90% by weight, particularly preferably 70 to 85% by weight.
- the content of the compound (B) in the resin composition of the present invention is, for example, 5 to 40% by weight, preferably 10 to 35% by weight, based on the total amount (100% by weight) of the curable compound contained in the resin composition. Particularly preferred is 15 to 30% by weight.
- the ratio of the content of the compound (A) and the compound (B) contained in the resin composition of the present invention is, for example, 60:40 to 95: 5, preferably 65:35. ⁇ 90: 10, particularly preferably 70:30 to 85:15.
- the total content of the compound (A) and the compound (B) in the resin composition of the present invention is, for example, 50% by weight or more, preferably 60% of the total amount (100% by weight) of the curable compound contained in the resin composition.
- % By weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.
- the upper limit is 100% by weight.
- the content of the cationic photopolymerization initiator (C) in the resin composition of the present invention is preferably 0.01 to 15 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the curable compound contained in the resin composition. 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, and most preferably 0.1 to 3 parts by weight.
- the resin composition of the present invention contains the compound (A) and the compound (B) as the curable compound in the above range, the fluidity is appropriately reduced by irradiation with ultraviolet rays and led to a semi-cured state, and the state is maintained. can do. Therefore, for example, when the resin composition of the present invention is used as a fill material, the outflow from the dam can be prevented. Moreover, even if it irradiates with ultraviolet rays, it can be kept in a semi-cured state (that is, in a state where adhesion is maintained) until heat treatment is performed, and the curing reaction can be resumed by adjusting the timing of the heat treatment. The time can be set arbitrarily.
- the viscosity after ultraviolet irradiation becomes too high, and the followability with respect to steps such as elements and electrodes. Decreases, and a gap is formed between the bonded substrate and the sealing accuracy tends to decrease.
- the content of the compound (A) exceeds the above range (or if the content of the compound (B) is below the above range)
- the fluidity cannot be lowered even when irradiated with ultraviolet rays.
- the resin composition of the present invention is used as a fill material, it may be difficult to prevent outflow from a dam.
- the resin composition of the present invention is excellent in fluidity until it is irradiated with ultraviolet rays, and the viscosity at 25 ° C. is, for example, 10 mPa ⁇ s or more and less than 30 mPa ⁇ s, preferably 15 to 25 mPa ⁇ s. Therefore, it can discharge favorably using liquid fixed-quantity discharge apparatuses, such as a dispenser, an inkjet coating device, etc.
- the viscosity of the resin composition can be measured using an E-type viscometer or a rheometer.
- the resin composition of the present invention comprises a compound (A) having an action of trapping an acid generated from the photocationic polymerization initiator (C) and suppressing the progress of the curing reaction, and the acid or photocationic polymerization initiator (C ),
- the compound (B) that undergoes a curing reaction by a radical body, which is a decomposition product of the compound (B) contains both the compound (B) and the curing reaction of the compound (B) is suppressed to the extent that the fluidity is lowered. Curing does not proceed until disappears. In other words, the curing retardation is exhibited and the semi-cured state is maintained.
- the resin composition of the present invention can moderately reduce fluidity by irradiating with ultraviolet rays
- a polymer compound for example, petroleum resin
- the ultraviolet irradiation is preferably performed by irradiating light of 1000 mJ / cm 2 or more with a mercury lamp or the like.
- the viscosity of the resin composition immediately after UV irradiation (irradiation amount: 1500 mJ / cm 2 ) at 25 ° C. is, for example, 30 to 2000 mPa ⁇ s, preferably 30 to 1000 mPa ⁇ s.
- the resin composition of the present invention can maintain a semi-cured state until heat treatment is performed, and the resin composition 30 minutes after irradiation with ultraviolet rays (irradiation amount: 1500 mJ / cm 2 ).
- the viscosity at 25 ° C. is, for example, 30 to 2500 mPa ⁇ s, preferably 30 to 1500 mPa ⁇ s.
- the resin composition of the present invention can be subjected to heat treatment after being irradiated with ultraviolet rays to release the acid trapped in the compound (A), whereby the curing reaction is restarted, and a cured product can be quickly formed after the heat treatment. it can.
- the heat treatment is performed, for example, at a temperature of 50 to 200 ° C. (more preferably 50 to 170 ° C., more preferably 50 to 150 ° C.) for 10 to 600 minutes (more preferably 10 to 360 minutes, still more preferably 15 to 180). Heating for a minute) is preferred.
- the resin composition of the present invention has the above characteristics, when it is used as a sealant for an organic EL device, the resin composition that has been subjected to ultraviolet irradiation in advance and has reduced fluidity is applied to the organic EL device.
- the organic EL element can be bonded to the organic EL element while preventing the resin composition from flowing out of the dam, and then the organic EL element can be sealed without being directly exposed to ultraviolet rays by performing a heat treatment.
- the cured product of the resin composition of the present invention can be obtained by subjecting the resin composition to ultraviolet irradiation under the above-mentioned conditions and further subjecting it to a heat treatment under the above-mentioned conditions.
- the refractive index of the cured product of the resin composition of the present invention with respect to light having a wavelength of 589.3 nm (sodium D line) at 25 ° C. is, for example, 1.65 or more, preferably 1.68 or more.
- cured material can be measured by the method based on JISK7142, or the method using a prism coupler, for example.
- the cured product has low moisture permeability, and the moisture permeability (g / m 2 ⁇ day ⁇ atm) of the cured product (thickness: 100 ⁇ m) is, for example, 100 or less, preferably 50 or less, particularly preferably 35. Hereinafter, it is most preferably 25 or less.
- the moisture permeation amount is a value obtained by measuring the moisture permeation amount of a cured product adjusted to a thickness of 100 ⁇ m in accordance with JIS L 1099 and JIS Z 0208 under the conditions of 60 ° C. and 90% RH.
- the cured product has low outgassing properties, and the amount of outgas of the cured product (60 mg) is, for example, 1000 ppm or less (preferably 200 ppm or less, particularly preferably 100 ppm or less).
- the outgas amount can be measured by the head space GC / MS.
- the resin composition of the present invention has a low viscosity and excellent coating properties and acetone solubility until it is irradiated with ultraviolet rays. Moreover, by irradiating with ultraviolet rays, the fluidity can be lowered moderately to be in a semi-cured state, and the semi-cured state can be maintained until heat treatment is performed. And after irradiating with ultraviolet rays, the curing reaction can be restarted by further heat treatment, and then cured rapidly to form a cured product having high refractive index, low moisture permeability, and low outgassing properties. be able to.
- a sealant for example, a sealant (particularly, a fill material) for a top emission type organic EL device, a light extraction layer material for a bottom emission type organic EL device, a solar cell material, a lens material (particularly, a high refractive index lens material) ) And the like.
- the resin composition of the present invention when used as a sealant in the process of producing an organic EL device, reflection of light at the interface with a high refractive index member can be suppressed, and light extraction efficiency is improved.
- an organic EL device having high efficiency, high brightness, and long life can be obtained.
- the method for producing an organic EL device of the present invention is characterized by sealing an organic EL element (particularly, a top emission type organic EL element) through the following steps 1 and 2.
- Step 1 UV coating is applied to the coating film made of the resin composition described above.
- Step 2 The coating film after UV irradiation obtained through Step 1 is bonded to the element mounting surface of the substrate on which the organic EL element is mounted. Heat treatment
- an organic EL device can be sealed while preventing deterioration of the device due to ultraviolet irradiation, and a long-life and highly reliable organic EL device can be provided.
- the ultraviolet irradiation and heat treatment methods can be performed in the same manner as the ultraviolet irradiation and heat treatment of the above resin composition.
- the production method of the present invention includes the following method 1.
- ⁇ Method 1 See FIG. 1>
- Step 1-1 Applying the above-mentioned resin composition on the lid to form a coating film / lid laminate
- Step 1-2 Irradiating the coating film with ultraviolet rays
- Step 2-1 An organic EL element on the substrate Install and bond the UV / irradiated coating film / lid laminate on the organic EL element installation surface so that the coating film surface faces the element installation surface
- Step 2-2 Heat treatment is performed to cure the coating film
- a moisture-proof substrate as the lid (lid) or substrate, for example, a glass substrate such as soda glass or non-alkali glass; a metal substrate such as stainless steel or aluminum; Polyfluorinated ethylene polymers such as fluorinated ethylene chloride (PCTFE), polyvinylidene fluoride (PVDF), copolymers of PCTFE and PVDF, copolymers of PVDF and polyfluorinated ethylene chloride, polyimide, polycarbonate, dicyclo Examples thereof include cycloolefin resins such as pentadiene, polyesters such as polyethylene terephthalate, and resin base materials such as polyethylene and polystyrene.
- PCTFE fluorinated ethylene chloride
- PVDF polyvinylidene fluoride
- copolymers of PCTFE and PVDF copolymers of PVDF and polyfluorinated ethylene chloride
- polyimide polycarbonate
- dicyclo Examples thereof include cycloolefin resins such
- the organic EL element includes an anode / light emitting layer / negative electrode laminate. If necessary, a passivation film such as a SiN film may be provided.
- the coating film made of the resin composition of the present invention forms a dam by applying a dam material on a lid (lid), and uses a liquid dispensing apparatus such as a dispenser or an inkjet coating apparatus in the dam. And can be formed by discharging the resin composition.
- the thickness of the coating film is not particularly limited as long as the purpose of protecting the organic EL element from moisture and the like can be achieved.
- the resin composition of this invention is excellent in acetone solubility, the said apparatus etc. can wash
- the resin composition at the time of bonding is bonded to the organic EL element after the fluidity of the resin composition is appropriately reduced by irradiating the coating film made of the resin composition of the present invention with ultraviolet rays. Things can be prevented from flowing out of the dam.
- the organic EL element can be sealed without being exposed to ultraviolet rays, and the organic EL elements do not have deterioration due to ultraviolet rays.
- the curing reaction is resumed by performing the heat treatment after the bonding, even if the bonding work is delayed, the bonding is not difficult.
- an organic EL element can be sealed with the hardened
- the viscosity of the resin composition is a value measured at 25 ° C. and a shear rate of 20 (1 / s) using a rheometer (trade name “Physica® MCR301”, manufactured by Anton® Paar).
- reaction solution was stirred for 6 hours, then cooled to 0 ° C., and then slowly quenched by dropwise addition of water, and transferred to a separatory funnel.
- the aqueous layer was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Thereafter, the organic layer was separated and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off to obtain a liquid crude product.
- Example 1 MPV (82 parts by weight), VCZ (17 parts by weight), and a photocationic polymerization initiator (1 part by weight) were put into a self-revolving stirring and deaerator (model: AR-250, manufactured by Shinky Corporation). And stirred to obtain a resin composition (1).
- the obtained resin composition (1) was poured into a mold and irradiated with ultraviolet rays from a distance of 10 cm with a 200 W / cm high-pressure mercury lamp (irradiation amount: 1500 mJ / cm 2 ).
- the viscosity before ultraviolet irradiation, immediately after ultraviolet irradiation, and 30 minutes after ultraviolet irradiation was measured, respectively, and the viscosity raise degree after ultraviolet irradiation was computed from the following formula.
- Viscosity increase degree after ultraviolet irradiation viscosity 30 minutes after ultraviolet irradiation / viscosity immediately after ultraviolet irradiation
- the resin composition (1) after ultraviolet irradiation is subjected to heat treatment (100 ° C., 1 hour) to obtain a cured product (1 ) (Thickness: 100 ⁇ m).
- UV delayed curing dam material (3,4,3 ′, 4′-diepoxy) 30 parts by weight of bicyclohexyl, liquid bisphenol F diglycidyl ether (trade name “YL-983U”, manufactured by Mitsubishi Chemical Corporation) 70 Parts by weight, 2- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, 1,3,4,6-tetraglycidylglycoluril (trade name "TG-G ”, 2.5 parts by weight, manufactured by Shikoku Kasei Kogyo Co., Ltd., talc (average particle size 1.5 ⁇ m, tabular particles, trade name“ FG-15 ”, manufactured by Nippon Talc Co., Ltd.), 52 parts by weight, spacer particles (Average particle size 15 ⁇ m, trade name “SD-DB”, manufactured by Hayakawa Rubber Co., Ltd.)
- the viscosity of the obtained UV delayed dam material was 150 Pa ⁇ s. Further, the viscosity immediately after the UV delayed dam material was irradiated with ultraviolet rays from a distance of 10 cm with a 200 W / cm high-pressure mercury lamp (irradiation amount: 1500 mJ / cm 2 ) was 1500,000 Pa ⁇ s. Furthermore, the viscosity for 30 minutes after the ultraviolet irradiation was 1570000 Pa ⁇ s.
- the viscosity of the dam material is a value measured using a rheometer (trade name “Physica MCR301”, manufactured by Anton Paar) at 25 ° C. and a shear rate of 2.5 (1 / s). .
- the UV delayed curing dam material was applied to the glass (76 mm ⁇ 52 mm) surface using an auto dispenser to form a 50 mm ⁇ 35 mm dam, and the fill material (obtained in Examples or Comparative Examples) was formed in the dam.
- a total of 15 drops (80 to 120 mg) of the resin composition) were dropped one by one at a distance of 5 mm or more from the dam so that the drops did not touch.
- ultraviolet rays were irradiated from a location 10 cm away from the glass surface (irradiation amount: 1500 mJ / cm 2 ).
- OPP-EO-VE (2-phenylphenoxy) ethyl vinyl ether obtained in Preparation Example 1, molecular weight: 240.16 HRD-01: 2- (o-phenylphenoxy) ethyl acrylate, molecular weight: 268, trade name “HRD-01”, manufactured by Nippon Touch Technofine Chemical Co., Ltd.
- HRD-01 2- (o-phenylphenoxy) ethyl acrylate
- SY-OPG o-phenylphenol glycidyl ether, trade name “SY-OPG”, manufactured by Sakamoto Pharmaceutical Co., Ltd.
- Neopolymer 120 petroleum resin, weight average molecular weight: 1500 SP value at 25 ° C .: 11.2, trade name “Neopolymer 120”, manufactured by JX Nippon Mining & Energy Corporation [Photocationic polymerization initiator (C)] Photocationic polymerization initiator: 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate
- the resin composition of the present invention After irradiating the resin composition of the present invention with ultraviolet rays, it is bonded to a substrate provided with an organic EL element, and heat treatment is performed after the bonding, thereby suppressing the outflow from the dam and making it difficult to bond.
- the organic EL element can be sealed with a cured product having a high refractive index, a low moisture permeability, and a low outgassing property without being directly exposed to ultraviolet rays. . Therefore, the resin composition of the present invention can be preferably used as a sealant for top emission type organic EL devices, a light extraction layer material for bottom emission type organic EL devices, a solar cell material, a lens material, and the like.
Abstract
Provided is a resin composition capable of being used as a fill material when sealing an organic EL element using a dam-and-fill encapsulation method, wherein the resin composition has superior coating properties and acetone solubility, allows for the timing of thickening and curing to be designated with discretion, and is capable of forming a cured product having a high refractive index, low moisture permeability, and low levels of outgassing. The resin composition of the present invention comprises a compound (A) represented by formula (a), at least one compound (B) selected from among the compound represented by formula (b-1) and the compound represented by formula (b-2), and a photocationic polymerization initiator (C).
Description
本発明は、ダムアンドフィル工法により有機エレクトロルミネッセンス素子を封止する際に、フィル材として使用可能な樹脂組成物に関する。本願は、２０１６年４月１日に日本に出願した、特願２０１６－０７４５１７号の優先権を主張し、その内容をここに援用する。
The present invention relates to a resin composition that can be used as a fill material when an organic electroluminescence element is sealed by a dam and fill method. This application claims the priority of Japanese Patent Application No. 2016-074517 for which it applied to Japan on April 1, 2016, and uses the content here.
有機エレクトロルミネッセンス（以後、「有機ＥＬ」と称する場合がある）素子を含む有機ＥＬデバイスは、耐衝撃性や視認性の高さと発光色の多様性から、フルカラーのフラットパネルディスプレーとして、又はＬＥＤに代わるものとして期待されている。有機ＥＬデバイスには、光取り出し方式の違いから、トップ・エミッション型とボトム・エミッション型の２種類がある。
An organic EL device including an organic electroluminescence (hereinafter sometimes referred to as “organic EL”) element is used as a full-color flat panel display or an LED because of high impact resistance, high visibility, and a variety of emission colors. Expected to replace. There are two types of organic EL devices, a top emission type and a bottom emission type, due to differences in light extraction methods.
しかし、有機ＥＬ素子は他の電子部品に比べて水分の影響を受けやすく、有機ＥＬ素子内に浸入した水分によって電極の酸化や有機物の変性等が引き起こされ、発光特性が著しく低下することが問題であった。この問題を解決する方法としては、有機ＥＬ素子の周りを低透湿性の樹脂で封止（若しくは、被覆）する方法が知られている。
However, organic EL elements are more susceptible to moisture than other electronic components, and moisture that penetrates into the organic EL elements can cause electrode oxidation or organic modification, resulting in a significant decrease in light emission characteristics. Met. As a method for solving this problem, a method of sealing (or covering) the periphery of the organic EL element with a low moisture-permeable resin is known.
前記樹脂で封止する方法としては、基板上に形成した有機ＥＬ素子の周りを紫外線照射で硬化する樹脂組成物で充填し、その後、前記樹脂組成物を硬化させることにより封止する方法（１）や、リッド（蓋）に樹脂組成物を塗布し、紫外線を照射した後に有機ＥＬ素子を形成した基板と貼り合わせて封止する方法（２）が知られている。
As a method for sealing with the resin, a method of sealing by filling the periphery of the organic EL element formed on the substrate with a resin composition that is cured by ultraviolet irradiation, and then curing the resin composition (1) And a method (2) in which a resin composition is applied to a lid (lid) and irradiated with ultraviolet rays, and then bonded to a substrate on which an organic EL element is formed and sealed (2).
上記方法（１）は、有機ＥＬ素子が紫外線に直に曝されることにより発光特性が低下することが問題であった。その他、高コントラストを有する有機ＥＬデバイスを形成するためにカラーフィルターを有機ＥＬ素子の上部に配置する場合には、カラーフィルターによって紫外線が遮られるため樹脂組成物が硬化しにくくなることが問題であった。
The method (1) has a problem in that the light emission characteristics are deteriorated by directly exposing the organic EL element to ultraviolet rays. In addition, when a color filter is disposed on top of an organic EL element in order to form an organic EL device having high contrast, the problem is that the resin composition is difficult to cure because the color filter blocks ultraviolet rays. It was.
一方、上記方法（２）では、有機ＥＬ素子を紫外線に直に曝すことは避けられるが、紫外線照射により樹脂組成物の硬化が速やかに進行するため、貼り合わせ作業が遅滞すると貼り合わせが困難となる事態が発生し、歩留まりが低下することが問題であった。
On the other hand, in the above method (2), it is possible to avoid directly exposing the organic EL element to ultraviolet rays, but since the curing of the resin composition proceeds rapidly due to ultraviolet irradiation, it is difficult to perform the bonding when the bonding operation is delayed. It was a problem that the yield would be reduced.
特許文献１には、エポキシ化合物と、光カチオン重合開始剤と、硬化遅延剤としてのクラウンエーテルやポリエーテル類とを含有する樹脂組成物は、紫外線照射後、硬化反応が徐々に進行するため、上記方法（２）において前記組成物を使用すれば、有機ＥＬ素子を紫外線に直に曝すことなく封止することができると記載されている。しかし、クラウンエーテルやポリエーテル類は光カチオン重合開始剤から発生する酸により分解してアウトガスを発生し、そのアウトガスにより有機ＥＬ素子が劣化することが問題であった。
Patent Document 1 discloses that a resin composition containing an epoxy compound, a cationic photopolymerization initiator, and a crown ether or a polyether as a curing retarder gradually progresses after the ultraviolet irradiation, It is described that when the composition is used in the method (2), the organic EL device can be sealed without being directly exposed to ultraviolet rays. However, there has been a problem that crown ethers and polyethers are decomposed by an acid generated from a photocationic polymerization initiator to generate outgas, and the organic EL element is deteriorated by the outgas.
また、樹脂組成物の硬化物には、有機ＥＬ素子との界面で光の反射を生じにくくするため、高い屈折率を有することが求められる。そして、高屈折率を有する硬化物を形成する樹脂としては、ビス（４－ビニルチオフェニル）スルフィド誘導体が知られている（特許文献２）。
Further, the cured product of the resin composition is required to have a high refractive index in order to make it difficult for light to be reflected at the interface with the organic EL element. As a resin for forming a cured product having a high refractive index, a bis (4-vinylthiophenyl) sulfide derivative is known (Patent Document 2).
しかし、前記ビス（４－ビニルチオフェニル）スルフィド誘導体は粘度が低く、これを含む樹脂組成物を例えばダムアンドフィル工法により有機ＥＬ素子を封止する際にフィル材として使用すると、上記方法（２）において基板と貼り合わせる際等にダムから流出しやすいことが問題であった。
However, the bis (4-vinylthiophenyl) sulfide derivative has a low viscosity, and when the resin composition containing the bis (4-vinylthiophenyl) sulfide derivative is used as a fill material when sealing an organic EL device by, for example, a dam and fill method, the above method (2 ) Is likely to flow out of the dam when bonded to the substrate.
フィル材がダムから流出するのを防止する方法としては、増粘効果に優れた高分子化合物（例えば、石油樹脂等）を添加して流動性を低下させることが考えられるが、石油樹脂はアウトガスの発生源となることが問題であった。また、高分子化合物は工業用洗浄剤として多用されるアセトンに不溶性を示すものが多く、アセトン不溶性の高分子化合物を添加した樹脂組成物をディスペンサー等の液体定量吐出装置やインクジェット塗布装置等を使用して塗布した場合、前記装置等内部をアセトンで洗浄できないことが問題であった。更に、ダムからの流出を防止できる程度に増粘すると、前記装置等を使用して吐出することが困難となる場合があり、前記装置等からの良好な吐出性、前記装置等内部の洗浄性、及びダムからの流出防止性を兼ね備えることは非常に困難であった。
As a method for preventing the fill material from flowing out of the dam, it is conceivable to add a polymer compound (for example, petroleum resin) having an excellent thickening effect to lower the fluidity. It was a problem to become a source of In addition, many polymer compounds are insoluble in acetone, which is often used as an industrial cleaner, and a resin composition containing an acetone-insoluble polymer compound is used in a liquid dispensing device such as a dispenser or an inkjet coating device. When the coating was applied, the problem was that the inside of the apparatus or the like could not be cleaned with acetone. Furthermore, if the viscosity is increased to such an extent that it can be prevented from flowing out of the dam, it may be difficult to discharge using the device, etc., good dischargeability from the device, etc., cleanability inside the device, etc. It was very difficult to combine the prevention of spillage from the dam.
従って、本発明の目的は、ダムアンドフィル工法により有機ＥＬ素子を封止する際に、フィル材として使用できる樹脂組成物であって、塗布性及びアセトン溶解性に優れ、増粘及び硬化のタイミングを任意に設定することができ、高屈折率、低透湿性、及び低アウトガス性を有する硬化物を形成することができる樹脂組成物を提供することにある。
本発明の他の目的は、前記樹脂組成物の硬化物によって有機ＥＬ素子が封止された構成を有する有機ＥＬデバイスを提供することにある。 Accordingly, an object of the present invention is a resin composition that can be used as a fill material when sealing an organic EL element by a dam and fill method, and is excellent in applicability and acetone solubility, and has a timing of thickening and curing. It is an object to provide a resin composition capable of forming a cured product having a high refractive index, a low moisture permeability, and a low outgassing property.
Another object of the present invention is to provide an organic EL device having a configuration in which an organic EL element is sealed with a cured product of the resin composition.
本発明の他の目的は、前記樹脂組成物の硬化物によって有機ＥＬ素子が封止された構成を有する有機ＥＬデバイスを提供することにある。 Accordingly, an object of the present invention is a resin composition that can be used as a fill material when sealing an organic EL element by a dam and fill method, and is excellent in applicability and acetone solubility, and has a timing of thickening and curing. It is an object to provide a resin composition capable of forming a cured product having a high refractive index, a low moisture permeability, and a low outgassing property.
Another object of the present invention is to provide an organic EL device having a configuration in which an organic EL element is sealed with a cured product of the resin composition.
本発明者は上記課題を解決するため鋭意検討した結果、下記事項を見いだした。
１．１分子中に反応性官能基を２つ有するフェニルスルフィド化合物（Ａ）と、１分子中に重合性不飽和基を１つ有する特定の化合物（Ｂ）と、光カチオン重合開始剤（Ｃ）とを含有する樹脂組成物は、低粘度で塗布性に優れ、且つアセトン溶解性に優れること
２．前記樹脂組成物に紫外線照射を施すと、前記（Ａ）は硬化遅延性を発揮し、同時に、前記（Ｂ）は硬化性を発揮することにより、樹脂組成物の硬化反応が、適度に増粘した状態（すなわち、半硬化状態）で一旦停止すること
３．一旦停止していた硬化反応は、加熱処理を施すことで再開し、その後は速やかに硬化物を形成することができること
４．得られる硬化物は高屈折率、低透湿性、及び低アウトガス性を兼ね備えること
本発明はこれらの知見に基づいて完成させたものである。 As a result of intensive studies to solve the above problems, the present inventors have found the following matters.
1.1 Phenyl sulfide compound (A) having two reactive functional groups in a molecule, a specific compound (B) having one polymerizable unsaturated group in one molecule, a photocationic polymerization initiator (C 1) is low in viscosity, excellent in coatability and excellent in acetone solubility. When the resin composition is irradiated with ultraviolet rays, the (A) exhibits curing retardation, and at the same time, the (B) exhibits curing properties, so that the curing reaction of the resin composition is moderately thickened. 2. Stop once in a finished state (ie, semi-cured state) 3. The curing reaction once stopped can be resumed by applying heat treatment, and thereafter a cured product can be formed quickly. The obtained cured product has high refractive index, low moisture permeability, and low outgassing properties. The present invention has been completed based on these findings.
１．１分子中に反応性官能基を２つ有するフェニルスルフィド化合物（Ａ）と、１分子中に重合性不飽和基を１つ有する特定の化合物（Ｂ）と、光カチオン重合開始剤（Ｃ）とを含有する樹脂組成物は、低粘度で塗布性に優れ、且つアセトン溶解性に優れること
２．前記樹脂組成物に紫外線照射を施すと、前記（Ａ）は硬化遅延性を発揮し、同時に、前記（Ｂ）は硬化性を発揮することにより、樹脂組成物の硬化反応が、適度に増粘した状態（すなわち、半硬化状態）で一旦停止すること
３．一旦停止していた硬化反応は、加熱処理を施すことで再開し、その後は速やかに硬化物を形成することができること
４．得られる硬化物は高屈折率、低透湿性、及び低アウトガス性を兼ね備えること
本発明はこれらの知見に基づいて完成させたものである。 As a result of intensive studies to solve the above problems, the present inventors have found the following matters.
1.1 Phenyl sulfide compound (A) having two reactive functional groups in a molecule, a specific compound (B) having one polymerizable unsaturated group in one molecule, a photocationic polymerization initiator (C 1) is low in viscosity, excellent in coatability and excellent in acetone solubility. When the resin composition is irradiated with ultraviolet rays, the (A) exhibits curing retardation, and at the same time, the (B) exhibits curing properties, so that the curing reaction of the resin composition is moderately thickened. 2. Stop once in a finished state (ie, semi-cured state) 3. The curing reaction once stopped can be resumed by applying heat treatment, and thereafter a cured product can be formed quickly. The obtained cured product has high refractive index, low moisture permeability, and low outgassing properties. The present invention has been completed based on these findings.
すなわち、本発明は、下記化合物（Ａ）と下記化合物（Ｂ）と光カチオン重合開始剤（Ｃ）を含む樹脂組成物を提供する。
化合物（Ａ）：下記式（ａ）
（式中、Ｒaは反応性官能基を示す。Ｒbはハロゲン原子、アルキル基、ハロアルキル基、アリール基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシアルキル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいスルホ基、ニトロ基、シアノ基、又は保護基で保護されていてもよいアシル基を示す。Ｒcは単結合又は連結基を示す。ｍは０～４の整数を示し、ｎは０～１０の整数を示す。尚、２つのＲaは、それぞれ同一であってもよく異なっていてもよい。また、複数のＲb及びｍは、それぞれ同一であってもよく異なっていてもよい）
で表される化合物
化合物（Ｂ）：下記式（b-1）
（式中、Ｙは単結合又は連結基を示し、Ｒ1は水素原子又はメチル基を示す）
で表される化合物、及び下記式（b-2）
（式中、Ｒ1は水素原子又はメチル基を示し、Ｒ2は炭化水素基を示す。ｔは０以上の整数を示し、ｔが２以上の整数である場合、複数のＲ2はそれぞれ同一であってもよく、異なっていてもよい。Ｒ2が複数存在する場合、それらは互いに結合して、式中の芳香環を構成する炭素原子と共に環を形成していてもよい。Ｌは連結基を示す）
で表される化合物から選択される少なくとも１種の化合物 That is, this invention provides the resin composition containing the following compound (A), the following compound (B), and a photocationic polymerization initiator (C).
Compound (A): Formula (a) below
(In the formula, R a represents a reactive functional group. R b represents a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, or an optionally protected group with a protecting group. A hydroxyalkyl group, an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protecting group; An acyl group which may be protected, R c represents a single bond or a linking group, m represents an integer of 0 to 4, n represents an integer of 0 to 10. Note that two R a are And each of R b and m may be the same or different.)
Compound represented by formula (B): Formula (b-1) below
(Wherein Y represents a single bond or a linking group, and R 1 represents a hydrogen atom or a methyl group)
And a compound represented by the following formula (b-2)
(In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrocarbon group, t represents an integer of 0 or more, and when t is an integer of 2 or more, a plurality of R 2 are the same. In the case where a plurality of R 2 are present, they may be bonded to each other to form a ring together with the carbon atoms constituting the aromatic ring in the formula. Group)
At least one compound selected from the compounds represented by
化合物（Ａ）：下記式（ａ）
で表される化合物
化合物（Ｂ）：下記式（b-1）
で表される化合物、及び下記式（b-2）
で表される化合物から選択される少なくとも１種の化合物 That is, this invention provides the resin composition containing the following compound (A), the following compound (B), and a photocationic polymerization initiator (C).
Compound (A): Formula (a) below
Compound represented by formula (B): Formula (b-1) below
And a compound represented by the following formula (b-2)
At least one compound selected from the compounds represented by
本発明は、また、式（ａ）中のＲaが、ビニル基又はアリル基である前記の樹脂組成物を提供する。
The present invention also provides the above resin composition, wherein R a in the formula (a) is a vinyl group or an allyl group.
本発明は、また、式（b-2）で表される化合物が、下記式（b-2-1）
（式中、Ｒ1は水素原子又はメチル基を示し、Ｌは連結基を示す）
で表される化合物である前記の樹脂組成物を提供する。 In the present invention, the compound represented by the formula (b-2) is represented by the following formula (b-2-1):
(Wherein R 1 represents a hydrogen atom or a methyl group, and L represents a linking group)
The resin composition is a compound represented by:
で表される化合物である前記の樹脂組成物を提供する。 In the present invention, the compound represented by the formula (b-2) is represented by the following formula (b-2-1):
The resin composition is a compound represented by:
本発明は、また、化合物（Ａ）と化合物（Ｂ）の含有量の比（前者：後者（重量比））が６０：４０～９５：５であり、化合物（Ａ）と化合物（Ｂ）の合計含有量が、樹脂組成物に含まれる硬化性化合物全量の５０重量％以上である前記の樹脂組成物を提供する。
In the present invention, the content ratio of the compound (A) to the compound (B) (the former: the latter (weight ratio)) is 60:40 to 95: 5, and the compound (A) and the compound (B) Provided is the above resin composition having a total content of 50% by weight or more of the total amount of the curable compound contained in the resin composition.
本発明は、また、２５℃における粘度が１０ｍＰａ・ｓ以上、３０ｍＰａ・ｓ未満である前記の樹脂組成物を提供する。
The present invention also provides the above resin composition having a viscosity at 25 ° C. of 10 mPa · s or more and less than 30 mPa · s.
本発明は、また、有機エレクトロルミネッセンス素子封止剤である前記の樹脂組成物を提供する。
The present invention also provides the resin composition as described above, which is an organic electroluminescence device sealant.
本発明は、また、下記工程１及び２を経て有機エレクトロルミネッセンス素子を封止することを特徴とする有機エレクトロルミネッセンスデバイスの製造方法を提供する。
工程１：前記樹脂組成物からなる塗膜に、紫外線照射を施す
工程２：有機エレクトロルミネッセンス素子を設置した基板の素子設置面に、工程１を経て得られた紫外線照射後の塗膜を貼り合わせて加熱処理を施す The present invention also provides a method for producing an organic electroluminescent device, wherein the organic electroluminescent element is sealed through the following steps 1 and 2.
Step 1: UV irradiation is performed on the coating film made of the resin composition. Step 2: The UV-irradiated coating film obtained throughStep 1 is bonded to the element mounting surface of the substrate on which the organic electroluminescence element is mounted. Heat treatment
工程１：前記樹脂組成物からなる塗膜に、紫外線照射を施す
工程２：有機エレクトロルミネッセンス素子を設置した基板の素子設置面に、工程１を経て得られた紫外線照射後の塗膜を貼り合わせて加熱処理を施す The present invention also provides a method for producing an organic electroluminescent device, wherein the organic electroluminescent element is sealed through the
Step 1: UV irradiation is performed on the coating film made of the resin composition. Step 2: The UV-irradiated coating film obtained through
本発明は、また、前記の樹脂組成物の硬化物で素子が封止された構成を有する有機エレクトロルミネッセンスデバイスを提供する。
The present invention also provides an organic electroluminescence device having a structure in which an element is sealed with a cured product of the resin composition.
すなわち、本発明は、以下に関する。
［１］ 式（ａ）で表される化合物（Ａ）と、式（b-1）で表される化合物、及び下記式（b-2）で表される化合物から選択される少なくとも１種の化合物（Ｂ）と、光カチオン重合開始剤（Ｃ）を含む樹脂組成物。
［２］ 式（ａ）中のＲaがカチオン重合性基である、［１］に記載の樹脂組成物。
［３］ 式（ａ）中のＲaがビニル基、アリル基、エポキシ基、グリシジル基、及びオキセタニル基から選択される基である、［１］に記載の樹脂組成物。
［４］ 式（ａ）中のＲaが、ビニル基又はアリル基である、［１］に記載の樹脂組成物。
［５］ 式（ａ）中のＲcが二価の炭化水素基、カルボニル基、エーテル結合、チオエーテル結合、エステル結合、アミド結合、カーボネート結合、及びこれらが複数個連結した基から選択される基である、［１］～［４］の何れか１つに記載の樹脂組成物。
［６］ 化合物（Ａ）の分子量が１０００以下（好ましくは７００以下、最も好ましくは５００以下）である、［１］～［５］の何れか１つに記載の樹脂組成物。
［７］ 化合物（Ａ）の分子量が３０２～１０００（好ましくは３０２～７００、最も好ましくは３０２～５００）である、［１］～［５］の何れか１つに記載の樹脂組成物。
［８］ 化合物（Ａ）が式（ａ’）で表される化合物である、［１］～［７］の何れか１つに記載の樹脂組成物。
［９］ 化合物（Ａ）が式（a'-1）～（a'-12）で示される化合物から選択される少なくとも１種の化合物である、［１］～［７］の何れか１つに記載の樹脂組成物。
［１０］ 式（b-1）中のＹが二価の炭化水素基（好ましくは、Ｃ1-18アルキレン基、Ｃ2-8アルケニレン基、Ｃ6-10のアリーレン基、及びこれらが単結合を介して連結した基から選択される基）、カルボニル基、エーテル結合、エステル結合、アミド結合、カーボネート結合、及びこれらが複数個連結した基から選択される基である、［１］～［９］の何れか１つに記載の樹脂組成物。
［１１］ 式（b-1）で表される化合物の分子量が１０００～７０（好ましくは７００～１００、特に好ましくは４００～１５０）である、［１］～［１０］の何れか１つに記載の樹脂組成物。
［１２］ 式（b-1）で表される化合物がＮ－ビニルカルバゾール、Ｎ－アリルカルバゾール、Ｎ－（メタ）アクリロイルカルバゾール、及びＮ－（ビニルベンジル）カルバゾールから選択される少なくとも１種の化合物である、［１］～［１１］の何れか１つに記載の樹脂組成物。
［１３］ 式（b-2）中のＬが二価の炭化水素基（好ましくは、Ｃ1-18アルキレン基、Ｃ2-8アルケニレン基、Ｃ6-10のアリーレン基、及びこれらが単結合を介して連結した基から選択される基）、カルボニル基、エーテル結合、チオエーテル結合、エステル結合、アミド結合、カーボネート結合、及びこれらが複数個連結した基から選択される基である、［１］～［１２］の何れか１つに記載の樹脂組成物。
［１４］ 式（b-2）で表される化合物の分子量が１０００～７０（好ましくは７００～１００、特に好ましくは４００～１５０）である、［１］～［１３］の何れか１つに記載の樹脂組成物。
［１５］ 式（b-2）で表される化合物が、式（b-2-1）で表される化合物である、［１］～［１４］の何れか１つに記載の樹脂組成物。
［１６］ 化合物（Ａ）と化合物（Ｂ）と光カチオン重合開始剤（Ｃ）以外の化合物の含有量が樹脂組成物全量の４０重量％以下（好ましくは２０重量％以下、特に好ましくは１０重量％以下）である、［１］～［１５］の何れか１つに記載の樹脂組成物。
［１７］ 化合物（Ａ）と化合物（Ｂ）と光カチオン重合開始剤（Ｃ）の合計含有量が樹脂組成物全量の６０重量％以上（好ましくは８０重量％以上、特に好ましくは９０重量％以上）である、［１］～［１６］の何れか１つに記載の樹脂組成物。
［１８］ 重量平均分子量が１０００超（好ましくは５０００超、特に好ましくは１００００超）の高分子化合物の含有量が５重量％以下（好ましくは３重量％以下、特に好ましくは１重量％以下）である、［１］～［１７］の何れか１つに記載の樹脂組成物。
［１９］ 溶解度パラメーター（２５℃におけるＳＰ値；Fedorsの式で算出される値）が８．５以上の化合物の含有量が５重量％以下（好ましくは３重量％以下、特に好ましくは１重量％以下）である、［１］～［１８］の何れか１つに記載の樹脂組成物。
［２０］ 重量平均分子量が１０００超（好ましくは５０００超、特に好ましくは１００００超）の高分子化合物と溶解度パラメーター（２５℃におけるＳＰ値；Fedorsの式で算出される値）が８．５以上の化合物の合計含有量が５重量％以下（好ましくは３重量％以下、特に好ましくは１重量％以下）である、［１］～［１９］の何れか１つに記載の樹脂組成物。
［２１］ 化合物（Ａ）と化合物（Ｂ）の含有量の比（前者：後者（重量比））が６０：４０～９５：５（好ましくは６５：３５～９０：１０、特に好ましくは７０：３０～８５：１５）であり、化合物（Ａ）と化合物（Ｂ）の合計含有量が、樹脂組成物に含まれる硬化性化合物全量の５０重量％以上（好ましくは６０重量％以上、より好ましくは７０重量％以上、特に好ましくは８０重量％以上、最も好ましくは９０重量％以上）である、［１］～［２０］の何れか１つに記載の樹脂組成物。
［２２］ 化合物（Ａ）の含有量が樹脂組成物に含まれる硬化性化合物全量（１００重量％）の４５～９５重量％（好ましくは６０～９５重量％、より好ましくは６５～９０重量％、特に好ましくは７０～８５重量％）である、［１］～［２１］の何れか１つに記載の樹脂組成物。
［２３］ 化合物（Ｂ）の含有量が樹脂組成物に含まれる硬化性化合物全量（１００重量％）の５～４０重量％（好ましくは１０～３５重量％、特に好ましくは１５～３０重量％）である、［１］～［２２］の何れか１つに記載の樹脂組成物。
［２４］ 光カチオン重合開始剤（Ｃ）の含有量が樹脂組成物に含まれる硬化性化合物１００重量部に対して０．０１～１５重量部（好ましくは０．０１～１０重量部、特に好ましくは０．０５～５重量部、最も好ましくは０．１～３重量部）である、［１］～［２３］の何れか１つに記載の樹脂組成物。
［２５］ ２５℃における、紫外線未照射の場合の粘度が１０ｍＰａ・ｓ以上、３０ｍＰａ・ｓ未満（好ましくは１５～２５ｍＰａ・ｓ）である、［１］～［２４］の何れか１つに記載の樹脂組成物。
［２６］ 紫外線照射（照射量：１５００ｍＪ／ｃｍ2）直後の、２５℃における粘度が３０～２０００ｍＰａ・ｓ（好ましくは３０～１０００ｍＰａ・ｓ）である、［１］～［２５］の何れか１つに記載の樹脂組成物。
［２７］ 紫外線照射（照射量：１５００ｍＪ／ｃｍ2）後３０分の、２５℃における粘度が３０～２５００ｍＰａ・ｓ（好ましくは３０～１５００ｍＰａ・ｓ）である、［１］～［２６］の何れか１つに記載の樹脂組成物。
［２８］ 紫外線照射直後から紫外線照射後３０分の間の粘度の上昇度（紫外線照射後３０分の粘度／紫外線照射直後の粘度）が１．３０以下（好ましくは１．２０以下）である、［１］～［２７］の何れか１つに記載の樹脂組成物。
［２９］ 有機エレクトロルミネッセンス素子封止剤である、［１］～［２８］の何れか１つに記載の樹脂組成物。
［３０］ 下記工程１及び２を経て有機エレクトロルミネッセンス素子を封止することを特徴とする有機エレクトロルミネッセンスデバイスの製造方法。
工程１：［１］～［２９］の何れか１つに記載の樹脂組成物からなる塗膜に、紫外線照射を施す
工程２：有機エレクトロルミネッセンス素子を設置した基板の素子設置面に、工程１を経て得られた紫外線照射後の塗膜を貼り合わせて加熱処理を施す
［３１］ ［１］～［２９］の何れか１つに記載の樹脂組成物の硬化物で素子が封止された構成を有する有機エレクトロルミネッセンスデバイス。
［３２］ 硬化物が、２５℃における波長５８９．３ｎｍの光に対する屈折率が１．６５以上（好ましくは１．６８以上）である硬化物である、［３１］に記載の有機エレクトロルミネッセンスデバイス。
［３３］ 硬化物が、厚さ１００μｍの硬化物の透湿量（ｇ／ｍ2・ｄａｙ・ａｔｍ）が１００以下（好ましくは５０以下、特に好ましくは３５以下、最も好ましくは２５以下）である硬化物である、［３１］又は［３２］に記載の有機エレクトロルミネッセンスデバイス。
［３４］ 硬化物が、６０ｍｇの硬化物のアウトガス量が１０００ｐｐｍ以下（好ましくは２００ｐｐｍ以下、特に好ましくは１００ｐｐｍ以下）である硬化物である、［３１］～［３３］の何れか１つに記載の有機エレクトロルミネッセンスデバイス。 That is, the present invention relates to the following.
[1] At least one selected from the compound (A) represented by the formula (a), the compound represented by the formula (b-1), and the compound represented by the following formula (b-2) The resin composition containing a compound (B) and a photocationic polymerization initiator (C).
[2] The resin composition according to [1], wherein R a in the formula (a) is a cationically polymerizable group.
[3] The resin composition according to [1], wherein R a in the formula (a) is a group selected from a vinyl group, an allyl group, an epoxy group, a glycidyl group, and an oxetanyl group.
[4] The resin composition according to [1], wherein R a in the formula (a) is a vinyl group or an allyl group.
[5] A group in which R c in formula (a) is selected from a divalent hydrocarbon group, a carbonyl group, an ether bond, a thioether bond, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these are linked. The resin composition according to any one of [1] to [4], wherein
[6] The resin composition according to any one of [1] to [5], wherein the molecular weight of the compound (A) is 1000 or less (preferably 700 or less, most preferably 500 or less).
[7] The resin composition according to any one of [1] to [5], wherein the molecular weight of the compound (A) is 302 to 1000 (preferably 302 to 700, most preferably 302 to 500).
[8] The resin composition according to any one of [1] to [7], wherein the compound (A) is a compound represented by the formula (a ′).
[9] Any one of [1] to [7], wherein the compound (A) is at least one compound selected from the compounds represented by the formulas (a′-1) to (a′-12) The resin composition described in 1.
[10] Y in formula (b-1) is a divalent hydrocarbon group (preferably a C 1-18 alkylene group, a C 2-8 alkenylene group, a C 6-10 arylene group, and a single bond thereof. [1] to [9] which are groups selected from a group selected from a group linked via a carbonyl group, an ether bond, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these groups are linked. ] The resin composition as described in any one of.
[11] In any one of [1] to [10], the compound represented by the formula (b-1) has a molecular weight of 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). The resin composition as described.
[12] At least one compound in which the compound represented by the formula (b-1) is selected from N-vinylcarbazole, N-allylcarbazole, N- (meth) acryloylcarbazole, and N- (vinylbenzyl) carbazole The resin composition according to any one of [1] to [11].
[13] L in the formula (b-2) is a divalent hydrocarbon group (preferably a C 1-18 alkylene group, a C 2-8 alkenylene group, a C 6-10 arylene group, or a single bond thereof) A group selected from a group linked through a carbonyl group, an ether bond, a thioether bond, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these are linked, [1] -The resin composition as described in any one of [12].
[14] In any one of [1] to [13], the molecular weight of the compound represented by the formula (b-2) is 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). The resin composition as described.
[15] The resin composition according to any one of [1] to [14], wherein the compound represented by the formula (b-2) is a compound represented by the formula (b-2-1) .
[16] The content of the compound other than the compound (A), the compound (B), and the photocationic polymerization initiator (C) is 40% by weight or less (preferably 20% by weight or less, particularly preferably 10% by weight) of the total amount of the resin composition. % Or less), the resin composition according to any one of [1] to [15].
[17] The total content of the compound (A), the compound (B) and the photocationic polymerization initiator (C) is 60% by weight or more (preferably 80% by weight or more, particularly preferably 90% by weight or more) of the total amount of the resin composition. The resin composition according to any one of [1] to [16].
[18] The content of the polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5000, particularly preferably more than 10,000) is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight or less). The resin composition according to any one of [1] to [17].
[19] The content of a compound having a solubility parameter (SP value at 25 ° C .; a value calculated by the formula of Fedors) of 8.5 or more is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight) The resin composition according to any one of [1] to [18], wherein:
[20] A polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5000, particularly preferably more than 10,000) and a solubility parameter (SP value at 25 ° C .; a value calculated by the Fedors formula) is 8.5 or more. The resin composition according to any one of [1] to [19], wherein the total content of the compounds is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight or less).
[21] The content ratio of the compound (A) to the compound (B) (the former: the latter (weight ratio)) is 60:40 to 95: 5 (preferably 65:35 to 90:10, particularly preferably 70: 30 to 85:15), and the total content of the compound (A) and the compound (B) is 50% by weight or more (preferably 60% by weight or more, more preferably, the total amount of the curable compound contained in the resin composition). The resin composition according to any one of [1] to [20], which is 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.
[22] The content of the compound (A) is 45 to 95% (preferably 60 to 95% by weight, more preferably 65 to 90% by weight) of the total amount (100% by weight) of the curable compound contained in the resin composition. The resin composition according to any one of [1] to [21], particularly preferably 70 to 85% by weight).
[23] The content of the compound (B) is 5 to 40% by weight (preferably 10 to 35% by weight, particularly preferably 15 to 30% by weight) of the total amount (100% by weight) of the curable compound contained in the resin composition. The resin composition according to any one of [1] to [22].
[24] The content of the photocationic polymerization initiator (C) is 0.01 to 15 parts by weight (preferably 0.01 to 10 parts by weight, particularly preferably 100 parts by weight of the curable compound contained in the resin composition). Is 0.05 to 5 parts by weight, and most preferably 0.1 to 3 parts by weight). The resin composition according to any one of [1] to [23].
[25] The viscosity according to any one of [1] to [24], in which the viscosity at 25 ° C. when not irradiated with ultraviolet rays is 10 mPa · s or more and less than 30 mPa · s (preferably 15 to 25 mPa · s). Resin composition.
[26] Any one of [1] to [25], wherein the viscosity at 25 ° C. immediately after ultraviolet irradiation (irradiation amount: 1500 mJ / cm 2 ) is 30 to 2000 mPa · s (preferably 30 to 1000 mPa · s). The resin composition as described in one.
[27] Any of [1] to [26], wherein the viscosity at 25 ° C. is 30 to 2500 mPa · s (preferably 30 to 1500 mPa · s) 30 minutes after ultraviolet irradiation (irradiation amount: 1500 mJ / cm 2 ). The resin composition as described in any one.
[28] The degree of increase in viscosity during 30 minutes after ultraviolet irradiation (viscosity for 30 minutes after ultraviolet irradiation / viscosity immediately after ultraviolet irradiation) is 1.30 or less (preferably 1.20 or less). [1] The resin composition according to any one of [27].
[29] The resin composition according to any one of [1] to [28], which is an organic electroluminescent device sealant.
[30] A method for producing an organic electroluminescent device, wherein the organic electroluminescent element is sealed through the following steps 1 and 2.
Step 1: UV coating is applied to the coating film made of the resin composition according to any one of [1] to [29] Step 2:Step 1 is applied to the element mounting surface of the substrate on which the organic electroluminescence element is mounted. [31] The device was sealed with a cured product of the resin composition as described in any one of [1] to [29], after the ultraviolet-irradiated coating film obtained through the above was pasted and heat-treated An organic electroluminescence device having a configuration.
[32] The organic electroluminescent device according to [31], wherein the cured product is a cured product having a refractive index of 1.65 or more (preferably 1.68 or more) with respect to light having a wavelength of 589.3 nm at 25 ° C.
[33] The moisture permeability (g / m 2 · day · atm) of the cured product having a thickness of 100 μm is 100 or less (preferably 50 or less, particularly preferably 35 or less, most preferably 25 or less). The organic electroluminescence device according to [31] or [32], which is a cured product.
[34] The cured product according to any one of [31] to [33], wherein the cured product is a cured product in which an outgas amount of 60 mg of the cured product is 1000 ppm or less (preferably 200 ppm or less, particularly preferably 100 ppm or less). Organic electroluminescence device.
［１］ 式（ａ）で表される化合物（Ａ）と、式（b-1）で表される化合物、及び下記式（b-2）で表される化合物から選択される少なくとも１種の化合物（Ｂ）と、光カチオン重合開始剤（Ｃ）を含む樹脂組成物。
［２］ 式（ａ）中のＲaがカチオン重合性基である、［１］に記載の樹脂組成物。
［３］ 式（ａ）中のＲaがビニル基、アリル基、エポキシ基、グリシジル基、及びオキセタニル基から選択される基である、［１］に記載の樹脂組成物。
［４］ 式（ａ）中のＲaが、ビニル基又はアリル基である、［１］に記載の樹脂組成物。
［５］ 式（ａ）中のＲcが二価の炭化水素基、カルボニル基、エーテル結合、チオエーテル結合、エステル結合、アミド結合、カーボネート結合、及びこれらが複数個連結した基から選択される基である、［１］～［４］の何れか１つに記載の樹脂組成物。
［６］ 化合物（Ａ）の分子量が１０００以下（好ましくは７００以下、最も好ましくは５００以下）である、［１］～［５］の何れか１つに記載の樹脂組成物。
［７］ 化合物（Ａ）の分子量が３０２～１０００（好ましくは３０２～７００、最も好ましくは３０２～５００）である、［１］～［５］の何れか１つに記載の樹脂組成物。
［８］ 化合物（Ａ）が式（ａ’）で表される化合物である、［１］～［７］の何れか１つに記載の樹脂組成物。
［９］ 化合物（Ａ）が式（a'-1）～（a'-12）で示される化合物から選択される少なくとも１種の化合物である、［１］～［７］の何れか１つに記載の樹脂組成物。
［１０］ 式（b-1）中のＹが二価の炭化水素基（好ましくは、Ｃ1-18アルキレン基、Ｃ2-8アルケニレン基、Ｃ6-10のアリーレン基、及びこれらが単結合を介して連結した基から選択される基）、カルボニル基、エーテル結合、エステル結合、アミド結合、カーボネート結合、及びこれらが複数個連結した基から選択される基である、［１］～［９］の何れか１つに記載の樹脂組成物。
［１１］ 式（b-1）で表される化合物の分子量が１０００～７０（好ましくは７００～１００、特に好ましくは４００～１５０）である、［１］～［１０］の何れか１つに記載の樹脂組成物。
［１２］ 式（b-1）で表される化合物がＮ－ビニルカルバゾール、Ｎ－アリルカルバゾール、Ｎ－（メタ）アクリロイルカルバゾール、及びＮ－（ビニルベンジル）カルバゾールから選択される少なくとも１種の化合物である、［１］～［１１］の何れか１つに記載の樹脂組成物。
［１３］ 式（b-2）中のＬが二価の炭化水素基（好ましくは、Ｃ1-18アルキレン基、Ｃ2-8アルケニレン基、Ｃ6-10のアリーレン基、及びこれらが単結合を介して連結した基から選択される基）、カルボニル基、エーテル結合、チオエーテル結合、エステル結合、アミド結合、カーボネート結合、及びこれらが複数個連結した基から選択される基である、［１］～［１２］の何れか１つに記載の樹脂組成物。
［１４］ 式（b-2）で表される化合物の分子量が１０００～７０（好ましくは７００～１００、特に好ましくは４００～１５０）である、［１］～［１３］の何れか１つに記載の樹脂組成物。
［１５］ 式（b-2）で表される化合物が、式（b-2-1）で表される化合物である、［１］～［１４］の何れか１つに記載の樹脂組成物。
［１６］ 化合物（Ａ）と化合物（Ｂ）と光カチオン重合開始剤（Ｃ）以外の化合物の含有量が樹脂組成物全量の４０重量％以下（好ましくは２０重量％以下、特に好ましくは１０重量％以下）である、［１］～［１５］の何れか１つに記載の樹脂組成物。
［１７］ 化合物（Ａ）と化合物（Ｂ）と光カチオン重合開始剤（Ｃ）の合計含有量が樹脂組成物全量の６０重量％以上（好ましくは８０重量％以上、特に好ましくは９０重量％以上）である、［１］～［１６］の何れか１つに記載の樹脂組成物。
［１８］ 重量平均分子量が１０００超（好ましくは５０００超、特に好ましくは１００００超）の高分子化合物の含有量が５重量％以下（好ましくは３重量％以下、特に好ましくは１重量％以下）である、［１］～［１７］の何れか１つに記載の樹脂組成物。
［１９］ 溶解度パラメーター（２５℃におけるＳＰ値；Fedorsの式で算出される値）が８．５以上の化合物の含有量が５重量％以下（好ましくは３重量％以下、特に好ましくは１重量％以下）である、［１］～［１８］の何れか１つに記載の樹脂組成物。
［２０］ 重量平均分子量が１０００超（好ましくは５０００超、特に好ましくは１００００超）の高分子化合物と溶解度パラメーター（２５℃におけるＳＰ値；Fedorsの式で算出される値）が８．５以上の化合物の合計含有量が５重量％以下（好ましくは３重量％以下、特に好ましくは１重量％以下）である、［１］～［１９］の何れか１つに記載の樹脂組成物。
［２１］ 化合物（Ａ）と化合物（Ｂ）の含有量の比（前者：後者（重量比））が６０：４０～９５：５（好ましくは６５：３５～９０：１０、特に好ましくは７０：３０～８５：１５）であり、化合物（Ａ）と化合物（Ｂ）の合計含有量が、樹脂組成物に含まれる硬化性化合物全量の５０重量％以上（好ましくは６０重量％以上、より好ましくは７０重量％以上、特に好ましくは８０重量％以上、最も好ましくは９０重量％以上）である、［１］～［２０］の何れか１つに記載の樹脂組成物。
［２２］ 化合物（Ａ）の含有量が樹脂組成物に含まれる硬化性化合物全量（１００重量％）の４５～９５重量％（好ましくは６０～９５重量％、より好ましくは６５～９０重量％、特に好ましくは７０～８５重量％）である、［１］～［２１］の何れか１つに記載の樹脂組成物。
［２３］ 化合物（Ｂ）の含有量が樹脂組成物に含まれる硬化性化合物全量（１００重量％）の５～４０重量％（好ましくは１０～３５重量％、特に好ましくは１５～３０重量％）である、［１］～［２２］の何れか１つに記載の樹脂組成物。
［２４］ 光カチオン重合開始剤（Ｃ）の含有量が樹脂組成物に含まれる硬化性化合物１００重量部に対して０．０１～１５重量部（好ましくは０．０１～１０重量部、特に好ましくは０．０５～５重量部、最も好ましくは０．１～３重量部）である、［１］～［２３］の何れか１つに記載の樹脂組成物。
［２５］ ２５℃における、紫外線未照射の場合の粘度が１０ｍＰａ・ｓ以上、３０ｍＰａ・ｓ未満（好ましくは１５～２５ｍＰａ・ｓ）である、［１］～［２４］の何れか１つに記載の樹脂組成物。
［２６］ 紫外線照射（照射量：１５００ｍＪ／ｃｍ2）直後の、２５℃における粘度が３０～２０００ｍＰａ・ｓ（好ましくは３０～１０００ｍＰａ・ｓ）である、［１］～［２５］の何れか１つに記載の樹脂組成物。
［２７］ 紫外線照射（照射量：１５００ｍＪ／ｃｍ2）後３０分の、２５℃における粘度が３０～２５００ｍＰａ・ｓ（好ましくは３０～１５００ｍＰａ・ｓ）である、［１］～［２６］の何れか１つに記載の樹脂組成物。
［２８］ 紫外線照射直後から紫外線照射後３０分の間の粘度の上昇度（紫外線照射後３０分の粘度／紫外線照射直後の粘度）が１．３０以下（好ましくは１．２０以下）である、［１］～［２７］の何れか１つに記載の樹脂組成物。
［２９］ 有機エレクトロルミネッセンス素子封止剤である、［１］～［２８］の何れか１つに記載の樹脂組成物。
［３０］ 下記工程１及び２を経て有機エレクトロルミネッセンス素子を封止することを特徴とする有機エレクトロルミネッセンスデバイスの製造方法。
工程１：［１］～［２９］の何れか１つに記載の樹脂組成物からなる塗膜に、紫外線照射を施す
工程２：有機エレクトロルミネッセンス素子を設置した基板の素子設置面に、工程１を経て得られた紫外線照射後の塗膜を貼り合わせて加熱処理を施す
［３１］ ［１］～［２９］の何れか１つに記載の樹脂組成物の硬化物で素子が封止された構成を有する有機エレクトロルミネッセンスデバイス。
［３２］ 硬化物が、２５℃における波長５８９．３ｎｍの光に対する屈折率が１．６５以上（好ましくは１．６８以上）である硬化物である、［３１］に記載の有機エレクトロルミネッセンスデバイス。
［３３］ 硬化物が、厚さ１００μｍの硬化物の透湿量（ｇ／ｍ2・ｄａｙ・ａｔｍ）が１００以下（好ましくは５０以下、特に好ましくは３５以下、最も好ましくは２５以下）である硬化物である、［３１］又は［３２］に記載の有機エレクトロルミネッセンスデバイス。
［３４］ 硬化物が、６０ｍｇの硬化物のアウトガス量が１０００ｐｐｍ以下（好ましくは２００ｐｐｍ以下、特に好ましくは１００ｐｐｍ以下）である硬化物である、［３１］～［３３］の何れか１つに記載の有機エレクトロルミネッセンスデバイス。 That is, the present invention relates to the following.
[1] At least one selected from the compound (A) represented by the formula (a), the compound represented by the formula (b-1), and the compound represented by the following formula (b-2) The resin composition containing a compound (B) and a photocationic polymerization initiator (C).
[2] The resin composition according to [1], wherein R a in the formula (a) is a cationically polymerizable group.
[3] The resin composition according to [1], wherein R a in the formula (a) is a group selected from a vinyl group, an allyl group, an epoxy group, a glycidyl group, and an oxetanyl group.
[4] The resin composition according to [1], wherein R a in the formula (a) is a vinyl group or an allyl group.
[5] A group in which R c in formula (a) is selected from a divalent hydrocarbon group, a carbonyl group, an ether bond, a thioether bond, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these are linked. The resin composition according to any one of [1] to [4], wherein
[6] The resin composition according to any one of [1] to [5], wherein the molecular weight of the compound (A) is 1000 or less (preferably 700 or less, most preferably 500 or less).
[7] The resin composition according to any one of [1] to [5], wherein the molecular weight of the compound (A) is 302 to 1000 (preferably 302 to 700, most preferably 302 to 500).
[8] The resin composition according to any one of [1] to [7], wherein the compound (A) is a compound represented by the formula (a ′).
[9] Any one of [1] to [7], wherein the compound (A) is at least one compound selected from the compounds represented by the formulas (a′-1) to (a′-12) The resin composition described in 1.
[10] Y in formula (b-1) is a divalent hydrocarbon group (preferably a C 1-18 alkylene group, a C 2-8 alkenylene group, a C 6-10 arylene group, and a single bond thereof. [1] to [9] which are groups selected from a group selected from a group linked via a carbonyl group, an ether bond, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these groups are linked. ] The resin composition as described in any one of.
[11] In any one of [1] to [10], the compound represented by the formula (b-1) has a molecular weight of 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). The resin composition as described.
[12] At least one compound in which the compound represented by the formula (b-1) is selected from N-vinylcarbazole, N-allylcarbazole, N- (meth) acryloylcarbazole, and N- (vinylbenzyl) carbazole The resin composition according to any one of [1] to [11].
[13] L in the formula (b-2) is a divalent hydrocarbon group (preferably a C 1-18 alkylene group, a C 2-8 alkenylene group, a C 6-10 arylene group, or a single bond thereof) A group selected from a group linked through a carbonyl group, an ether bond, a thioether bond, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these are linked, [1] -The resin composition as described in any one of [12].
[14] In any one of [1] to [13], the molecular weight of the compound represented by the formula (b-2) is 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). The resin composition as described.
[15] The resin composition according to any one of [1] to [14], wherein the compound represented by the formula (b-2) is a compound represented by the formula (b-2-1) .
[16] The content of the compound other than the compound (A), the compound (B), and the photocationic polymerization initiator (C) is 40% by weight or less (preferably 20% by weight or less, particularly preferably 10% by weight) of the total amount of the resin composition. % Or less), the resin composition according to any one of [1] to [15].
[17] The total content of the compound (A), the compound (B) and the photocationic polymerization initiator (C) is 60% by weight or more (preferably 80% by weight or more, particularly preferably 90% by weight or more) of the total amount of the resin composition. The resin composition according to any one of [1] to [16].
[18] The content of the polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5000, particularly preferably more than 10,000) is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight or less). The resin composition according to any one of [1] to [17].
[19] The content of a compound having a solubility parameter (SP value at 25 ° C .; a value calculated by the formula of Fedors) of 8.5 or more is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight) The resin composition according to any one of [1] to [18], wherein:
[20] A polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5000, particularly preferably more than 10,000) and a solubility parameter (SP value at 25 ° C .; a value calculated by the Fedors formula) is 8.5 or more. The resin composition according to any one of [1] to [19], wherein the total content of the compounds is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight or less).
[21] The content ratio of the compound (A) to the compound (B) (the former: the latter (weight ratio)) is 60:40 to 95: 5 (preferably 65:35 to 90:10, particularly preferably 70: 30 to 85:15), and the total content of the compound (A) and the compound (B) is 50% by weight or more (preferably 60% by weight or more, more preferably, the total amount of the curable compound contained in the resin composition). The resin composition according to any one of [1] to [20], which is 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.
[22] The content of the compound (A) is 45 to 95% (preferably 60 to 95% by weight, more preferably 65 to 90% by weight) of the total amount (100% by weight) of the curable compound contained in the resin composition. The resin composition according to any one of [1] to [21], particularly preferably 70 to 85% by weight).
[23] The content of the compound (B) is 5 to 40% by weight (preferably 10 to 35% by weight, particularly preferably 15 to 30% by weight) of the total amount (100% by weight) of the curable compound contained in the resin composition. The resin composition according to any one of [1] to [22].
[24] The content of the photocationic polymerization initiator (C) is 0.01 to 15 parts by weight (preferably 0.01 to 10 parts by weight, particularly preferably 100 parts by weight of the curable compound contained in the resin composition). Is 0.05 to 5 parts by weight, and most preferably 0.1 to 3 parts by weight). The resin composition according to any one of [1] to [23].
[25] The viscosity according to any one of [1] to [24], in which the viscosity at 25 ° C. when not irradiated with ultraviolet rays is 10 mPa · s or more and less than 30 mPa · s (preferably 15 to 25 mPa · s). Resin composition.
[26] Any one of [1] to [25], wherein the viscosity at 25 ° C. immediately after ultraviolet irradiation (irradiation amount: 1500 mJ / cm 2 ) is 30 to 2000 mPa · s (preferably 30 to 1000 mPa · s). The resin composition as described in one.
[27] Any of [1] to [26], wherein the viscosity at 25 ° C. is 30 to 2500 mPa · s (preferably 30 to 1500 mPa · s) 30 minutes after ultraviolet irradiation (irradiation amount: 1500 mJ / cm 2 ). The resin composition as described in any one.
[28] The degree of increase in viscosity during 30 minutes after ultraviolet irradiation (viscosity for 30 minutes after ultraviolet irradiation / viscosity immediately after ultraviolet irradiation) is 1.30 or less (preferably 1.20 or less). [1] The resin composition according to any one of [27].
[29] The resin composition according to any one of [1] to [28], which is an organic electroluminescent device sealant.
[30] A method for producing an organic electroluminescent device, wherein the organic electroluminescent element is sealed through the following
Step 1: UV coating is applied to the coating film made of the resin composition according to any one of [1] to [29] Step 2:
[32] The organic electroluminescent device according to [31], wherein the cured product is a cured product having a refractive index of 1.65 or more (preferably 1.68 or more) with respect to light having a wavelength of 589.3 nm at 25 ° C.
[33] The moisture permeability (g / m 2 · day · atm) of the cured product having a thickness of 100 μm is 100 or less (preferably 50 or less, particularly preferably 35 or less, most preferably 25 or less). The organic electroluminescence device according to [31] or [32], which is a cured product.
[34] The cured product according to any one of [31] to [33], wherein the cured product is a cured product in which an outgas amount of 60 mg of the cured product is 1000 ppm or less (preferably 200 ppm or less, particularly preferably 100 ppm or less). Organic electroluminescence device.
本発明の樹脂組成物は上記構成を有するため、紫外線を照射するまでは低粘度で流動性に優れ、液体定量吐出装置等を使用して良好に吐出することができる。また、工業用洗浄剤として用いられるアセトンに対して優れた溶解性を示すため、アセトンを用いて前記装置等内部を容易に洗浄することができる。更に、紫外線を照射することにより流動性を低下させることができ、例えば、ダムアンドフィル工法により有機ＥＬ素子を封止する際に、本発明の樹脂組成物をフィル材として使用する場合は、ダム内に吐出した後に紫外線を照射することにより、ダムからの流出を防止することができる。また、紫外線を照射しても加熱処理を施すまでは半硬化状態のまま硬化反応の進行を停止させることができ、加熱処理を施すタイミングを調整することで、硬化反応の再開時期を任意に設定することができる。そして、紫外線照射後に加熱処理を施すことで速やかに硬化して、高屈折率、低透湿性、及び低アウトガス性を有する硬化物を形成することができる。
そのため、本発明の樹脂組成物に紫外線を照射した後に、有機ＥＬ素子を備えた基板に貼り合わせ、貼り合わせ後に加熱処理を施すことにより、ダムからの流出を抑制しつつ、且つ貼り合わせ困難となる事態を生じることなく、貼り合わせ作業を行うことができ、有機ＥＬ素子を紫外線に直に曝すことなく、高屈折率、低透湿性、及び低アウトガス性を兼ね備えた硬化物で封止することができる。
このため、本発明の樹脂組成物は、特に、トップ・エミッション型有機ＥＬデバイスの封止剤（特に、フィル材）、ボトム・エミッション型有機ＥＬデバイスの光取り出し層材料、太陽電池材料、レンズ材料等として好ましく使用できる。
特に、本発明の樹脂組成物を封止剤として使用すると、光の取り出し効率に優れ、高効率、高輝度、長寿命を有する有機ＥＬデバイスが得られる。また、本発明の樹脂組成物をレンズ材料として使用すると、高屈折率を有するレンズが得られ、レンズの薄膜化、軽量化が可能であり、当該レンズを含む電子機器のデザイン性を向上することができる。 Since the resin composition of the present invention has the above-described configuration, it is low in viscosity and excellent in fluidity until it is irradiated with ultraviolet rays, and can be discharged satisfactorily using a liquid dispensing apparatus or the like. Moreover, since the solubility which was excellent with respect to acetone used as an industrial cleaning agent is shown, the inside of the said apparatus etc. can be easily wash | cleaned using acetone. Furthermore, the fluidity can be reduced by irradiating with ultraviolet rays. For example, when the resin composition of the present invention is used as a fill material when sealing an organic EL element by a dam and fill method, Outflow from the dam can be prevented by irradiating ultraviolet rays after being discharged into the interior. In addition, the progress of the curing reaction can be stopped in the semi-cured state until the heat treatment is performed even after irradiation with ultraviolet rays, and the timing for restarting the curing reaction can be arbitrarily set by adjusting the timing for performing the heat treatment. can do. And it can harden | cure rapidly by performing heat processing after ultraviolet irradiation, and the hardened | cured material which has a high refractive index, low moisture permeability, and low outgassing property can be formed.
Therefore, after irradiating the resin composition of the present invention with ultraviolet rays, it is bonded to a substrate provided with an organic EL element, and heat treatment is performed after the bonding, thereby suppressing the outflow from the dam and bonding difficult. It is possible to perform the laminating operation without causing a situation to occur, and seal with a cured product having high refractive index, low moisture permeability, and low outgassing property without directly exposing the organic EL element to ultraviolet rays. Can do.
For this reason, the resin composition of the present invention includes, in particular, a sealant (in particular, a fill material) for a top emission type organic EL device, a light extraction layer material for a bottom emission type organic EL device, a solar cell material, and a lens material. Etc. can be preferably used.
In particular, when the resin composition of the present invention is used as a sealant, an organic EL device having excellent light extraction efficiency, high efficiency, high luminance, and long life can be obtained. Further, when the resin composition of the present invention is used as a lens material, a lens having a high refractive index can be obtained, and the lens can be made thinner and lighter, and the design of an electronic device including the lens can be improved. Can do.
そのため、本発明の樹脂組成物に紫外線を照射した後に、有機ＥＬ素子を備えた基板に貼り合わせ、貼り合わせ後に加熱処理を施すことにより、ダムからの流出を抑制しつつ、且つ貼り合わせ困難となる事態を生じることなく、貼り合わせ作業を行うことができ、有機ＥＬ素子を紫外線に直に曝すことなく、高屈折率、低透湿性、及び低アウトガス性を兼ね備えた硬化物で封止することができる。
このため、本発明の樹脂組成物は、特に、トップ・エミッション型有機ＥＬデバイスの封止剤（特に、フィル材）、ボトム・エミッション型有機ＥＬデバイスの光取り出し層材料、太陽電池材料、レンズ材料等として好ましく使用できる。
特に、本発明の樹脂組成物を封止剤として使用すると、光の取り出し効率に優れ、高効率、高輝度、長寿命を有する有機ＥＬデバイスが得られる。また、本発明の樹脂組成物をレンズ材料として使用すると、高屈折率を有するレンズが得られ、レンズの薄膜化、軽量化が可能であり、当該レンズを含む電子機器のデザイン性を向上することができる。 Since the resin composition of the present invention has the above-described configuration, it is low in viscosity and excellent in fluidity until it is irradiated with ultraviolet rays, and can be discharged satisfactorily using a liquid dispensing apparatus or the like. Moreover, since the solubility which was excellent with respect to acetone used as an industrial cleaning agent is shown, the inside of the said apparatus etc. can be easily wash | cleaned using acetone. Furthermore, the fluidity can be reduced by irradiating with ultraviolet rays. For example, when the resin composition of the present invention is used as a fill material when sealing an organic EL element by a dam and fill method, Outflow from the dam can be prevented by irradiating ultraviolet rays after being discharged into the interior. In addition, the progress of the curing reaction can be stopped in the semi-cured state until the heat treatment is performed even after irradiation with ultraviolet rays, and the timing for restarting the curing reaction can be arbitrarily set by adjusting the timing for performing the heat treatment. can do. And it can harden | cure rapidly by performing heat processing after ultraviolet irradiation, and the hardened | cured material which has a high refractive index, low moisture permeability, and low outgassing property can be formed.
Therefore, after irradiating the resin composition of the present invention with ultraviolet rays, it is bonded to a substrate provided with an organic EL element, and heat treatment is performed after the bonding, thereby suppressing the outflow from the dam and bonding difficult. It is possible to perform the laminating operation without causing a situation to occur, and seal with a cured product having high refractive index, low moisture permeability, and low outgassing property without directly exposing the organic EL element to ultraviolet rays. Can do.
For this reason, the resin composition of the present invention includes, in particular, a sealant (in particular, a fill material) for a top emission type organic EL device, a light extraction layer material for a bottom emission type organic EL device, a solar cell material, and a lens material. Etc. can be preferably used.
In particular, when the resin composition of the present invention is used as a sealant, an organic EL device having excellent light extraction efficiency, high efficiency, high luminance, and long life can be obtained. Further, when the resin composition of the present invention is used as a lens material, a lens having a high refractive index can be obtained, and the lens can be made thinner and lighter, and the design of an electronic device including the lens can be improved. Can do.
［化合物（Ａ）］
本発明における化合物（Ａ）は、上記式（ａ）で表される化合物（硬化性化合物）である。上記式（ａ）中の２つのＲaは反応性官能基（重合性官能基）を示す。前記２つのＲaはそれぞれ同一であってもよいし、異なっていてもよい。前記反応性官能基としては、例えば、ビニル基、アリル基、エポキシ基、グリシジル基、オキセタニル基等のカチオン重合性基を挙げることができる。本発明においては、なかでも、ビニル基又はアリル基が好ましい。 [Compound (A)]
The compound (A) in the present invention is a compound (curable compound) represented by the above formula (a). Two R a in the above formula (a) represent a reactive functional group (polymerizable functional group). The two R a may be respectively identical or different. Examples of the reactive functional group include a cationic polymerizable group such as a vinyl group, an allyl group, an epoxy group, a glycidyl group, and an oxetanyl group. In the present invention, among them, a vinyl group or an allyl group is preferable.
本発明における化合物（Ａ）は、上記式（ａ）で表される化合物（硬化性化合物）である。上記式（ａ）中の２つのＲaは反応性官能基（重合性官能基）を示す。前記２つのＲaはそれぞれ同一であってもよいし、異なっていてもよい。前記反応性官能基としては、例えば、ビニル基、アリル基、エポキシ基、グリシジル基、オキセタニル基等のカチオン重合性基を挙げることができる。本発明においては、なかでも、ビニル基又はアリル基が好ましい。 [Compound (A)]
The compound (A) in the present invention is a compound (curable compound) represented by the above formula (a). Two R a in the above formula (a) represent a reactive functional group (polymerizable functional group). The two R a may be respectively identical or different. Examples of the reactive functional group include a cationic polymerizable group such as a vinyl group, an allyl group, an epoxy group, a glycidyl group, and an oxetanyl group. In the present invention, among them, a vinyl group or an allyl group is preferable.
上記式（ａ）中の複数のＲbは、同一又は異なって、ハロゲン原子、アルキル基、ハロアルキル基、アリール基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシアルキル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいスルホ基、ニトロ基、シアノ基、又は保護基で保護されていてもよいアシル基を示す。
A plurality of R b in the formula (a) may be the same or different and may be protected with a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, or a protecting group. A good hydroxyalkyl group, an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protecting group An acyl group which may be protected with
上記Ｒbにおけるハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等を挙げることができる。上記Ｒbにおけるアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のＣ1-10（好ましくはＣ1-5）アルキル基等を挙げることができる。上記Ｒbにおけるハロアルキル基としては、例えば、クロロメチル基、トリフルオロメチル基、トリフルオロエチル基、ペンタフルオロエチル基等のＣ1-10（好ましくはＣ1-5）ハロアルキル基等を挙げることができる。上記Ｒbにおけるアリール基としては、例えば、フェニル基、ナフチル基等を挙げることができる。尚、上記アリール基の芳香環は、例えば、フッ素原子等のハロゲン原子、メチル基等のＣ1-4アルキル基、トリフルオロメチル基等のＣ1-5ハロアルキル基、ヒドロキシル基、メトキシ基等のＣ1-4アルコキシ基、アミノ基、ジアルキルアミノ基、カルボキシル基、メトキシカルボニル基等のＣ1-4アルコキシカルボニル基、ニトロ基、シアノ基、アセチル基等のアシル基（特に、Ｃ1-6脂肪族アシル基）等の置換基を有していてもよい。
Examples of the halogen atom for R b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group in R b include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, hexyl group, heptyl group, octyl group, and nonyl group. And a C 1-10 (preferably C 1-5 ) alkyl group such as a decyl group. Examples of the haloalkyl group for R b include C 1-10 (preferably C 1-5 ) haloalkyl groups such as a chloromethyl group, a trifluoromethyl group, a trifluoroethyl group, and a pentafluoroethyl group. it can. Examples of the aryl group for R b include a phenyl group and a naphthyl group. The aromatic ring of the aryl group includes, for example, a halogen atom such as a fluorine atom, a C 1-4 alkyl group such as a methyl group, a C 1-5 haloalkyl group such as a trifluoromethyl group, a hydroxyl group, and a methoxy group. C 1-4 alkoxy group, an amino group, a dialkylamino group, a carboxyl group, C 1-4 alkoxycarbonyl group such as methoxycarbonyl group, a nitro group, a cyano group, an acyl group such as an acetyl group (in particular, C 1-6 aliphatic Group (s) such as a group acyl group).
上記Ｒbにおけるヒドロキシアルキル基としては、例えば、ヒドロキシメチル基等の、Ｃ1-10アルキル基が有する水素原子の少なくとも１つがヒドロキシル基で置換されたＣ1-10（好ましくはＣ1-5）ヒドロキシアルキル基等を挙げることができる。上記Ｒbにおけるヒドロキシル基の保護基、ヒドロキシアルキル基の保護基としては、有機合成の分野で慣用の保護基［例えば、アルキル基（例えば、メチル基、ｔ－ブチル基等のＣ1-4アルキル基等）；アルケニル基（例えば、アリル基等）；シクロアルキル基（例えば、シクロヘキシル基等）；アリール基（例えば、２，４－ジニトロフェニル基等）；アラルキル基（例えば、ベンジル基等）；置換メチル基（例えば、メトキシメチル基、メチルチオメチル基、ベンジルオキシメチル基、ｔ－ブトキシメチル基、２－メトキシエトキシメチル基等）、置換エチル基（例えば、１－エトキシエチル基等）、テトラヒドロピラニル基、テトラヒドロフラニル基、１－ヒドロキシアルキル基（例えば、１－ヒドロキシエチル基等）等のヒドロキシル基とアセタール又はヘミアセタール基を形成可能な基；アシル基（例えば、ホルミル基、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、ピバロイル基等のＣ1-6脂肪族アシル基；アセトアセチル基；ベンゾイル基等の芳香族アシル基等）；アルコキシカルボニル基（例えば、メトキシカルボニル基等のＣ1-4アルコキシ－カルボニル基等）；アラルキルオキシカルボニル基；置換又は無置換カルバモイル基；置換シリル基（例えば、トリメチルシリル基等）；分子内にヒドロキシル基やヒドロキシメチル基が２以上存在するときには置換基を有していてもよい二価の炭化水素基（例えば、メチリデン基、エチリデン基、イソプロピリデン基、シクロペンチリデン基、シクロヘキシリデン基、ベンジリデン基等）等］を挙げることができる。
Examples of the hydroxyalkyl group for R b include C 1-10 (preferably C 1-5 ) in which at least one hydrogen atom of the C 1-10 alkyl group such as hydroxymethyl group is substituted with a hydroxyl group. A hydroxyalkyl group etc. can be mentioned. As the protecting group for hydroxyl group and hydroxyalkyl group in R b , a protecting group commonly used in the field of organic synthesis [for example, alkyl group (for example, C 1-4 alkyl such as methyl group, t-butyl group, etc.) Alkenyl group (eg, allyl group); cycloalkyl group (eg, cyclohexyl group); aryl group (eg, 2,4-dinitrophenyl group); aralkyl group (eg, benzyl group); A substituted methyl group (eg, methoxymethyl group, methylthiomethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl group, etc.), tetrahydropyrani Hydroxyl groups, tetrahydrofuranyl groups, 1-hydroxyalkyl groups (for example, 1-hydroxyethyl group, etc.) Groups and acetal or hemiacetal group capable of forming group; an acyl group (e.g., formyl group, acetyl group, a propionyl group, a butyryl group, an isobutyryl group, C 1-6 aliphatic acyl group such as pivaloyl group; acetoacetyl group; An aromatic acyl group such as a benzoyl group); an alkoxycarbonyl group (eg, a C 1-4 alkoxy-carbonyl group such as a methoxycarbonyl group); an aralkyloxycarbonyl group; a substituted or unsubstituted carbamoyl group; a substituted silyl group (eg, Dimethyl hydrocarbon group (for example, methylidene group, ethylidene group, isopropylidene group, cyclopropylene group) which may have a substituent when there are two or more hydroxyl groups or hydroxymethyl groups in the molecule. Pentylidene group, cyclohexylidene group, benzylidene group, etc.)] Can do.
上記Ｒbにおけるアミノ基の保護基としては、有機合成の分野で慣用の保護基（例えば、上記ヒドロキシル基の保護基として例示したアルキル基、アラルキル基、アシル基、アルコキシカルボニル基等）を挙げることができる。
Examples of the protecting group for the amino group in R b include protecting groups commonly used in the field of organic synthesis (eg, alkyl groups, aralkyl groups, acyl groups, alkoxycarbonyl groups and the like exemplified as the protecting groups for the hydroxyl group). Can do.
上記Ｒbにおけるカルボキシル基の保護基、スルホ基の保護基としては、有機合成の分野で慣用の保護基［例えば、アルコキシ基（例えば、メトキシ基、エトキシ基、ブトキシ基等のＣ1-6アルコキシ基等）、シクロアルキルオキシ基、アリールオキシ基、アラルキルオキシ基、トリアルキルシリルオキシ基、置換基を有していてもよいアミノ基、ヒドラジノ基、アルコキシカルボニルヒドラジノ基、アラルキルカルボニルヒドラジノ基等］を挙げることができる。
Examples of the protecting group for carboxyl group and sulfo group for R b include protecting groups commonly used in the field of organic synthesis [eg, alkoxy groups (eg, C 1-6 alkoxy such as methoxy group, ethoxy group, butoxy group, etc.). Group, etc.), cycloalkyloxy group, aryloxy group, aralkyloxy group, trialkylsilyloxy group, optionally substituted amino group, hydrazino group, alkoxycarbonylhydrazino group, aralkylcarbonylhydrazino group, etc. ] Can be mentioned.
上記Ｒbにおけるアシル基としては、例えば、ホルミル基、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、ピバロイル基等のＣ1-6脂肪族アシル基；アセトアセチル基；ベンゾイル基等の芳香族アシル基等を挙げることができる。上記アシル基の保護基としては、有機合成の分野で慣用の保護基を使用できる。上記アシル基が保護された形態としては、例えば、アセタール（ヘミアセタールを含む）等を挙げることができる。
Examples of the acyl group in R b include C 1-6 aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, and pivaloyl group; aromatic acyl groups such as acetoacetyl group; Groups and the like. As the protecting group for the acyl group, a protecting group commonly used in the field of organic synthesis can be used. Examples of the form in which the acyl group is protected include acetal (including hemiacetal).
式（ａ）中の１つの芳香環に複数のＲbが結合する場合（すなわち、式（ａ）中のｍが２～４の場合）、前記複数個のＲbから選択される２個以上の基は互いに結合して、芳香環を構成する炭素原子と共に環（例えば、５員の脂環式炭素環、６員の脂環式炭素環、２以上の脂環式炭素環（単環）の縮合環等の脂環式炭素環；５員のラクトン環、６員のラクトン環等のラクトン環等）を形成していてもよい。
When a plurality of R b bonds to one aromatic ring in the formula (a) (that is, when m in the formula (a) is 2 to 4), two or more selected from the plurality of R b Are bonded together to form a ring together with carbon atoms constituting an aromatic ring (for example, a 5-membered alicyclic carbocyclic ring, a 6-membered alicyclic carbocyclic ring, two or more alicyclic carbocyclic rings (monocyclic)). A alicyclic carbocyclic ring such as a condensed ring of the above; a lactone ring such as a 5-membered lactone ring or a 6-membered lactone ring).
上記式（ａ）中のＲcは、単結合又は連結基（１以上の原子を有する二価の基）を示す。前記連結基としては、例えば、二価の炭化水素基、カルボニル基（－ＣＯ－）、エーテル結合（－Ｏ－）、チオエーテル結合（－Ｓ－）、エステル結合（－ＣＯＯ－）、アミド結合（－ＣＯＮＨ－）、カーボネート結合（－ＯＣＯＯ－）、及びこれらが複数個連結した基等を挙げることができる。上記連結基は、水酸基、カルボキシル基等の置換基を有していてもよく、このような連結基としては、例えば、１以上の水酸基を有する二価の炭化水素基等を挙げることができる。
R c in the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond ( -CONH-), carbonate bond (-OCOO-), and a group in which a plurality of these are linked. The linking group may have a substituent such as a hydroxyl group or a carboxyl group, and examples of such a linking group include a divalent hydrocarbon group having one or more hydroxyl groups.
上記二価の炭化水素基としては、炭素数が１～１８の直鎖又は分岐鎖状のアルキレン基、二価の脂環式炭化水素基等を挙げることができる。炭素数が１～１８の直鎖又は分岐鎖状のアルキレン基としては、例えば、メチレン基、メチルメチレン基、ジメチルメチレン基、エチレン基、プロピレン基、トリメチレン基等を挙げることができる。二価の脂環式炭化水素基としては、例えば、１，２－シクロペンチレン基、１，３－シクロペンチレン基、シクロペンチリデン基、１，２－シクロヘキシレン基、１，３－シクロヘキシレン基、１，４－シクロヘキシレン基、シクロヘキシリデン基等のシクロアルキレン基（シクロアルキリデン基を含む）等を挙げることができる。
Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group. Examples include cycloalkylene groups (including cycloalkylidene groups) such as a silene group, 1,4-cyclohexylene group, and cyclohexylidene group.
化合物（Ａ）の分子量は特に限定されないが、化合物（Ｂ）との相溶性の点で、１０００以下が好ましく、特に好ましくは７００以下、最も好ましくは５００以下である。尚、分子量の下限は３０２である。
The molecular weight of the compound (A) is not particularly limited, but is preferably 1000 or less, particularly preferably 700 or less, and most preferably 500 or less in terms of compatibility with the compound (B). The lower limit of the molecular weight is 302.
上記式（ａ）中の複数のｍは、同一又は異なって、０～４の整数を示す。また、ｎ（ｎが付された括弧内の構造単位の繰り返し数）は、０～１０の整数を示す。
In the above formula (a), a plurality of m are the same or different and represent an integer of 0 to 4. N (the number of repeating structural units in parentheses to which n is attached) represents an integer of 0 to 10.
上記式（ａ）中のｎは、なかでも、樹脂組成物の粘度を広い範囲で調整することができる点で０～３が好ましく、特に好ましくは０である。即ち、化合物（Ａ）としては、下記式（ａ’）で表される化合物が特に好ましい。
（式中、Ｒa、Ｒb、ｍは、前記に同じ）
In the above formula (a), n is preferably 0 to 3 and particularly preferably 0 in that the viscosity of the resin composition can be adjusted in a wide range. That is, as the compound (A), a compound represented by the following formula (a ′) is particularly preferable.
(Wherein R a , R b and m are the same as above)
化合物（Ａ）としては、下記式（a'-1）～（a'-12）で示される化合物等を挙げることができる。
Examples of the compound (A) include compounds represented by the following formulas (a′-1) to (a′-12).
化合物（Ａ）は、公知乃至慣用の方法によって製造することができる。例えば、４，４’－チオビスベンゼンチオール等を原料とし、これに塩基の存在下でハロゲン化ビニル、ハロゲン化アリル、（メタ）アクリル酸のハロゲン化物、エピハロヒドリン等を反応させる方法等を挙げることができる。また、式（ａ）中のＲaがビニル基である化合物は、４，４’－チオビスベンゼンチオールとジハロエタンとを反応させ、続いて、脱ハロゲン化水素する方法によっても製造することができる。
Compound (A) can be produced by a known or conventional method. For example, a method in which 4,4′-thiobisbenzenethiol or the like is used as a raw material and reacted with vinyl halide, allyl halide, halide of (meth) acrylic acid, epihalohydrin, etc. in the presence of a base. Can do. A compound in which R a in formula (a) is a vinyl group can also be produced by a method of reacting 4,4′-thiobisbenzenethiol and dihaloethane, followed by dehydrohalogenation. .
化合物（Ａ）は、低粘度でアセトン溶解性に優れる。また、紫外線照射により光カチオン重合開始剤（Ｃ）から発生する酸をトラップすることにより硬化遅延性を発揮する。紫外線を照射後、加熱処理を施すと、化合物（Ａ）はトラップした酸を放出して速やかに硬化し、高屈折率、低透湿性、及び低アウトガス性を有する硬化物を形成することができる。
Compound (A) has low viscosity and excellent acetone solubility. Moreover, the curing delay property is exhibited by trapping the acid generated from the photocationic polymerization initiator (C) by ultraviolet irradiation. When heat treatment is performed after irradiation with ultraviolet rays, the compound (A) releases the trapped acid and quickly cures to form a cured product having a high refractive index, low moisture permeability, and low outgassing properties. .
［化合物（Ｂ）］
本発明における化合物（Ｂ）には、化合物（b-1）、及び化合物（b-2）から選択される少なくとも１種の化合物が含まれる。 [Compound (B)]
The compound (B) in the present invention includes at least one compound selected from the compound (b-1) and the compound (b-2).
本発明における化合物（Ｂ）には、化合物（b-1）、及び化合物（b-2）から選択される少なくとも１種の化合物が含まれる。 [Compound (B)]
The compound (B) in the present invention includes at least one compound selected from the compound (b-1) and the compound (b-2).
（化合物（b-1））
本発明における化合物（b-1）は、下記式（b-1）で表される化合物（カチオン及びラジカル重合性化合物）である。化合物（b-1）は、光カチオン重合開始剤（Ｃ）から発生する酸によって急速に重合反応が進行する。そのため、上記化合物（Ａ）が光カチオン重合開始剤（Ｃ）から発生する酸をトラップするまでのわずかな時間に、重合反応を進行させることができる。また、光カチオン重合開始剤（Ｃ）に紫外線を照射すると、前記光カチオン重合開始剤（Ｃ）は紫外線を吸収して分解してラジカル体を形成し、当該ラジカル体が水素を引き抜くことで酸を発生するものであるが、化合物（b-1）は、前記ラジカル体とも反応して重合反応を進行させることができる。そのため、光カチオン重合開始剤（Ｃ）から発生する酸をトラップする作用を有する上記化合物（Ａ）との共存下でも、ある程度重合反応を進行させることができ、本発明の樹脂組成物を半硬化状態へと導くことができる。
（式中、Ｙは単結合又は連結基を示し、Ｒ1は水素原子又はメチル基を示す）
(Compound (b-1))
The compound (b-1) in the present invention is a compound (cation and radical polymerizable compound) represented by the following formula (b-1). The compound (b-1) undergoes a rapid polymerization reaction by the acid generated from the photocationic polymerization initiator (C). Therefore, the polymerization reaction can be allowed to proceed in a short time until the compound (A) traps the acid generated from the photocationic polymerization initiator (C). Further, when the photocationic polymerization initiator (C) is irradiated with ultraviolet rays, the photocationic polymerization initiator (C) absorbs the ultraviolet rays and decomposes to form a radical body, and the radical body extracts hydrogen to remove the acid. However, the compound (b-1) can also react with the radical body to cause a polymerization reaction to proceed. Therefore, the polymerization reaction can proceed to some extent even in the presence of the compound (A) having an action of trapping an acid generated from the photocationic polymerization initiator (C), and the resin composition of the present invention is semi-cured. Can lead to a state.
(Wherein Y represents a single bond or a linking group, and R 1 represents a hydrogen atom or a methyl group)
本発明における化合物（b-1）は、下記式（b-1）で表される化合物（カチオン及びラジカル重合性化合物）である。化合物（b-1）は、光カチオン重合開始剤（Ｃ）から発生する酸によって急速に重合反応が進行する。そのため、上記化合物（Ａ）が光カチオン重合開始剤（Ｃ）から発生する酸をトラップするまでのわずかな時間に、重合反応を進行させることができる。また、光カチオン重合開始剤（Ｃ）に紫外線を照射すると、前記光カチオン重合開始剤（Ｃ）は紫外線を吸収して分解してラジカル体を形成し、当該ラジカル体が水素を引き抜くことで酸を発生するものであるが、化合物（b-1）は、前記ラジカル体とも反応して重合反応を進行させることができる。そのため、光カチオン重合開始剤（Ｃ）から発生する酸をトラップする作用を有する上記化合物（Ａ）との共存下でも、ある程度重合反応を進行させることができ、本発明の樹脂組成物を半硬化状態へと導くことができる。
The compound (b-1) in the present invention is a compound (cation and radical polymerizable compound) represented by the following formula (b-1). The compound (b-1) undergoes a rapid polymerization reaction by the acid generated from the photocationic polymerization initiator (C). Therefore, the polymerization reaction can be allowed to proceed in a short time until the compound (A) traps the acid generated from the photocationic polymerization initiator (C). Further, when the photocationic polymerization initiator (C) is irradiated with ultraviolet rays, the photocationic polymerization initiator (C) absorbs the ultraviolet rays and decomposes to form a radical body, and the radical body extracts hydrogen to remove the acid. However, the compound (b-1) can also react with the radical body to cause a polymerization reaction to proceed. Therefore, the polymerization reaction can proceed to some extent even in the presence of the compound (A) having an action of trapping an acid generated from the photocationic polymerization initiator (C), and the resin composition of the present invention is semi-cured. Can lead to a state.
上記式中、Ｙは単結合又は連結基を示す。前記連結基としては、例えば、二価の炭化水素基、カルボニル基（－ＣＯ－）、エーテル結合（－Ｏ－）、エステル結合（－ＣＯＯ－）、アミド結合（－ＣＯＮＨ－）、カーボネート結合（－ＯＣＯＯ－）、及びこれらが複数個連結した基等を挙げることができる。前記二価の炭化水素基としては、例えば、炭素数が１～１８の直鎖又は分岐鎖状のアルキレン基；ビニレン基、プロペニレン基、１－ブテニレン基、２－ブテニレン基、ブタジエニレン基、ペンテニレン基、ヘキセニレン基、ヘプテニレン基、オクテニレン基等の炭素数２～８の直鎖又は分岐鎖状のアルケニレン基；炭素数５～６の二価の脂環式炭化水素基、炭素数６～１０の二価の芳香族炭化水素基（例えば、フェニレン基等）、及びこれらが単結合を介して連結した基等を挙げることができる。
In the above formula, Y represents a single bond or a linking group. Examples of the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond (—CONH—), a carbonate bond ( -OCOO-) and a group in which a plurality of these are linked. Examples of the divalent hydrocarbon group include, for example, a linear or branched alkylene group having 1 to 18 carbon atoms; vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group A straight or branched alkenylene group having 2 to 8 carbon atoms such as a hexenylene group, a heptenylene group or an octenylene group; a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms; Valent aromatic hydrocarbon group (for example, phenylene group, etc.) and a group in which these are linked through a single bond.
化合物（b-1）の分子量（若しくは重量平均分子量）は、例えば１０００～７０程度（好ましくは７００～１００、特に好ましくは４００～１５０）であることが、本発明の樹脂組成物が良好な流動性を具備することができる点で好ましい。尚、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）により測定される標準ポリスチレン換算の分子量である。
The molecular weight (or weight average molecular weight) of the compound (b-1) is, for example, about 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). It is preferable at the point which can provide the property. The weight average molecular weight is a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).
化合物（b-1）としては、例えば、Ｎ－ビニルカルバゾール、Ｎ－アリルカルバゾール、Ｎ－（メタ）アクリロイルカルバゾール、Ｎ－（ビニルベンジル）カルバゾール等を挙げることができる。これらは１種を単独で、又は２種以上を組み合わせて使用することができる。
Examples of the compound (b-1) include N-vinylcarbazole, N-allylcarbazole, N- (meth) acryloylcarbazole, N- (vinylbenzyl) carbazole and the like. These can be used alone or in combination of two or more.
（化合物（b-2））
本発明における化合物（b-2）は、下記式（b-2）で表される化合物（ラジカル重合性化合物）である。光カチオン重合開始剤（Ｃ）に紫外線を照射すると、前記光カチオン重合開始剤（Ｃ）は紫外線を吸収して分解してラジカル体を形成し、当該ラジカル体が水素を引き抜くことで酸を発生するものであるが、化合物（b-2）は、前記ラジカル体と反応することにより硬化反応が進行し、本発明の樹脂組成物を半硬化状態へ導く。
(Compound (b-2))
The compound (b-2) in the present invention is a compound (radical polymerizable compound) represented by the following formula (b-2). When the photocationic polymerization initiator (C) is irradiated with ultraviolet rays, the photocationic polymerization initiator (C) absorbs the ultraviolet rays and decomposes to form radicals, which generate acids by extracting hydrogen. However, the compound (b-2) undergoes a curing reaction by reacting with the radical body, leading to the semi-cured state of the resin composition of the present invention.
本発明における化合物（b-2）は、下記式（b-2）で表される化合物（ラジカル重合性化合物）である。光カチオン重合開始剤（Ｃ）に紫外線を照射すると、前記光カチオン重合開始剤（Ｃ）は紫外線を吸収して分解してラジカル体を形成し、当該ラジカル体が水素を引き抜くことで酸を発生するものであるが、化合物（b-2）は、前記ラジカル体と反応することにより硬化反応が進行し、本発明の樹脂組成物を半硬化状態へ導く。
The compound (b-2) in the present invention is a compound (radical polymerizable compound) represented by the following formula (b-2). When the photocationic polymerization initiator (C) is irradiated with ultraviolet rays, the photocationic polymerization initiator (C) absorbs the ultraviolet rays and decomposes to form radicals, which generate acids by extracting hydrogen. However, the compound (b-2) undergoes a curing reaction by reacting with the radical body, leading to the semi-cured state of the resin composition of the present invention.
上記式中、Ｒ1は水素原子又はメチル基を示し、Ｒ2は炭化水素基を示す。ｔは０以上の整数を示し、ｔが２以上の整数である場合、複数のＲ2はそれぞれ同一であってもよく、異なっていてもよい。Ｒ2が複数存在する場合、それらは互いに結合して、式中の芳香環を構成する炭素原子と共に環を形成していてもよい。Ｌは連結基を示す。
In the above formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrocarbon group. t represents an integer of 0 or more, and when t is an integer of 2 or more, the plurality of R 2 may be the same or different. When a plurality of R 2 are present, they may be bonded to each other to form a ring together with the carbon atoms constituting the aromatic ring in the formula. L represents a linking group.
前記Ｒ2における炭化水素基には、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、及びこれらの結合した基が含まれる。
The hydrocarbon group in R 2 includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded.
前記脂肪族炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓ－ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、デシル基、ドデシル基等の炭素数１～２０（好ましくは１～１０、さらに好ましくは１～３）程度のアルキル基；ビニル基、アリル基、１－ブテニル基等の炭素数２～２０（好ましくは２～１０、さらに好ましくは２～３）程度のアルケニル基；エチニル基、プロピニル基等の炭素数２～２０（好ましくは２～１０、さらに好ましくは２～３）程度のアルキニル基等を挙げることができる。
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a decyl group, and a dodecyl group. An alkyl group having about 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 3 carbon atoms) such as vinyl group, allyl group, 1-butenyl group, etc. More preferred is an alkenyl group having about 2 to 3); an alkynyl group having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as an ethynyl group and a propynyl group.
前記脂環式炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基等の３～２０員（好ましくは３～１５員、さらに好ましくは５～８員）程度のシクロアルキル基；シクロペンテニル基、シクロへキセニル基等の３～２０員（好ましくは３～１５員、さらに好ましくは５～８員）程度のシクロアルケニル基；パーヒドロナフタレン－１－イル基、ノルボルニル基、アダマンチル基、テトラシクロ［４．４．０．１2,5．１7,10］ドデカン－３－イル基等の橋かけ環式炭化水素基等を挙げることができる。
Examples of the alicyclic hydrocarbon group include 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group. A cycloalkenyl group of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as a cyclopentenyl group and a cyclohexenyl group; a perhydronaphthalen-1-yl group , Norbornyl group, adamantyl group, tetracyclo [4.4.0.1 2,5 . And a bridged cyclic hydrocarbon group such as a 1,7,10 ] dodecan-3-yl group.
前記芳香族炭化水素基としては、フェニル基、ナフチル基等の炭素数６～１４（好ましくは６～１０）程度の芳香族炭化水素基を挙げることができる。
Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as a phenyl group and a naphthyl group.
前記式（b-2）中のＲ２が複数存在する場合において、これらが互いに結合して、式中の芳香環を構成する炭素原子と共に形成していてもよい環としては、例えば、３～２０員の非芳香族性炭素環や３～２０員の非芳香族性複素環が挙げられる。
In the case where there are a plurality of R2s in the formula (b-2), examples of the ring that may be bonded together to form a carbon atom that constitutes the aromatic ring in the formula include 3 to 20 Examples include a non-aromatic carbocycle having 3 members and a non-aromatic heterocycle having 3 to 20 members.
上記炭化水素基は置換基を１種又は２種以上有していてもよい。前記置換基としては、例えば、フッ素原子等のハロゲン原子、トリフルオロメチル基等のＣ1-5ハロアルキル基、ヒドロキシル基、アミノ基、ジアルキルアミノ基、カルボキシル基、ニトロ基、シアノ基等を挙げることができる。
The hydrocarbon group may have one or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a C 1-5 haloalkyl group such as a trifluoromethyl group, a hydroxyl group, an amino group, a dialkylamino group, a carboxyl group, a nitro group, and a cyano group. Can do.
前記式（b-2）中のＲ2としては、なかでも、芳香族炭化水素基が好ましい。
R 2 in the formula (b-2) is preferably an aromatic hydrocarbon group.
前記式（b-2）中のｔは０以上の整数を示す。ｔは、例えば０～３の整数であり、好ましくは１以上の整数（例えば１～３の整数）である。
T in the formula (b-2) represents an integer of 0 or more. t is, for example, an integer of 0 to 3, and is preferably an integer of 1 or more (eg, an integer of 1 to 3).
Ｌは連結基を示す。前記連結基は１以上の原子を有する二価の基であり、例えば、二価の炭化水素基、カルボニル基（－ＣＯ－）、エーテル結合（－Ｏ－）、チオエーテル結合（－Ｓ－）、エステル結合（－ＣＯＯ－）、アミド結合（－ＣＯＮＨ－）、カーボネート結合（－ＯＣＯＯ－）、及びこれらが複数個連結した基等を挙げることができる。前記二価の炭化水素基としては、上記式（b-1）中のＹにおける例と同様の例を挙げることができる。
L represents a linking group. The linking group is a divalent group having one or more atoms. For example, a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), Examples thereof include an ester bond (—COO—), an amide bond (—CONH—), a carbonate bond (—OCOO—), and a group in which a plurality of these are linked. Examples of the divalent hydrocarbon group include the same examples as those in Y in the above formula (b-1).
化合物（b-2）の分子量（若しくは重量平均分子量）は、例えば１０００～７０程度（好ましくは７００～１００、特に好ましくは４００～１５０）であることが、本発明の樹脂組成物が良好な流動性を具備することができる点で好ましい。尚、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）により測定される標準ポリスチレン換算の分子量である。
The molecular weight (or weight average molecular weight) of the compound (b-2) is, for example, about 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). It is preferable at the point which can provide the property. The weight average molecular weight is a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).
化合物（b-2）としては、なかでも上述の化合物(Ａ)との相溶性に優れ、高屈折率、低透湿性、及び低アウトガス性を有する硬化物を形成することができる点で、下記式（b-2-1）で表される化合物が好ましい。尚、下記式中、Ｒ1、Ｌは前記に同じ。
The compound (b-2) is excellent in compatibility with the above-described compound (A), and can form a cured product having a high refractive index, low moisture permeability, and low outgassing property. A compound represented by formula (b-2-1) is preferred. In the following formulae, R 1 and L are the same as described above.
本発明の樹脂組成物は、上記化合物（Ａ）と共に、化合物（Ｂ）として、化合物（b-1）、及び化合物（b-2）から選択される少なくとも１種の化合物を含有する。そして、本発明の樹脂組成物に紫外線照射を行うと、上記化合物（Ａ）は光カチオン重合開始剤（Ｃ）から発生する酸をトラップして硬化遅延性を発揮する一方で、化合物（Ｂ）はある程度硬化反応を進行させるため、これらの作用が組み合わさることによって半硬化状態となる。
The resin composition of the present invention contains at least one compound selected from the compound (b-1) and the compound (b-2) as the compound (B) together with the compound (A). When the resin composition of the present invention is irradiated with ultraviolet rays, the compound (A) traps an acid generated from the photocationic polymerization initiator (C) and exhibits curing retardation, while the compound (B) Since the curing reaction proceeds to some extent, a combination of these actions results in a semi-cured state.
本発明における化合物（Ｂ）は低粘度でアセトン溶解性に優れる。また、硬化することにより高屈折率、低透湿性、及び低アウトガス性を有する硬化物を形成することができる。
Compound (B) in the present invention has low viscosity and excellent acetone solubility. Moreover, the hardened | cured material which has a high refractive index, low moisture permeability, and low outgas property can be formed by hardening.
［光カチオン重合開始剤（Ｃ）］
光カチオン重合開始剤は、紫外線の照射によって分解してラジカル体を形成し、当該ラジカル体が水素を引き抜くことで酸を発生して硬化性化合物の硬化反応を開始させる化合物である。光カチオン重合開始剤は、光を吸収するカチオン部と酸の発生源となるアニオン部からなる。 [Photocationic polymerization initiator (C)]
The cationic photopolymerization initiator is a compound that decomposes by irradiation with ultraviolet rays to form a radical body, and the radical body extracts hydrogen to generate an acid to initiate a curing reaction of the curable compound. The cationic photopolymerization initiator is composed of a cation moiety that absorbs light and an anion moiety that is a source of acid generation.
光カチオン重合開始剤は、紫外線の照射によって分解してラジカル体を形成し、当該ラジカル体が水素を引き抜くことで酸を発生して硬化性化合物の硬化反応を開始させる化合物である。光カチオン重合開始剤は、光を吸収するカチオン部と酸の発生源となるアニオン部からなる。 [Photocationic polymerization initiator (C)]
The cationic photopolymerization initiator is a compound that decomposes by irradiation with ultraviolet rays to form a radical body, and the radical body extracts hydrogen to generate an acid to initiate a curing reaction of the curable compound. The cationic photopolymerization initiator is composed of a cation moiety that absorbs light and an anion moiety that is a source of acid generation.
本発明の光カチオン重合開始剤としては、例えば、ジアゾニウム塩系化合物、ヨードニウム塩系化合物、スルホニウム塩系化合物、ホスホニウム塩系化合物、セレニウム塩系化合物、オキソニウム塩系化合物、アンモニウム塩系化合物、臭素塩系化合物等を挙げることができる。
Examples of the photocationic polymerization initiator of the present invention include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salts. And the like, and the like.
なかでも、スルホニウム塩系化合物を使用することが、硬化性に優れた硬化物を形成することができる点で好ましい。スルホニウム塩系化合物のカチオン部としては、例えば、（４－ヒドロキシフェニル）メチルベンジルスルホニウムイオン、トリフェニルスルホニウムイオン、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムイオン、トリ－ｐ－トリルスルホニウムイオン等のアリールスルホニウムイオン（特に、トリアリールスルホニウムイオン）を挙げることができる。
Among these, the use of a sulfonium salt compound is preferable in that a cured product having excellent curability can be formed. Examples of the cation moiety of the sulfonium salt compound include aryls such as (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and tri-p-tolylsulfonium ion. Examples include sulfonium ions (particularly triarylsulfonium ions).
光カチオン重合開始剤のアニオン部としては、例えば、ＢＦ4
-、Ｂ（Ｃ6Ｆ5）4
-、ＰＦ6
-、［（Ｒｆ）kＰＦ6-k］-（Ｒｆ：水素原子の８０％以上がフッ素原子で置換されたアルキル基、ｋ：１～５の整数）、ＡｓＦ6
-、ＳｂＦ6
-、ＳｂＦ5ＯＨ-等を挙げることができる。
Examples of the anion part of the cationic photopolymerization initiator include BF 4 − , B (C 6 F 5 ) 4 − , PF 6 − , [(Rf) k PF 6−k ] − (Rf: 80% of hydrogen atoms) The above is an alkyl group substituted with a fluorine atom, k: an integer of 1 to 5), AsF 6 − , SbF 6 − , SbF 5 OH − and the like.
本発明の光カチオン重合開始剤としては、例えば、（４－ヒドロキシフェニル）メチルベンジ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、４－（４－ビフェニリルチオ）フェニル－４－ビフェニリル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、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、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ァート、４－（４－ビフェニリルチオ）フェニル－４－ビフェニリルフェニルスルホニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート、商品名「サイラキュアＵＶＩ－６９７０」、「サイラキュアＵＶＩ－６９７４」、「サイラキュアＵＶＩ－６９９０」、「サイラキュアＵＶＩ－９５０」（以上、米国ユニオンカーバイド社製）、「イルガキュア２５０」、「イルガキュア２６１」、「イルガキュア２６４」（以上、ＢＡＳＦ社製）、「アデカオプトマーＳＰ－１５０」、「アデカオプトマーＳＰ－１５１」、「アデカオプトマーＳＰ－１７０」、「アデカオプトマーＳＰ－１７１」（以上、（株）ＡＤＥＫＡ製）、「ＣＧ－２４－６１」（ＢＡＳＦ社製）、「ＤＡＩＣＡＴ II」（（株）ダイセル製）、「ＵＶＡＣ１５９０」、「ＵＶＡＣ１５９１」（以上、ダイセル・サイテック（株）製）、「ＣＩ－２０６４」、「ＣＩ－２６３９」、「ＣＩ－２６２４」、「ＣＩ－２４８１」、「ＣＩ－２７３４」、「ＣＩ－２８５５」、「ＣＩ－２８２３」、「ＣＩ－２７５８」、「ＣＩＴ－１６８２」（以上、日本曹達（株）製）、「ＰＩ－２０７４」（ローディア社製、テトラキス（ペンタフルオロフェニルボレート）トリルクミルヨードニウム塩）、「ＦＦＣ５０９」（３Ｍ社製）、「ＢＢＩ－１０２」、「ＢＢＩ－１０１」、「ＢＢＩ－１０３」、「ＭＰＩ－１０３」、「ＴＰＳ－１０３」、「ＭＤＳ－１０３」、「ＤＴＳ－１０３」、「ＮＡＴ－１０３」、「ＮＤＳ－１０３」（以上、ミドリ化学（株）製）、「ＣＤ－１０１０」、「ＣＤ－１０１１」、「ＣＤ－１０１２」（米国、Ｓａｒｔｏｍｅｒ社製）、「ＣＰＩ－１００Ｐ」、「ＣＰＩ－１０１Ａ」（以上、サンアプロ（株）製）等の市販品を使用できる。
Examples of the photocationic polymerization initiator of the present invention include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (penta Fluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4- (4-biphenylylthio) phenyl-4 -Biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, trade names “Syracure UVI-6970”, “Syracure UVI-6974”, “Syracure “VI-6990”, “Syracure UVI-950” (manufactured by Union Carbide, USA), “Irgacure 250”, “Irgacure 261”, “Irgacure 264” (manufactured by BASF), “Adekaoptomer SP-150” "Adekaoptomer SP-151", "Adekaoptomer SP-170", "Adekaoptomer SP-171" (manufactured by ADEKA), "CG-24-61" (manufactured by BASF) "DAICAT II" (manufactured by Daicel Corp.), "UVAC1590", "UVAC1591" (manufactured by Daicel Cytec Corp.), "CI-2064", "CI-2638", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", “CIT-1682” (manufactured by Nippon Soda Co., Ltd.), “PI-2074” (manufactured by Rhodia, tetrakis (pentafluorophenylborate) tricumyl iodonium salt), “FFC509” (manufactured by 3M), “ "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS- 103 ”(manufactured by Midori Chemical Co., Ltd.),“ CD-1010 ”,“ CD-1011 ”,“ CD-1012 ”(manufactured by Sartomer, USA),“ CPI-100P ”,“ CPI-101A ”( As described above, commercially available products such as San Apro Co., Ltd. can be used.
［他の添加剤］
本発明の樹脂組成物は、更に、必要に応じて、例えば、硬化性化合物（化合物（Ａ）、（Ｂ）を除く）、フィラー、シランカップリング剤、重合禁止剤、酸化防止剤、光安定剤、可塑剤、レベリング剤、消泡剤、顔料、有機溶剤、紫外線吸収剤、イオン吸着体、蛍光体、離型剤、レオロジーコントロール剤等の慣用の添加剤を含有していてもよい。これらの含有量は、樹脂組成物全量の例えば４０重量％以下、好ましくは２０重量％以下、特に好ましくは１０重量％以下である。また、本発明の樹脂組成物は石油樹脂等の重量平均分子量が１０００超（好ましくは５０００超、特に好ましくは１００００超）の高分子化合物及び／又は溶解度パラメーター（２５℃におけるＳＰ値；Fedorsの式で算出される値）が８．５以上の化合物を含有していても良いがその含有量は、例えば５重量％以下、好ましくは３重量％以下、特に好ましくは１重量％以下である。高分子化合物の含有量が上記範囲を上回ると、アセトン溶解性が低下し、液体定量吐出装置等の内部をアセトンで洗浄することが困難となるため好ましくない。 [Other additives]
The resin composition of the present invention may further include, for example, a curable compound (excluding compounds (A) and (B)), a filler, a silane coupling agent, a polymerization inhibitor, an antioxidant, and a light stabilizer, as necessary. Conventional additives such as an agent, a plasticizer, a leveling agent, an antifoaming agent, a pigment, an organic solvent, an ultraviolet absorber, an ion adsorbent, a phosphor, a release agent, and a rheology control agent may be contained. The content thereof is, for example, 40% by weight or less, preferably 20% by weight or less, particularly preferably 10% by weight or less, based on the total amount of the resin composition. The resin composition of the present invention is a polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5000, particularly preferably more than 10,000) and / or a solubility parameter (SP value at 25 ° C .; Fedors formula) May contain a compound having a value of 8.5 or more, but the content thereof is, for example, 5% by weight or less, preferably 3% by weight or less, particularly preferably 1% by weight or less. If the content of the polymer compound exceeds the above range, the acetone solubility is lowered, and it is difficult to wash the inside of the liquid quantitative discharge device or the like with acetone.
本発明の樹脂組成物は、更に、必要に応じて、例えば、硬化性化合物（化合物（Ａ）、（Ｂ）を除く）、フィラー、シランカップリング剤、重合禁止剤、酸化防止剤、光安定剤、可塑剤、レベリング剤、消泡剤、顔料、有機溶剤、紫外線吸収剤、イオン吸着体、蛍光体、離型剤、レオロジーコントロール剤等の慣用の添加剤を含有していてもよい。これらの含有量は、樹脂組成物全量の例えば４０重量％以下、好ましくは２０重量％以下、特に好ましくは１０重量％以下である。また、本発明の樹脂組成物は石油樹脂等の重量平均分子量が１０００超（好ましくは５０００超、特に好ましくは１００００超）の高分子化合物及び／又は溶解度パラメーター（２５℃におけるＳＰ値；Fedorsの式で算出される値）が８．５以上の化合物を含有していても良いがその含有量は、例えば５重量％以下、好ましくは３重量％以下、特に好ましくは１重量％以下である。高分子化合物の含有量が上記範囲を上回ると、アセトン溶解性が低下し、液体定量吐出装置等の内部をアセトンで洗浄することが困難となるため好ましくない。 [Other additives]
The resin composition of the present invention may further include, for example, a curable compound (excluding compounds (A) and (B)), a filler, a silane coupling agent, a polymerization inhibitor, an antioxidant, and a light stabilizer, as necessary. Conventional additives such as an agent, a plasticizer, a leveling agent, an antifoaming agent, a pigment, an organic solvent, an ultraviolet absorber, an ion adsorbent, a phosphor, a release agent, and a rheology control agent may be contained. The content thereof is, for example, 40% by weight or less, preferably 20% by weight or less, particularly preferably 10% by weight or less, based on the total amount of the resin composition. The resin composition of the present invention is a polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5000, particularly preferably more than 10,000) and / or a solubility parameter (SP value at 25 ° C .; Fedors formula) May contain a compound having a value of 8.5 or more, but the content thereof is, for example, 5% by weight or less, preferably 3% by weight or less, particularly preferably 1% by weight or less. If the content of the polymer compound exceeds the above range, the acetone solubility is lowered, and it is difficult to wash the inside of the liquid quantitative discharge device or the like with acetone.
また、本発明の樹脂組成物は光カチオン重合開始剤（Ｃ）以外の重合開始剤（例えば、光ラジカル重合開始剤等）を含有していても良いが、本発明の樹脂組成物に含まれる重合開始剤全量における光カチオン重合開始剤（Ｃ）の占める割合は、例えば６０重量％以上、好ましくは８０重量％以上、特に好ましくは９０重量％以上である。尚、上限は１００重量％である。また、本発明の樹脂組成物における光ラジカル重合開始剤の含有量は、本発明の樹脂組成物に含まれる重合開始剤全量の例えば１０重量％以下（なかでも５重量％以下、特に１重量％以下）であることが好ましく、実質的に含まないことが最も好ましい。光ラジカル重合開始剤の含有量が上記範囲を上回ると、紫外線照射後の粘度が高くなり過ぎ、接着性を維持することが困難となる傾向がある。
The resin composition of the present invention may contain a polymerization initiator other than the photocationic polymerization initiator (C) (for example, a radical photopolymerization initiator), but is included in the resin composition of the present invention. The proportion of the photocationic polymerization initiator (C) in the total amount of the polymerization initiator is, for example, 60% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more. The upper limit is 100% by weight. The content of the photo radical polymerization initiator in the resin composition of the present invention is, for example, 10% by weight or less (in particular, 5% by weight or less, particularly 1% by weight) of the total amount of the polymerization initiator contained in the resin composition of the present invention. Or less), and most preferably not substantially contained. When the content of the photo radical polymerization initiator exceeds the above range, the viscosity after ultraviolet irradiation becomes too high, and it tends to be difficult to maintain adhesiveness.
＜樹脂組成物、およびその製造方法＞
本発明の樹脂組成物は、上述の化合物（Ａ）、化合物（Ｂ）、光カチオン重合開始剤（Ｃ）、及び必要に応じてその他の成分を、均一に混合することにより製造することができる。尚、化合物（Ａ）、化合物（Ｂ）、光カチオン重合開始剤（Ｃ）は、それぞれ、１種を単独で、又は２種以上を組み合わせて使用することができる。本発明の樹脂組成物を得るにあたっては、各成分を自公転式撹拌脱泡装置、ホモジナイザー、プラネタリーミキサー、３本ロールミル、ビーズミル等の一般的に知られる混合用機器を使用してなるべく均一になるように、撹拌、溶解、混合、分散等を行うことが望ましい。尚、各成分は、同時に混合してもよいし、逐次混合してもよい。 <Resin composition and production method thereof>
The resin composition of the present invention can be produced by uniformly mixing the above-described compound (A), compound (B), photocationic polymerization initiator (C), and other components as necessary. . In addition, a compound (A), a compound (B), and a photocationic polymerization initiator (C) can each be used individually by 1 type or in combination of 2 or more types. In obtaining the resin composition of the present invention, each component is made as uniform as possible by using generally known mixing equipment such as a revolving and stirring agitation / deaerator, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. It is desirable to perform stirring, dissolution, mixing, dispersion, and the like. Each component may be mixed simultaneously or sequentially.
本発明の樹脂組成物は、上述の化合物（Ａ）、化合物（Ｂ）、光カチオン重合開始剤（Ｃ）、及び必要に応じてその他の成分を、均一に混合することにより製造することができる。尚、化合物（Ａ）、化合物（Ｂ）、光カチオン重合開始剤（Ｃ）は、それぞれ、１種を単独で、又は２種以上を組み合わせて使用することができる。本発明の樹脂組成物を得るにあたっては、各成分を自公転式撹拌脱泡装置、ホモジナイザー、プラネタリーミキサー、３本ロールミル、ビーズミル等の一般的に知られる混合用機器を使用してなるべく均一になるように、撹拌、溶解、混合、分散等を行うことが望ましい。尚、各成分は、同時に混合してもよいし、逐次混合してもよい。 <Resin composition and production method thereof>
The resin composition of the present invention can be produced by uniformly mixing the above-described compound (A), compound (B), photocationic polymerization initiator (C), and other components as necessary. . In addition, a compound (A), a compound (B), and a photocationic polymerization initiator (C) can each be used individually by 1 type or in combination of 2 or more types. In obtaining the resin composition of the present invention, each component is made as uniform as possible by using generally known mixing equipment such as a revolving and stirring agitation / deaerator, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. It is desirable to perform stirring, dissolution, mixing, dispersion, and the like. Each component may be mixed simultaneously or sequentially.
本発明の樹脂組成物における化合物（Ａ）の含有量は、樹脂組成物に含まれる硬化性化合物全量（１００重量％）の、例えば４５～９５重量％、好ましくは６０～９５重量％、より好ましくは６５～９０重量％、特に好ましくは７０～８５重量％である。
The content of the compound (A) in the resin composition of the present invention is, for example, 45 to 95% by weight, preferably 60 to 95% by weight, more preferably the total amount (100% by weight) of the curable compound contained in the resin composition. Is 65 to 90% by weight, particularly preferably 70 to 85% by weight.
また、本発明の樹脂組成物における化合物（Ｂ）の含有量は、樹脂組成物に含まれる硬化性化合物全量（１００重量％）の、例えば５～４０重量％、好ましくは１０～３５重量％、特に好ましくは１５～３０重量％である。
The content of the compound (B) in the resin composition of the present invention is, for example, 5 to 40% by weight, preferably 10 to 35% by weight, based on the total amount (100% by weight) of the curable compound contained in the resin composition. Particularly preferred is 15 to 30% by weight.
また、本発明の樹脂組成物に含まれる化合物（Ａ）と化合物（Ｂ）の含有量の比（前者：後者（重量比））は、例えば６０：４０～９５：５、好ましくは６５：３５～９０：１０、特に好ましくは７０：３０～８５：１５である。
The ratio of the content of the compound (A) and the compound (B) contained in the resin composition of the present invention (the former: the latter (weight ratio)) is, for example, 60:40 to 95: 5, preferably 65:35. ˜90: 10, particularly preferably 70:30 to 85:15.
更に、本発明の樹脂組成物における化合物（Ａ）と化合物（Ｂ）の合計含有量は、樹脂組成物に含まれる硬化性化合物全量（１００重量％）の、例えば５０重量％以上、好ましくは６０重量％以上、より好ましくは７０重量％以上、特に好ましくは８０重量％以上、最も好ましくは９０重量％以上である。尚、上限は１００重量％である。
Furthermore, the total content of the compound (A) and the compound (B) in the resin composition of the present invention is, for example, 50% by weight or more, preferably 60% of the total amount (100% by weight) of the curable compound contained in the resin composition. % By weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. The upper limit is 100% by weight.
本発明の樹脂組成物における光カチオン重合開始剤（Ｃ）の含有量は、樹脂組成物に含まれる硬化性化合物１００重量部に対して、例えば０．０１～１５重量部が好ましく、より好ましくは０．０１～１０重量部、特に好ましくは０．０５～５重量部、最も好ましくは０．１～３重量部である。
The content of the cationic photopolymerization initiator (C) in the resin composition of the present invention is preferably 0.01 to 15 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the curable compound contained in the resin composition. 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, and most preferably 0.1 to 3 parts by weight.
本発明の樹脂組成物は、硬化性化合物として化合物（Ａ）と化合物（Ｂ）を上記範囲で含有するため、紫外線照射により適度に流動性を低下させ半硬化状態へ導かれ、その状態を保持することができる。そのため、例えば本発明の樹脂組成物をフィル材として使用した場合は、ダムからの流出を防止することができる。また、紫外線を照射しても加熱処理を施すまでは半硬化状態のまま（すなわち、接着性を維持した状態）で保持することができ、加熱処理のタイミングを調整することで、硬化反応の再開時期を任意に設定することができる。化合物（Ａ）の含有量が上記範囲を下回ると（若しくは、化合物（Ｂ）の含有量が上記範囲を上回ると）、紫外線照射後の粘度が高くなり過ぎ、素子や電極等の段差に対する追従性が低下し、貼り合わせ基板との間に隙間が生じることにより、封止精度が低下する傾向がある。一方、化合物（Ａ）の含有量が上記範囲を上回ると（若しくは、化合物（Ｂ）の含有量が上記範囲を下回ると）、紫外線を照射しても流動性を低下させることができず、例えば本発明の樹脂組成物をフィル材として使用した場合に、ダムからの流出を防止することが困難となる場合がある。
Since the resin composition of the present invention contains the compound (A) and the compound (B) as the curable compound in the above range, the fluidity is appropriately reduced by irradiation with ultraviolet rays and led to a semi-cured state, and the state is maintained. can do. Therefore, for example, when the resin composition of the present invention is used as a fill material, the outflow from the dam can be prevented. Moreover, even if it irradiates with ultraviolet rays, it can be kept in a semi-cured state (that is, in a state where adhesion is maintained) until heat treatment is performed, and the curing reaction can be resumed by adjusting the timing of the heat treatment. The time can be set arbitrarily. When the content of the compound (A) is lower than the above range (or when the content of the compound (B) is higher than the above range), the viscosity after ultraviolet irradiation becomes too high, and the followability with respect to steps such as elements and electrodes. Decreases, and a gap is formed between the bonded substrate and the sealing accuracy tends to decrease. On the other hand, if the content of the compound (A) exceeds the above range (or if the content of the compound (B) is below the above range), the fluidity cannot be lowered even when irradiated with ultraviolet rays. When the resin composition of the present invention is used as a fill material, it may be difficult to prevent outflow from a dam.
本発明の樹脂組成物は、紫外線を照射するまでは流動性に優れ、２５℃における粘度は例えば１０ｍＰａ・ｓ以上、３０ｍＰａ・ｓ未満、好ましくは１５～２５ｍＰａ・ｓである。そのため、ディスペンサー等の液体定量吐出装置やインクジェット塗布装置等を使用して良好に吐出することができる。尚、樹脂組成物の粘度はＥ型粘度計又はレオメーターを使用して測定することができる。
The resin composition of the present invention is excellent in fluidity until it is irradiated with ultraviolet rays, and the viscosity at 25 ° C. is, for example, 10 mPa · s or more and less than 30 mPa · s, preferably 15 to 25 mPa · s. Therefore, it can discharge favorably using liquid fixed-quantity discharge apparatuses, such as a dispenser, an inkjet coating device, etc. The viscosity of the resin composition can be measured using an E-type viscometer or a rheometer.
本発明の樹脂組成物は、光カチオン重合開始剤（Ｃ）から発生する酸をトラップして硬化反応の進行を抑制する作用を有する化合物（Ａ）と、前記酸若しくは光カチオン重合開始剤（Ｃ）の分解物であるラジカル体によって硬化反応が進行する化合物（Ｂ）を共に含有するため、紫外線照射を行うと、化合物（Ｂ）の硬化反応は流動性が低下する程度で留められ、接着性が消失するまで硬化が進行することはない。すなわち、硬化遅延性を発揮して半硬化状態が維持される。
The resin composition of the present invention comprises a compound (A) having an action of trapping an acid generated from the photocationic polymerization initiator (C) and suppressing the progress of the curing reaction, and the acid or photocationic polymerization initiator (C ), The compound (B) that undergoes a curing reaction by a radical body, which is a decomposition product of the compound (B), contains both the compound (B) and the curing reaction of the compound (B) is suppressed to the extent that the fluidity is lowered. Curing does not proceed until disappears. In other words, the curing retardation is exhibited and the semi-cured state is maintained.
本発明の樹脂組成物は、紫外線を照射することで流動性を適度に低下させることができるため、増粘性を付与する目的で一般的に用いられる高分子化合物（例えば、石油樹脂等）等を添加する必要がない。そのため、アセトン溶解性に優れる。また、添加物由来のアウトガスの発生を防止することもできる。
Since the resin composition of the present invention can moderately reduce fluidity by irradiating with ultraviolet rays, a polymer compound (for example, petroleum resin) generally used for the purpose of imparting thickening is used. There is no need to add. Therefore, it is excellent in acetone solubility. Moreover, generation | occurrence | production of the outgas derived from an additive can also be prevented.
前記紫外線照射は、水銀ランプ等で１０００ｍＪ／ｃｍ2以上の光を照射することが好ましい。
The ultraviolet irradiation is preferably performed by irradiating light of 1000 mJ / cm 2 or more with a mercury lamp or the like.
紫外線照射（照射量：１５００ｍＪ／ｃｍ2）直後の樹脂組成物の２５℃における粘度は、例えば３０～２０００ｍＰａ・ｓ、好ましくは３０～１０００ｍＰａ・ｓである。
The viscosity of the resin composition immediately after UV irradiation (irradiation amount: 1500 mJ / cm 2 ) at 25 ° C. is, for example, 30 to 2000 mPa · s, preferably 30 to 1000 mPa · s.
また、本発明の樹脂組成物は紫外線を照射しても、加熱処理を施すまでは半硬化状態を維持することができ、紫外線照射（照射量：１５００ｍＪ／ｃｍ2）後３０分における樹脂組成物の２５℃における粘度は、例えば３０～２５００ｍＰａ・ｓ、好ましくは３０～１５００ｍＰａ・ｓである。すなわち、本発明の樹脂組成物は硬化遅延効果に優れ、紫外線照射直後から紫外線照射後３０分の間の粘度の上昇度（＝紫外線照射後３０分の粘度／紫外線照射直後の粘度）を、例えば１．３０以下、好ましくは１．２０以下に留めることができる。
Moreover, even if the resin composition of the present invention is irradiated with ultraviolet rays, it can maintain a semi-cured state until heat treatment is performed, and the resin composition 30 minutes after irradiation with ultraviolet rays (irradiation amount: 1500 mJ / cm 2 ). The viscosity at 25 ° C. is, for example, 30 to 2500 mPa · s, preferably 30 to 1500 mPa · s. That is, the resin composition of the present invention has an excellent curing delay effect, and the degree of increase in viscosity during the period from 30 minutes after ultraviolet irradiation to 30 minutes after ultraviolet irradiation (= viscosity 30 minutes after ultraviolet irradiation / viscosity immediately after ultraviolet irradiation), for example, It can be kept at 1.30 or less, preferably 1.20 or less.
本発明の樹脂組成物は紫外線を照射後、加熱処理を施して化合物（Ａ）にトラップされた酸を放出することにより硬化反応が再開し、加熱処理後は速やかに硬化物を形成することができる。
The resin composition of the present invention can be subjected to heat treatment after being irradiated with ultraviolet rays to release the acid trapped in the compound (A), whereby the curing reaction is restarted, and a cured product can be quickly formed after the heat treatment. it can.
前記加熱処理は、例えば、温度５０～２００℃（より好ましくは５０～１７０℃、さらに好ましくは５０～１５０℃）で、１０～６００分間（より好ましくは１０～３６０分間、さらに好ましくは１５～１８０分間）加熱することが好ましい。
The heat treatment is performed, for example, at a temperature of 50 to 200 ° C. (more preferably 50 to 170 ° C., more preferably 50 to 150 ° C.) for 10 to 600 minutes (more preferably 10 to 360 minutes, still more preferably 15 to 180). Heating for a minute) is preferred.
本発明の樹脂組成物は上記特性を有するため、有機ＥＬ素子の封止剤として使用する場合に、予め紫外線照射を施し、流動性を低下させた樹脂組成物を有機ＥＬ素子に適用することで、樹脂組成物がダムから流出することを防止しつつ有機ＥＬ素子と貼り合わせることができ、その後加熱処理を施すことにより、有機ＥＬ素子を直に紫外線に曝すことなく封止することができる。
Since the resin composition of the present invention has the above characteristics, when it is used as a sealant for an organic EL device, the resin composition that has been subjected to ultraviolet irradiation in advance and has reduced fluidity is applied to the organic EL device. The organic EL element can be bonded to the organic EL element while preventing the resin composition from flowing out of the dam, and then the organic EL element can be sealed without being directly exposed to ultraviolet rays by performing a heat treatment.
＜硬化物＞
本発明の樹脂組成物の硬化物は、樹脂組成物に上述の条件で紫外線照射を施し、更に上述の条件で加熱処理を施すことにより得られる。 <Hardened product>
The cured product of the resin composition of the present invention can be obtained by subjecting the resin composition to ultraviolet irradiation under the above-mentioned conditions and further subjecting it to a heat treatment under the above-mentioned conditions.
本発明の樹脂組成物の硬化物は、樹脂組成物に上述の条件で紫外線照射を施し、更に上述の条件で加熱処理を施すことにより得られる。 <Hardened product>
The cured product of the resin composition of the present invention can be obtained by subjecting the resin composition to ultraviolet irradiation under the above-mentioned conditions and further subjecting it to a heat treatment under the above-mentioned conditions.
本発明の樹脂組成物の硬化物の、２５℃における波長５８９．３ｎｍの光（ナトリウムＤ線）に対する屈折率は、例えば１．６５以上、好ましくは１．６８以上である。尚、硬化物の屈折率は、例えば、ＪＩＳ Ｋ ７１４２に準拠する方法や、プリズムカプラを用いる方法により測定することができる。
The refractive index of the cured product of the resin composition of the present invention with respect to light having a wavelength of 589.3 nm (sodium D line) at 25 ° C. is, for example, 1.65 or more, preferably 1.68 or more. In addition, the refractive index of hardened | cured material can be measured by the method based on JISK7142, or the method using a prism coupler, for example.
また、前記硬化物は低透湿性を有し、硬化物（厚さ：１００μｍ）の透湿量（ｇ／ｍ2・ｄａｙ・ａｔｍ）は、例えば１００以下、好ましくは５０以下、特に好ましくは３５以下、最も好ましくは２５以下である。尚、前記透湿量は、ＪＩＳ Ｌ １０９９およびＪＩＳ Ｚ ０２０８に準じて、厚み１００μｍに調整した硬化物の透湿量を、６０℃、９０％ＲＨの条件下で測定した値である。
The cured product has low moisture permeability, and the moisture permeability (g / m 2 · day · atm) of the cured product (thickness: 100 μm) is, for example, 100 or less, preferably 50 or less, particularly preferably 35. Hereinafter, it is most preferably 25 or less. The moisture permeation amount is a value obtained by measuring the moisture permeation amount of a cured product adjusted to a thickness of 100 μm in accordance with JIS L 1099 and JIS Z 0208 under the conditions of 60 ° C. and 90% RH.
更に、前記硬化物は低アウトガス性を有し、硬化物（６０ｍｇ）のアウトガス量は例えば１０００ｐｐｍ以下（好ましくは２００ｐｐｍ以下、特に好ましくは１００ｐｐｍ以下）である。尚、アウトガス量はヘッドスペースＧＣ／ＭＳにより測定することができる。
Furthermore, the cured product has low outgassing properties, and the amount of outgas of the cured product (60 mg) is, for example, 1000 ppm or less (preferably 200 ppm or less, particularly preferably 100 ppm or less). The outgas amount can be measured by the head space GC / MS.
本発明の樹脂組成物は上述の通り、紫外線を照射するまでは低粘度で塗布性及びアセトン溶解性に優れる。また、紫外線を照射することにより適度に流動性を低下させて半硬化状態とすることができ、加熱処理を施すまでは当該半硬化状態を保持することができる。そして、紫外線を照射後、更に加熱処理を施すことにより硬化反応を再開させることができ、その後速やかに硬化して、高屈折率、低透湿性、及び低アウトガス性を兼ね備えた硬化物を形成することができる。このため、例えば、トップ・エミッション型有機ＥＬデバイスの封止剤（特に、フィル材）、ボトム・エミッション型有機ＥＬデバイスの光取り出し層材料、太陽電池材料、レンズ材料（特に、高屈折率レンズ材料）等として好ましく使用できる。特に、本発明の樹脂組成物を、有機ＥＬデバイスを製造する工程において、封止剤として使用すると、高屈折率部材との界面における光の反射を抑制することができ、光の取り出し効率を向上することができ、高効率、高輝度、長寿命を有する有機ＥＬデバイスが得られる。
As described above, the resin composition of the present invention has a low viscosity and excellent coating properties and acetone solubility until it is irradiated with ultraviolet rays. Moreover, by irradiating with ultraviolet rays, the fluidity can be lowered moderately to be in a semi-cured state, and the semi-cured state can be maintained until heat treatment is performed. And after irradiating with ultraviolet rays, the curing reaction can be restarted by further heat treatment, and then cured rapidly to form a cured product having high refractive index, low moisture permeability, and low outgassing properties. be able to. For this reason, for example, a sealant (particularly, a fill material) for a top emission type organic EL device, a light extraction layer material for a bottom emission type organic EL device, a solar cell material, a lens material (particularly, a high refractive index lens material) ) And the like. In particular, when the resin composition of the present invention is used as a sealant in the process of producing an organic EL device, reflection of light at the interface with a high refractive index member can be suppressed, and light extraction efficiency is improved. Thus, an organic EL device having high efficiency, high brightness, and long life can be obtained.
＜有機ＥＬデバイスの製造方法＞
本発明の有機ＥＬデバイスの製造方法は、下記工程１及び２を経て有機ＥＬ素子（特に、トップ・エミッション型有機ＥＬ素子）を封止することを特徴とする。
工程１：上述の樹脂組成物からなる塗膜に、紫外線照射を施す
工程２：有機ＥＬ素子を設置した基板の素子設置面に、工程１を経て得られた紫外線照射後の塗膜を貼り合わせて加熱処理を施す <Method for manufacturing organic EL device>
The method for producing an organic EL device of the present invention is characterized by sealing an organic EL element (particularly, a top emission type organic EL element) through the following steps 1 and 2.
Step 1: UV coating is applied to the coating film made of the resin composition described above. Step 2: The coating film after UV irradiation obtained throughStep 1 is bonded to the element mounting surface of the substrate on which the organic EL element is mounted. Heat treatment
本発明の有機ＥＬデバイスの製造方法は、下記工程１及び２を経て有機ＥＬ素子（特に、トップ・エミッション型有機ＥＬ素子）を封止することを特徴とする。
工程１：上述の樹脂組成物からなる塗膜に、紫外線照射を施す
工程２：有機ＥＬ素子を設置した基板の素子設置面に、工程１を経て得られた紫外線照射後の塗膜を貼り合わせて加熱処理を施す <Method for manufacturing organic EL device>
The method for producing an organic EL device of the present invention is characterized by sealing an organic EL element (particularly, a top emission type organic EL element) through the following
Step 1: UV coating is applied to the coating film made of the resin composition described above. Step 2: The coating film after UV irradiation obtained through
本発明の製造方法によれば、紫外線照射による素子の劣化を防止しつつ、有機ＥＬ素子を封止することができ、長寿命で信頼性の高い有機ＥＬデバイスを提供することができる。尚、紫外線照射、及び加熱処理方法は上述の樹脂組成物の紫外線照射、及び加熱処理と同様の方法で行うことができる。
According to the production method of the present invention, an organic EL device can be sealed while preventing deterioration of the device due to ultraviolet irradiation, and a long-life and highly reliable organic EL device can be provided. The ultraviolet irradiation and heat treatment methods can be performed in the same manner as the ultraviolet irradiation and heat treatment of the above resin composition.
本発明の製造方法としては、より詳細には、下記方法１を挙げることができる。
＜方法１：図１参照＞
工程１－１：リッド上に上述の樹脂組成物を塗布して塗膜／リッド積層体を形成する
工程１－２：塗膜に紫外線照射を施す
工程２－１：基板上に有機ＥＬ素子を設置し、有機ＥＬ素子設置面に紫外線照射後の塗膜／リッド積層体を塗膜面が素子設置面に相対するように貼り合わせる
工程２－２：加熱処理を施して塗膜を硬化させる More specifically, the production method of the present invention includes the followingmethod 1.
<Method 1: See FIG. 1>
Step 1-1: Applying the above-mentioned resin composition on the lid to form a coating film / lid laminate Step 1-2: Irradiating the coating film with ultraviolet rays Step 2-1: An organic EL element on the substrate Install and bond the UV / irradiated coating film / lid laminate on the organic EL element installation surface so that the coating film surface faces the element installation surface Step 2-2: Heat treatment is performed to cure the coating film
＜方法１：図１参照＞
工程１－１：リッド上に上述の樹脂組成物を塗布して塗膜／リッド積層体を形成する
工程１－２：塗膜に紫外線照射を施す
工程２－１：基板上に有機ＥＬ素子を設置し、有機ＥＬ素子設置面に紫外線照射後の塗膜／リッド積層体を塗膜面が素子設置面に相対するように貼り合わせる
工程２－２：加熱処理を施して塗膜を硬化させる More specifically, the production method of the present invention includes the following
<Method 1: See FIG. 1>
Step 1-1: Applying the above-mentioned resin composition on the lid to form a coating film / lid laminate Step 1-2: Irradiating the coating film with ultraviolet rays Step 2-1: An organic EL element on the substrate Install and bond the UV / irradiated coating film / lid laminate on the organic EL element installation surface so that the coating film surface faces the element installation surface Step 2-2: Heat treatment is performed to cure the coating film
前記リッド（蓋）や基板としては防湿性基材を使用することが好ましく、例えば、ソーダガラス、無アルカリガラス等のガラス基材；ステンレス、アルミニウム等の金属基材；三フッ化ポリエチレン、ポリ三フッ化塩化エチレン（ＰＣＴＦＥ）、ポリビニリデンフルオライド（ＰＶＤＦ）、ＰＣＴＦＥとＰＶＤＦとの共重合体、ＰＶＤＦとポリフッ化塩化エチレンとの共重合体等のポリフッ化エチレン系ポリマー、ポリイミド、ポリカーボネート、ジシクロペンタジエン等のシクロオレフィン系樹脂、ポリエチレンテレフタレート等のポリエステル、ポリエチレン、ポリスチレン等の樹脂基材等を挙げることができる。尚、リッドと基板には、同一の基材を用いることができる。その場合、有機ＥＬ素子が設置されている方を基板と称し、有機ＥＬ素子が設置されていない方をリッドと称する。
It is preferable to use a moisture-proof substrate as the lid (lid) or substrate, for example, a glass substrate such as soda glass or non-alkali glass; a metal substrate such as stainless steel or aluminum; Polyfluorinated ethylene polymers such as fluorinated ethylene chloride (PCTFE), polyvinylidene fluoride (PVDF), copolymers of PCTFE and PVDF, copolymers of PVDF and polyfluorinated ethylene chloride, polyimide, polycarbonate, dicyclo Examples thereof include cycloolefin resins such as pentadiene, polyesters such as polyethylene terephthalate, and resin base materials such as polyethylene and polystyrene. The same base material can be used for the lid and the substrate. In that case, the direction in which the organic EL element is installed is referred to as a substrate, and the direction in which the organic EL element is not installed is referred to as a lid.
前記有機ＥＬ素子には、陽極／発光層／負極の積層体が含まれる。必要に応じてＳｉＮ膜等のパッシベーション膜を設けてもよい。
The organic EL element includes an anode / light emitting layer / negative electrode laminate. If necessary, a passivation film such as a SiN film may be provided.
本発明の樹脂組成物からなる塗膜は、例えば、リッド（蓋）上にダム材を塗布してダムを形成し、そのダム内にディスペンサー等の液体定量吐出装置やインクジェット塗布装置等を使用して前記樹脂組成物を吐出することにより形成することができる。塗膜の厚みは、有機ＥＬ素子を水分等から保護する目的を達成することができる範囲であれば特に制限されることはない。また、本発明の樹脂組成物はアセトン溶解性に優れるため、前記装置等は、その内部をアセトンを使用して容易に洗浄することができる。
The coating film made of the resin composition of the present invention, for example, forms a dam by applying a dam material on a lid (lid), and uses a liquid dispensing apparatus such as a dispenser or an inkjet coating apparatus in the dam. And can be formed by discharging the resin composition. The thickness of the coating film is not particularly limited as long as the purpose of protecting the organic EL element from moisture and the like can be achieved. Moreover, since the resin composition of this invention is excellent in acetone solubility, the said apparatus etc. can wash | clean the inside easily using acetone.
上記方法によれば、本発明の樹脂組成物からなる塗膜に紫外線を照射することにより、樹脂組成物の流動性を適度に低下させてから有機ＥＬ素子と貼り合わせるため、貼り合わせ時に樹脂組成物がダムから流出することを防止することができる。また、貼り合わせ後に加熱処理を施すことにより、紫外線に曝すことなく有機ＥＬ素子を封止することができ、有機ＥＬ素子は紫外線による劣化を有さない。また、貼り合わせ後に加熱処理を施して硬化反応を再開させるため、貼り合わせ作業が遅滞しても、貼り合わせ困難となることもない。そして、高屈折率、低透湿性、及び低アウトガス性を併せて有する硬化物で有機ＥＬ素子を封止して、有機ＥＬ素子を保護することができる。従って、上記方法により有機ＥＬ素子を封止して得られる有機ＥＬデバイスは、長寿命で信頼性が高い。
According to the above method, the resin composition at the time of bonding is bonded to the organic EL element after the fluidity of the resin composition is appropriately reduced by irradiating the coating film made of the resin composition of the present invention with ultraviolet rays. Things can be prevented from flowing out of the dam. In addition, by performing heat treatment after bonding, the organic EL element can be sealed without being exposed to ultraviolet rays, and the organic EL elements do not have deterioration due to ultraviolet rays. In addition, since the curing reaction is resumed by performing the heat treatment after the bonding, even if the bonding work is delayed, the bonding is not difficult. And an organic EL element can be sealed with the hardened | cured material which has high refractive index, low moisture permeability, and low outgassing property together, and can protect an organic EL element. Therefore, the organic EL device obtained by sealing the organic EL element by the above method has a long life and high reliability.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。尚、樹脂組成物の粘度は、レオメーター（商品名「Physica MCR301」、Anton Paar社製）を使用して測定した、２５℃、せん断速度が２０（１／ｓ）の時の値である。
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The viscosity of the resin composition is a value measured at 25 ° C. and a shear rate of 20 (1 / s) using a rheometer (trade name “Physica® MCR301”, manufactured by Anton® Paar).
製造例１
冷却管、撹拌器、及び温度計を備え付けた２Ｌの４口フラスコに水素化ナトリウム（５５重量％のミネラルオイルを含む）（１５．４ｇ、３５２．９ｍｍｏｌ）、及びＤＭＳＯ（５１０．６ｇ）を入れ、０℃に冷却した後、ここに、ｏ－フェニルフェノール（５０．６ｇ、２９７．３ｍｍｏｌ）をＤＭＳＯ（１９１．０ｇ）に溶解させた溶液を滴下した。その後、６０℃のオイルバスにつけ、２－クロロエチルビニルエーテル（３８．２ｇ、３５８．５ｍｍｏｌ）をＤＭＳＯ（６１．４ｇ）に溶解させた溶液を滴下した。反応液を６時間攪拌後、０℃に冷却してからゆっくり水を滴下してクエンチし、分液ロートに移した。水層を酢酸エチルで抽出し、有機層に飽和食塩水を加え洗浄した。その後、有機層を分け、無水硫酸ナトリウムで脱水した後、溶媒を留去して液状の粗生成物を得た。これをシリカゲルカラムクロマトグラフィー［展開溶媒：ヘキサン／酢酸エチル＝１０／１（体積比）］で精製して、下記式で表される、（２－フェニルフェノキシ）エチルビニルエーテル５５．５ｇ（収率：７８％、純度９８％）を無色透明液体として得た。
1H-NMR(500MHz,CDCl3):δ3.96(t,J=5.0Hz,2H)、4.17-4.21(m,3H)、6.44(dd,J=14.1,6.5Hz,1H)、6.98-7.01(m,1H)、7.04-7.07(m,1H)、7.28-7.41(m,6H)、7.56-7.57(m,2H)
Production Example 1
A 2 L 4-neck flask equipped with a condenser, stirrer, and thermometer was charged with sodium hydride (containing 55 wt% mineral oil) (15.4 g, 352.9 mmol), and DMSO (510.6 g). After cooling to 0 ° C., a solution in which o-phenylphenol (50.6 g, 297.3 mmol) was dissolved in DMSO (191.0 g) was added dropwise thereto. Thereafter, it was placed in an oil bath at 60 ° C., and a solution of 2-chloroethyl vinyl ether (38.2 g, 358.5 mmol) dissolved in DMSO (61.4 g) was added dropwise. The reaction solution was stirred for 6 hours, then cooled to 0 ° C., and then slowly quenched by dropwise addition of water, and transferred to a separatory funnel. The aqueous layer was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Thereafter, the organic layer was separated and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off to obtain a liquid crude product. This was purified by silica gel column chromatography [developing solvent: hexane / ethyl acetate = 10/1 (volume ratio)], and 55.5 g of (2-phenylphenoxy) ethyl vinyl ether represented by the following formula (yield: 78%, purity 98%) was obtained as a colorless transparent liquid.
1 H-NMR (500 MHz, CDCl 3 ): δ 3.96 (t, J = 5.0 Hz, 2H), 4.17-4.21 (m, 3H), 6.44 (dd, J = 14.1, 6.5 Hz, 1H), 6.98- 7.01 (m, 1H), 7.04-7.07 (m, 1H), 7.28-7.41 (m, 6H), 7.56-7.57 (m, 2H)
冷却管、撹拌器、及び温度計を備え付けた２Ｌの４口フラスコに水素化ナトリウム（５５重量％のミネラルオイルを含む）（１５．４ｇ、３５２．９ｍｍｏｌ）、及びＤＭＳＯ（５１０．６ｇ）を入れ、０℃に冷却した後、ここに、ｏ－フェニルフェノール（５０．６ｇ、２９７．３ｍｍｏｌ）をＤＭＳＯ（１９１．０ｇ）に溶解させた溶液を滴下した。その後、６０℃のオイルバスにつけ、２－クロロエチルビニルエーテル（３８．２ｇ、３５８．５ｍｍｏｌ）をＤＭＳＯ（６１．４ｇ）に溶解させた溶液を滴下した。反応液を６時間攪拌後、０℃に冷却してからゆっくり水を滴下してクエンチし、分液ロートに移した。水層を酢酸エチルで抽出し、有機層に飽和食塩水を加え洗浄した。その後、有機層を分け、無水硫酸ナトリウムで脱水した後、溶媒を留去して液状の粗生成物を得た。これをシリカゲルカラムクロマトグラフィー［展開溶媒：ヘキサン／酢酸エチル＝１０／１（体積比）］で精製して、下記式で表される、（２－フェニルフェノキシ）エチルビニルエーテル５５．５ｇ（収率：７８％、純度９８％）を無色透明液体として得た。
1H-NMR(500MHz,CDCl3):δ3.96(t,J=5.0Hz,2H)、4.17-4.21(m,3H)、6.44(dd,J=14.1,6.5Hz,1H)、6.98-7.01(m,1H)、7.04-7.07(m,1H)、7.28-7.41(m,6H)、7.56-7.57(m,2H)
A 2 L 4-neck flask equipped with a condenser, stirrer, and thermometer was charged with sodium hydride (containing 55 wt% mineral oil) (15.4 g, 352.9 mmol), and DMSO (510.6 g). After cooling to 0 ° C., a solution in which o-phenylphenol (50.6 g, 297.3 mmol) was dissolved in DMSO (191.0 g) was added dropwise thereto. Thereafter, it was placed in an oil bath at 60 ° C., and a solution of 2-chloroethyl vinyl ether (38.2 g, 358.5 mmol) dissolved in DMSO (61.4 g) was added dropwise. The reaction solution was stirred for 6 hours, then cooled to 0 ° C., and then slowly quenched by dropwise addition of water, and transferred to a separatory funnel. The aqueous layer was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Thereafter, the organic layer was separated and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off to obtain a liquid crude product. This was purified by silica gel column chromatography [developing solvent: hexane / ethyl acetate = 10/1 (volume ratio)], and 55.5 g of (2-phenylphenoxy) ethyl vinyl ether represented by the following formula (yield: 78%, purity 98%) was obtained as a colorless transparent liquid.
1 H-NMR (500 MHz, CDCl 3 ): δ 3.96 (t, J = 5.0 Hz, 2H), 4.17-4.21 (m, 3H), 6.44 (dd, J = 14.1, 6.5 Hz, 1H), 6.98- 7.01 (m, 1H), 7.04-7.07 (m, 1H), 7.28-7.41 (m, 6H), 7.56-7.57 (m, 2H)
実施例１
ＭＰＶ（８２重量部）、ＶＣＺ（１７重量部）、及び光カチオン重合開始剤（１重量部）を自公転式撹拌脱泡装置（型式：ＡＲ－２５０、（株）シンキー製）内に投入して撹拌し、樹脂組成物（１）を得た。
得られた樹脂組成物（１）を金型に注型し、２００Ｗ／ｃｍの高圧水銀灯で１０ｃｍの距離から紫外線を照射（照射量：１５００ｍＪ／ｃｍ2）した。
得られた樹脂組成物（１）について、紫外線照射前、紫外線照射直後、及び紫外線照射後３０分の粘度をそれぞれ測定し、紫外線照射後の粘度上昇度を下記式から算出した。
紫外線照射後の粘度上昇度＝紫外線照射後３０分の粘度／紫外線照射直後の粘度
また、紫外線照射後の樹脂組成物（１）に加熱処理（１００℃、１時間）を施して硬化物（１）（厚み：１００μｍ）を得た。 Example 1
MPV (82 parts by weight), VCZ (17 parts by weight), and a photocationic polymerization initiator (1 part by weight) were put into a self-revolving stirring and deaerator (model: AR-250, manufactured by Shinky Corporation). And stirred to obtain a resin composition (1).
The obtained resin composition (1) was poured into a mold and irradiated with ultraviolet rays from a distance of 10 cm with a 200 W / cm high-pressure mercury lamp (irradiation amount: 1500 mJ / cm 2 ).
About the obtained resin composition (1), the viscosity before ultraviolet irradiation, immediately after ultraviolet irradiation, and 30 minutes after ultraviolet irradiation was measured, respectively, and the viscosity raise degree after ultraviolet irradiation was computed from the following formula.
Viscosity increase degree after ultraviolet irradiation = viscosity 30 minutes after ultraviolet irradiation / viscosity immediately after ultraviolet irradiation Further, the resin composition (1) after ultraviolet irradiation is subjected to heat treatment (100 ° C., 1 hour) to obtain a cured product (1 ) (Thickness: 100 μm).
ＭＰＶ（８２重量部）、ＶＣＺ（１７重量部）、及び光カチオン重合開始剤（１重量部）を自公転式撹拌脱泡装置（型式：ＡＲ－２５０、（株）シンキー製）内に投入して撹拌し、樹脂組成物（１）を得た。
得られた樹脂組成物（１）を金型に注型し、２００Ｗ／ｃｍの高圧水銀灯で１０ｃｍの距離から紫外線を照射（照射量：１５００ｍＪ／ｃｍ2）した。
得られた樹脂組成物（１）について、紫外線照射前、紫外線照射直後、及び紫外線照射後３０分の粘度をそれぞれ測定し、紫外線照射後の粘度上昇度を下記式から算出した。
紫外線照射後の粘度上昇度＝紫外線照射後３０分の粘度／紫外線照射直後の粘度
また、紫外線照射後の樹脂組成物（１）に加熱処理（１００℃、１時間）を施して硬化物（１）（厚み：１００μｍ）を得た。 Example 1
MPV (82 parts by weight), VCZ (17 parts by weight), and a photocationic polymerization initiator (1 part by weight) were put into a self-revolving stirring and deaerator (model: AR-250, manufactured by Shinky Corporation). And stirred to obtain a resin composition (1).
The obtained resin composition (1) was poured into a mold and irradiated with ultraviolet rays from a distance of 10 cm with a 200 W / cm high-pressure mercury lamp (irradiation amount: 1500 mJ / cm 2 ).
About the obtained resin composition (1), the viscosity before ultraviolet irradiation, immediately after ultraviolet irradiation, and 30 minutes after ultraviolet irradiation was measured, respectively, and the viscosity raise degree after ultraviolet irradiation was computed from the following formula.
Viscosity increase degree after ultraviolet irradiation = viscosity 30 minutes after ultraviolet irradiation / viscosity immediately after ultraviolet irradiation Further, the resin composition (1) after ultraviolet irradiation is subjected to heat treatment (100 ° C., 1 hour) to obtain a cured product (1 ) (Thickness: 100 μm).
実施例２～７、比較例１～３
下記表に示す組成に変更した以外は実施例１と同様にして樹脂組成物及び硬化物を作製した。 Examples 2 to 7, Comparative Examples 1 to 3
A resin composition and a cured product were prepared in the same manner as in Example 1 except that the composition shown in the following table was changed.
下記表に示す組成に変更した以外は実施例１と同様にして樹脂組成物及び硬化物を作製した。 Examples 2 to 7, Comparative Examples 1 to 3
A resin composition and a cured product were prepared in the same manner as in Example 1 except that the composition shown in the following table was changed.
＜アセトン溶解性＞
実施例及び比較例で得られた樹脂組成物１ｇに対しアセトン１００ｍＬを添加し、マグネチックスターラーを用いて２５℃で１時間攪拌して得られたアセトン溶液について、透明性を目視で確認することにより、樹脂組成物のアセトン溶解性を評価した。 <Acetone solubility>
100 mL of acetone is added to 1 g of the resin compositions obtained in the examples and comparative examples, and the transparency of the acetone solution obtained by stirring at 25 ° C. for 1 hour using a magnetic stirrer is visually confirmed. Thus, the acetone solubility of the resin composition was evaluated.
実施例及び比較例で得られた樹脂組成物１ｇに対しアセトン１００ｍＬを添加し、マグネチックスターラーを用いて２５℃で１時間攪拌して得られたアセトン溶液について、透明性を目視で確認することにより、樹脂組成物のアセトン溶解性を評価した。 <Acetone solubility>
100 mL of acetone is added to 1 g of the resin compositions obtained in the examples and comparative examples, and the transparency of the acetone solution obtained by stirring at 25 ° C. for 1 hour using a magnetic stirrer is visually confirmed. Thus, the acetone solubility of the resin composition was evaluated.
＜ダムからの流出防止性＞
ＵＶ遅延硬化性ダム材の調製
（３，４，３’，４’－ジエポキシ）ビシクロヘキシル３０重量部、液状ビスフェノールＦジグリシジルエーテル（商品名「ＹＬ－９８３Ｕ」、三菱化学（株）製）７０重量部、４－（４－ビフェニリルチオ）フェニル－４－ビフェニリル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２重量部、１，３，４，６－テトラグリシジルグリコールウリル（商品名「ＴＧ－Ｇ」、四国化成工業（株）製）２．５重量部、タルク（平均粒子径１．５μｍ、平板状粒子、商品名「ＦＧ－１５」、日本タルク（株）製）５２重量部、スペーサー粒子（平均粒子径１５μｍ、商品名「ＳＤ－ＤＢ」、早川ゴム（株）製）０．５重量部を自公転式撹拌脱泡装置（型式：ＡＲ－２５０、（株）シンキー製）内に投入して撹拌し、ＵＶ遅延硬化性ダム材を得た。
得られたＵＶ遅延硬化性ダム材の粘度は１５０Ｐａ・ｓであった。また、このＵＶ遅延硬化性ダム材を２００Ｗ／ｃｍの高圧水銀灯で１０ｃｍの距離から紫外線を照射（照射量：１５００ｍＪ／ｃｍ2）した直後の粘度は１５０００００Ｐａ・ｓであった。さらに、紫外線照射後３０分の粘度は１５７００００Ｐａ・ｓであった。尚、ダム材の粘度は、レオメーター（商品名「Physica MCR301」、Anton Paar社製）を使用して測定した、２５℃、せん断速度が２．５（１／ｓ）の時の値である。 <Outflow prevention from dam>
Preparation of UV delayed curing dam material (3,4,3 ′, 4′-diepoxy) 30 parts by weight of bicyclohexyl, liquid bisphenol F diglycidyl ether (trade name “YL-983U”, manufactured by Mitsubishi Chemical Corporation) 70 Parts by weight, 2- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, 1,3,4,6-tetraglycidylglycoluril (trade name "TG-G ”, 2.5 parts by weight, manufactured by Shikoku Kasei Kogyo Co., Ltd., talc (average particle size 1.5 μm, tabular particles, trade name“ FG-15 ”, manufactured by Nippon Talc Co., Ltd.), 52 parts by weight, spacer particles (Average particle size 15 μm, trade name “SD-DB”, manufactured by Hayakawa Rubber Co., Ltd.) 0.5 parts by weight in a self-revolving stirring deaerator (model: AR-250, manufactured by Shinky Co., Ltd.) Charged and stirred to obtain a UV delay curable dam member.
The viscosity of the obtained UV delayed dam material was 150 Pa · s. Further, the viscosity immediately after the UV delayed dam material was irradiated with ultraviolet rays from a distance of 10 cm with a 200 W / cm high-pressure mercury lamp (irradiation amount: 1500 mJ / cm 2 ) was 1500,000 Pa · s. Furthermore, the viscosity for 30 minutes after the ultraviolet irradiation was 1570000 Pa · s. The viscosity of the dam material is a value measured using a rheometer (trade name “Physica MCR301”, manufactured by Anton Paar) at 25 ° C. and a shear rate of 2.5 (1 / s). .
ＵＶ遅延硬化性ダム材の調製
（３，４，３’，４’－ジエポキシ）ビシクロヘキシル３０重量部、液状ビスフェノールＦジグリシジルエーテル（商品名「ＹＬ－９８３Ｕ」、三菱化学（株）製）７０重量部、４－（４－ビフェニリルチオ）フェニル－４－ビフェニリル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２重量部、１，３，４，６－テトラグリシジルグリコールウリル（商品名「ＴＧ－Ｇ」、四国化成工業（株）製）２．５重量部、タルク（平均粒子径１．５μｍ、平板状粒子、商品名「ＦＧ－１５」、日本タルク（株）製）５２重量部、スペーサー粒子（平均粒子径１５μｍ、商品名「ＳＤ－ＤＢ」、早川ゴム（株）製）０．５重量部を自公転式撹拌脱泡装置（型式：ＡＲ－２５０、（株）シンキー製）内に投入して撹拌し、ＵＶ遅延硬化性ダム材を得た。
得られたＵＶ遅延硬化性ダム材の粘度は１５０Ｐａ・ｓであった。また、このＵＶ遅延硬化性ダム材を２００Ｗ／ｃｍの高圧水銀灯で１０ｃｍの距離から紫外線を照射（照射量：１５００ｍＪ／ｃｍ2）した直後の粘度は１５０００００Ｐａ・ｓであった。さらに、紫外線照射後３０分の粘度は１５７００００Ｐａ・ｓであった。尚、ダム材の粘度は、レオメーター（商品名「Physica MCR301」、Anton Paar社製）を使用して測定した、２５℃、せん断速度が２．５（１／ｓ）の時の値である。 <Outflow prevention from dam>
Preparation of UV delayed curing dam material (3,4,3 ′, 4′-diepoxy) 30 parts by weight of bicyclohexyl, liquid bisphenol F diglycidyl ether (trade name “YL-983U”, manufactured by Mitsubishi Chemical Corporation) 70 Parts by weight, 2- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, 1,3,4,6-tetraglycidylglycoluril (trade name "TG-G ”, 2.5 parts by weight, manufactured by Shikoku Kasei Kogyo Co., Ltd., talc (average particle size 1.5 μm, tabular particles, trade name“ FG-15 ”, manufactured by Nippon Talc Co., Ltd.), 52 parts by weight, spacer particles (Average particle size 15 μm, trade name “SD-DB”, manufactured by Hayakawa Rubber Co., Ltd.) 0.5 parts by weight in a self-revolving stirring deaerator (model: AR-250, manufactured by Shinky Co., Ltd.) Charged and stirred to obtain a UV delay curable dam member.
The viscosity of the obtained UV delayed dam material was 150 Pa · s. Further, the viscosity immediately after the UV delayed dam material was irradiated with ultraviolet rays from a distance of 10 cm with a 200 W / cm high-pressure mercury lamp (irradiation amount: 1500 mJ / cm 2 ) was 1500,000 Pa · s. Furthermore, the viscosity for 30 minutes after the ultraviolet irradiation was 1570000 Pa · s. The viscosity of the dam material is a value measured using a rheometer (trade name “Physica MCR301”, manufactured by Anton Paar) at 25 ° C. and a shear rate of 2.5 (1 / s). .
ガラス（７６ｍｍ×５２ｍｍ）表面に、オートディスペンサーを用いて前記ＵＶ遅延硬化性ダム材を塗布して５０ｍｍ×３５ｍｍのダムを形成し、前記ダム内にフィル材（実施例又は比較例で得られた樹脂組成物）を、ダムから５ｍｍ以上離れた箇所に１滴ずつ、液滴が接しないよう少し離して、計１５滴（８０～１２０ｍｇ）滴下した。
２００Ｗ／ｃｍの高圧水銀灯を用いて、ガラス面から１０ｃｍ離れたところから紫外線を照射（照射量：１５００ｍＪ／ｃｍ2）した。
３０分後、前記ガラス表面にもう１枚のガラス（７６ｍｍ×５２ｍｍ）を被せ、クリップで２枚のガラスをはさみ、真空チャンバーにて２．５ｔｏｒｒの圧力で貼り合わせた。貼り合わせたガラスを１００℃で１時間加熱することにより、ダムアンドフィル工法で封止されたガラス試験片を得た。ガラス試験片におけるダムとフィルの境界部をＣＣＤカメラにて観察し、下記基準でダムの流出防止性を評価した。
評価基準
○：フィルが流出するのを完全に防止できた
△：フィルが少量流出した
×：フィルが多量に流出した The UV delayed curing dam material was applied to the glass (76 mm × 52 mm) surface using an auto dispenser to form a 50 mm × 35 mm dam, and the fill material (obtained in Examples or Comparative Examples) was formed in the dam. A total of 15 drops (80 to 120 mg) of the resin composition) were dropped one by one at a distance of 5 mm or more from the dam so that the drops did not touch.
Using a 200 W / cm high-pressure mercury lamp, ultraviolet rays were irradiated from a location 10 cm away from the glass surface (irradiation amount: 1500 mJ / cm 2 ).
After 30 minutes, another glass (76 mm × 52 mm) was placed on the glass surface, the two glasses were sandwiched with clips, and were bonded together in a vacuum chamber at a pressure of 2.5 torr. The bonded glass was heated at 100 ° C. for 1 hour to obtain a glass test piece sealed by the dam and fill method. The boundary between the dam and the fill in the glass test piece was observed with a CCD camera, and the dam outflow prevention property was evaluated according to the following criteria.
Evaluation criteria ○: The outflow of fill was completely prevented. Δ: A small amount of fill flowed out. X: A large amount of fill flowed out.
２００Ｗ／ｃｍの高圧水銀灯を用いて、ガラス面から１０ｃｍ離れたところから紫外線を照射（照射量：１５００ｍＪ／ｃｍ2）した。
３０分後、前記ガラス表面にもう１枚のガラス（７６ｍｍ×５２ｍｍ）を被せ、クリップで２枚のガラスをはさみ、真空チャンバーにて２．５ｔｏｒｒの圧力で貼り合わせた。貼り合わせたガラスを１００℃で１時間加熱することにより、ダムアンドフィル工法で封止されたガラス試験片を得た。ガラス試験片におけるダムとフィルの境界部をＣＣＤカメラにて観察し、下記基準でダムの流出防止性を評価した。
評価基準
○：フィルが流出するのを完全に防止できた
△：フィルが少量流出した
×：フィルが多量に流出した The UV delayed curing dam material was applied to the glass (76 mm × 52 mm) surface using an auto dispenser to form a 50 mm × 35 mm dam, and the fill material (obtained in Examples or Comparative Examples) was formed in the dam. A total of 15 drops (80 to 120 mg) of the resin composition) were dropped one by one at a distance of 5 mm or more from the dam so that the drops did not touch.
Using a 200 W / cm high-pressure mercury lamp, ultraviolet rays were irradiated from a location 10 cm away from the glass surface (irradiation amount: 1500 mJ / cm 2 ).
After 30 minutes, another glass (76 mm × 52 mm) was placed on the glass surface, the two glasses were sandwiched with clips, and were bonded together in a vacuum chamber at a pressure of 2.5 torr. The bonded glass was heated at 100 ° C. for 1 hour to obtain a glass test piece sealed by the dam and fill method. The boundary between the dam and the fill in the glass test piece was observed with a CCD camera, and the dam outflow prevention property was evaluated according to the following criteria.
Evaluation criteria ○: The outflow of fill was completely prevented. Δ: A small amount of fill flowed out. X: A large amount of fill flowed out.
＜屈折率の測定＞
実施例及び比較例で得られた硬化物（厚み：１００μｍ）について、Ｍｏｄｅｌ ２０１０プリズムカプラ（メトリコン社製）を使用して、２５℃において、５８９．３ｎｍの光の屈折率を測定した。 <Measurement of refractive index>
About the cured | curing material (thickness: 100 micrometers) obtained by the Example and the comparative example, the refractive index of 589.3 nm light was measured at 25 degreeC using Model 2010 prism coupler (made by Metricon).
実施例及び比較例で得られた硬化物（厚み：１００μｍ）について、Ｍｏｄｅｌ ２０１０プリズムカプラ（メトリコン社製）を使用して、２５℃において、５８９．３ｎｍの光の屈折率を測定した。 <Measurement of refractive index>
About the cured | curing material (thickness: 100 micrometers) obtained by the Example and the comparative example, the refractive index of 589.3 nm light was measured at 25 degreeC using Model 2010 prism coupler (made by Metricon).
＜アウトガス量＞
実施例及び比較例で得られた硬化物（６０ｍｇ）をバイヤル瓶に入れ、紫外線照射（１５００ｍＪ／ｃｍ2）して１００℃の条件下で１時間静置した後、バイヤル瓶中のアウトガス量（単位：ｐｐｍ）を測定した。尚、トルエン標準液［標準物質としてトルエン：１００ｐｐｍ、溶媒としてヘキサン：６０ｍｇ］を用いて検量線を作成した。また、測定機器としては、商品名「ＨＰ－６８９０Ｎ」（ヒューレットパッカート社製）を使用し、カラムは商品名「ＤＢ－６２４」（アジレント社製）を使用した。 <Outgas amount>
The cured products (60 mg) obtained in Examples and Comparative Examples were put into a vial, and irradiated with ultraviolet rays (1500 mJ / cm 2 ) and allowed to stand at 100 ° C. for 1 hour, and then the amount of outgas in the vial ( Unit: ppm) was measured. A calibration curve was prepared using a toluene standard solution [toluene: 100 ppm as a standard substance and hexane: 60 mg as a solvent]. In addition, a trade name “HP-6890N” (manufactured by Hewlett-Packard) was used as the measuring instrument, and a trade name “DB-624” (manufactured by Agilent) was used as the column.
実施例及び比較例で得られた硬化物（６０ｍｇ）をバイヤル瓶に入れ、紫外線照射（１５００ｍＪ／ｃｍ2）して１００℃の条件下で１時間静置した後、バイヤル瓶中のアウトガス量（単位：ｐｐｍ）を測定した。尚、トルエン標準液［標準物質としてトルエン：１００ｐｐｍ、溶媒としてヘキサン：６０ｍｇ］を用いて検量線を作成した。また、測定機器としては、商品名「ＨＰ－６８９０Ｎ」（ヒューレットパッカート社製）を使用し、カラムは商品名「ＤＢ－６２４」（アジレント社製）を使用した。 <Outgas amount>
The cured products (60 mg) obtained in Examples and Comparative Examples were put into a vial, and irradiated with ultraviolet rays (1500 mJ / cm 2 ) and allowed to stand at 100 ° C. for 1 hour, and then the amount of outgas in the vial ( Unit: ppm) was measured. A calibration curve was prepared using a toluene standard solution [toluene: 100 ppm as a standard substance and hexane: 60 mg as a solvent]. In addition, a trade name “HP-6890N” (manufactured by Hewlett-Packard) was used as the measuring instrument, and a trade name “DB-624” (manufactured by Agilent) was used as the column.
＜水蒸気透過性＞
実施例及び比較例で得られた硬化物（厚み：１００μｍ）の透湿量（ｇ／ｍ2・ｄａｙ・ａｔｍ）を、ＪＩＳ Ｌ １０９９及びＪＩＳ Ｚ ０２０８（カップ法）に準じた方法で、６０℃、９０％ＲＨ条件下で測定して水蒸気透過性を評価した。 <Water vapor permeability>
The moisture permeation amount (g / m 2 · day · atm) of the cured products (thickness: 100 μm) obtained in the examples and comparative examples was determined according to JIS L 1099 and JIS Z 0208 (cup method). Water vapor permeability was evaluated by measurement under the conditions of 90 ° C. and 90% RH.
実施例及び比較例で得られた硬化物（厚み：１００μｍ）の透湿量（ｇ／ｍ2・ｄａｙ・ａｔｍ）を、ＪＩＳ Ｌ １０９９及びＪＩＳ Ｚ ０２０８（カップ法）に準じた方法で、６０℃、９０％ＲＨ条件下で測定して水蒸気透過性を評価した。 <Water vapor permeability>
The moisture permeation amount (g / m 2 · day · atm) of the cured products (thickness: 100 μm) obtained in the examples and comparative examples was determined according to JIS L 1099 and JIS Z 0208 (cup method). Water vapor permeability was evaluated by measurement under the conditions of 90 ° C. and 90% RH.
実施例及び比較例で用いた化合物は、以下の通りである。
［化合物（Ａ）］
ＭＰＶ：ビス（４－ビニルチオフェニル）スルフィド、分子量：３０２、商品名「ＭＰＶ」、住友精化（株）製
［化合物（Ｂ）］
ＶＣＺ：Ｎ－ビニルカルバゾール、分子量：１９３．２４、商品名「ＨＲＭ－Ｃ０１」、日触テクノファインケミカル（株）製
ＡＣＺ：Ｎ－アリルカルバゾール、分子量：２０７．１６、日触テクノファインケミカル（株）製
ＯＰＰ－ＥＯ－ＶＥ：調製例１で得られた（２－フェニルフェノキシ）エチルビニルエーテル、分子量：２４０．１６
ＨＲＤ－０１：２－（ｏ－フェニルフェノキシ）エチルアクリレート、分子量：２６８、商品名「ＨＲＤ－０１」、日触テクノファインケミカル（株）製
［その他の硬化性化合物］
ＳＹ－ＯＰＧ：ｏ－フェニルフェノールグリシジルエーテル、商品名「ＳＹ－ＯＰＧ」、阪本薬品工業（株）製
［非硬化性化合物］
ＰＶＣＺ：ポリ－Ｎ－ビニルカルバゾール、重量平均分子量：４５０００、２５℃におけるＳＰ値：５．６、商品名「ＰＶＣＺ」、丸善石油化学（株）製
ネオポリマー１２０：石油樹脂、重量平均分子量：１５００、２５℃におけるＳＰ値：１１．２、商品名「ネオポリマー１２０」、ＪＸ日鉱日石エネルギー（株）製
［光カチオン重合開始剤（Ｃ）］
光カチオン重合開始剤：４－（４－ビフェニリルチオ）フェニル－４－ビフェニリル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 The compounds used in Examples and Comparative Examples are as follows.
[Compound (A)]
MPV: bis (4-vinylthiophenyl) sulfide, molecular weight: 302, trade name “MPV”, manufactured by Sumitomo Seika Co., Ltd. [compound (B)]
VCZ: N-vinylcarbazole, molecular weight: 193.24, trade name “HRM-C01”, manufactured by Nippon Touche Technofine Chemical Co., Ltd. ACZ: N-allylcarbazole, molecular weight: 207.16, manufactured by Nippon Touche Technofine Chemical Co., Ltd. OPP-EO-VE: (2-phenylphenoxy) ethyl vinyl ether obtained in Preparation Example 1, molecular weight: 240.16
HRD-01: 2- (o-phenylphenoxy) ethyl acrylate, molecular weight: 268, trade name “HRD-01”, manufactured by Nippon Touch Technofine Chemical Co., Ltd. [other curable compounds]
SY-OPG: o-phenylphenol glycidyl ether, trade name “SY-OPG”, manufactured by Sakamoto Pharmaceutical Co., Ltd. [non-curable compound]
PVCZ: poly-N-vinylcarbazole, weight average molecular weight: 45000, SP value at 25 ° C .: 5.6, trade name “PVCZ”, Maruzen Petrochemical Co., Ltd. Neopolymer 120: petroleum resin, weight average molecular weight: 1500 SP value at 25 ° C .: 11.2, trade name “Neopolymer 120”, manufactured by JX Nippon Mining & Energy Corporation [Photocationic polymerization initiator (C)]
Photocationic polymerization initiator: 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate
［化合物（Ａ）］
ＭＰＶ：ビス（４－ビニルチオフェニル）スルフィド、分子量：３０２、商品名「ＭＰＶ」、住友精化（株）製
［化合物（Ｂ）］
ＶＣＺ：Ｎ－ビニルカルバゾール、分子量：１９３．２４、商品名「ＨＲＭ－Ｃ０１」、日触テクノファインケミカル（株）製
ＡＣＺ：Ｎ－アリルカルバゾール、分子量：２０７．１６、日触テクノファインケミカル（株）製
ＯＰＰ－ＥＯ－ＶＥ：調製例１で得られた（２－フェニルフェノキシ）エチルビニルエーテル、分子量：２４０．１６
ＨＲＤ－０１：２－（ｏ－フェニルフェノキシ）エチルアクリレート、分子量：２６８、商品名「ＨＲＤ－０１」、日触テクノファインケミカル（株）製
［その他の硬化性化合物］
ＳＹ－ＯＰＧ：ｏ－フェニルフェノールグリシジルエーテル、商品名「ＳＹ－ＯＰＧ」、阪本薬品工業（株）製
［非硬化性化合物］
ＰＶＣＺ：ポリ－Ｎ－ビニルカルバゾール、重量平均分子量：４５０００、２５℃におけるＳＰ値：５．６、商品名「ＰＶＣＺ」、丸善石油化学（株）製
ネオポリマー１２０：石油樹脂、重量平均分子量：１５００、２５℃におけるＳＰ値：１１．２、商品名「ネオポリマー１２０」、ＪＸ日鉱日石エネルギー（株）製
［光カチオン重合開始剤（Ｃ）］
光カチオン重合開始剤：４－（４－ビフェニリルチオ）フェニル－４－ビフェニリル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 The compounds used in Examples and Comparative Examples are as follows.
[Compound (A)]
MPV: bis (4-vinylthiophenyl) sulfide, molecular weight: 302, trade name “MPV”, manufactured by Sumitomo Seika Co., Ltd. [compound (B)]
VCZ: N-vinylcarbazole, molecular weight: 193.24, trade name “HRM-C01”, manufactured by Nippon Touche Technofine Chemical Co., Ltd. ACZ: N-allylcarbazole, molecular weight: 207.16, manufactured by Nippon Touche Technofine Chemical Co., Ltd. OPP-EO-VE: (2-phenylphenoxy) ethyl vinyl ether obtained in Preparation Example 1, molecular weight: 240.16
HRD-01: 2- (o-phenylphenoxy) ethyl acrylate, molecular weight: 268, trade name “HRD-01”, manufactured by Nippon Touch Technofine Chemical Co., Ltd. [other curable compounds]
SY-OPG: o-phenylphenol glycidyl ether, trade name “SY-OPG”, manufactured by Sakamoto Pharmaceutical Co., Ltd. [non-curable compound]
PVCZ: poly-N-vinylcarbazole, weight average molecular weight: 45000, SP value at 25 ° C .: 5.6, trade name “PVCZ”, Maruzen Petrochemical Co., Ltd. Neopolymer 120: petroleum resin, weight average molecular weight: 1500 SP value at 25 ° C .: 11.2, trade name “Neopolymer 120”, manufactured by JX Nippon Mining & Energy Corporation [Photocationic polymerization initiator (C)]
Photocationic polymerization initiator: 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate
本発明の樹脂組成物に紫外線を照射した後に、有機ＥＬ素子を備えた基板に貼り合わせ、貼り合わせ後に加熱処理を施すことにより、ダムからの流出を抑制しつつ、且つ貼り合わせ困難となる事態を生じることなく、貼り合わせ作業を行うことができ、有機ＥＬ素子を紫外線に直に曝すことなく、高屈折率、低透湿性、及び低アウトガス性を兼ね備えた硬化物で封止することができる。
そのため、本発明の樹脂組成物は、トップ・エミッション型有機ＥＬデバイスの封止剤、ボトム・エミッション型有機ＥＬデバイスの光取り出し層材料、太陽電池材料、レンズ材料等として好ましく使用できる。 After irradiating the resin composition of the present invention with ultraviolet rays, it is bonded to a substrate provided with an organic EL element, and heat treatment is performed after the bonding, thereby suppressing the outflow from the dam and making it difficult to bond. The organic EL element can be sealed with a cured product having a high refractive index, a low moisture permeability, and a low outgassing property without being directly exposed to ultraviolet rays. .
Therefore, the resin composition of the present invention can be preferably used as a sealant for top emission type organic EL devices, a light extraction layer material for bottom emission type organic EL devices, a solar cell material, a lens material, and the like.
そのため、本発明の樹脂組成物は、トップ・エミッション型有機ＥＬデバイスの封止剤、ボトム・エミッション型有機ＥＬデバイスの光取り出し層材料、太陽電池材料、レンズ材料等として好ましく使用できる。 After irradiating the resin composition of the present invention with ultraviolet rays, it is bonded to a substrate provided with an organic EL element, and heat treatment is performed after the bonding, thereby suppressing the outflow from the dam and making it difficult to bond. The organic EL element can be sealed with a cured product having a high refractive index, a low moisture permeability, and a low outgassing property without being directly exposed to ultraviolet rays. .
Therefore, the resin composition of the present invention can be preferably used as a sealant for top emission type organic EL devices, a light extraction layer material for bottom emission type organic EL devices, a solar cell material, a lens material, and the like.
１ リッド
２ ダム
３ ディスペンサー
４ 樹脂組成物
５ 基板
６ 陰極
７ 発光層
８ 陽極 1Lid 2 Dam 3 Dispenser 4 Resin Composition 5 Substrate 6 Cathode 7 Light-Emitting Layer 8 Anode
２ ダム
３ ディスペンサー
４ 樹脂組成物
５ 基板
６ 陰極
７ 発光層
８ 陽極 1
Claims (8)
- 下記化合物（Ａ）と下記化合物（Ｂ）と光カチオン重合開始剤（Ｃ）を含む樹脂組成物。
化合物（Ａ）：下記式（ａ）
で表される化合物
化合物（Ｂ）：下記式（b-1）
で表される化合物、及び下記式（b-2）
で表される化合物から選択される少なくとも１種の化合物 The resin composition containing the following compound (A), the following compound (B), and a photocationic polymerization initiator (C).
Compound (A): Formula (a) below
Compound represented by formula (B): Formula (b-1) below
And a compound represented by the following formula (b-2)
At least one compound selected from the compounds represented by - 式（ａ）中のＲaが、ビニル基又はアリル基である請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein R a in the formula (a) is a vinyl group or an allyl group.
- 式（b-2）で表される化合物が、下記式（b-2-1）
で表される化合物である請求項１又は２に記載の樹脂組成物。 The compound represented by the formula (b-2) is represented by the following formula (b-2-1)
The resin composition according to claim 1, wherein the resin composition is represented by the formula: - 化合物（Ａ）と化合物（Ｂ）の含有量の比（前者：後者（重量比））が６０：４０～９５：５であり、化合物（Ａ）と化合物（Ｂ）の合計含有量が、樹脂組成物に含まれる硬化性化合物全量の５０重量％以上である請求項１～３の何れか１項に記載の樹脂組成物。 The ratio of the content of compound (A) to compound (B) (the former: latter (weight ratio)) is 60:40 to 95: 5, and the total content of compound (A) and compound (B) is a resin. The resin composition according to any one of claims 1 to 3, which is 50% by weight or more of the total amount of the curable compound contained in the composition.
- ２５℃における粘度が１０ｍＰａ・ｓ以上、３０ｍＰａ・ｓ未満である請求項１～４の何れか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 4, which has a viscosity at 25 ° C of 10 mPa · s or more and less than 30 mPa · s.
- 有機エレクトロルミネッセンス素子封止剤である請求項１～５の何れか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, which is an organic electroluminescence device sealant.
- 下記工程１及び２を経て有機エレクトロルミネッセンス素子を封止することを特徴とする有機エレクトロルミネッセンスデバイスの製造方法。
工程１：請求項６に記載の樹脂組成物からなる塗膜に、紫外線照射を施す
工程２：有機エレクトロルミネッセンス素子を設置した基板の素子設置面に、工程１を経て得られた紫外線照射後の塗膜を貼り合わせて加熱処理を施す A method for producing an organic electroluminescent device, wherein the organic electroluminescent element is sealed through the following steps 1 and 2.
Step 1: Applying ultraviolet irradiation to the coating film comprising the resin composition according to claim 6 Step 2: Applying ultraviolet light obtained through Step 1 to the device mounting surface of the substrate on which the organic electroluminescence device is mounted Apply the heat treatment by bonding the coating film - 請求項６に記載の樹脂組成物の硬化物で素子が封止された構成を有する有機エレクトロルミネッセンスデバイス。 An organic electroluminescence device having a structure in which an element is sealed with a cured product of the resin composition according to claim 6.
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| KR1020177029440A KR101878117B1 (en) | 2016-04-01 | 2017-03-30 | Resin composition |
| JP2017534757A JP6211746B1 (en) | 2016-04-01 | 2017-03-30 | Resin composition |
| CN201780001410.XA CN107531817B (en) | 2016-04-01 | 2017-03-30 | Resin combination |
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| JP (1) | JP6211746B1 (en) |
| KR (1) | KR101878117B1 (en) |
| CN (1) | CN107531817B (en) |
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| WO (1) | WO2017170888A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019123760A1 (en) * | 2017-12-20 | 2019-06-27 | コニカミノルタ株式会社 | Organic electroluminescent element |
| WO2022203081A1 (en) * | 2021-03-26 | 2022-09-29 | パナソニックＩｐマネジメント株式会社 | Photocurable resin composition, optical component, method for producing optical component, and light emitting device |
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| CN116909061A (en) * | 2021-03-19 | 2023-10-20 | 三井化学株式会社 | Liquid crystal sealing agent, method for manufacturing liquid crystal display panel, and liquid crystal display panel |
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| JP2006003387A (en) * | 2004-06-15 | 2006-01-05 | Daiso Co Ltd | Photosensitive composition for volume phase type hologram recording, hologram recording medium and method for manufacturing same, and hologram recording method |
| JP2006003388A (en) * | 2004-06-15 | 2006-01-05 | Daiso Co Ltd | Photosensitive composition for volume phase type hologram recording, hologram recording medium and method for manufacturing same, and hologram recording method |
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| WO2022203081A1 (en) * | 2021-03-26 | 2022-09-29 | パナソニックＩｐマネジメント株式会社 | Photocurable resin composition, optical component, method for producing optical component, and light emitting device |
Also Published As
| Publication number | Publication date |
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| TWI613222B (en) | 2018-02-01 |
| CN107531817A (en) | 2018-01-02 |
| TW201805313A (en) | 2018-02-16 |
| CN107531817B (en) | 2019-03-15 |
| JP6211746B1 (en) | 2017-10-11 |
| JPWO2017170888A1 (en) | 2018-04-12 |
| KR20170122833A (en) | 2017-11-06 |
| KR101878117B1 (en) | 2018-07-12 |
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