JP6979326B2 - Adhesives for resin compositions and electronic components - Google Patents
Adhesives for resin compositions and electronic components Download PDFInfo
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- JP6979326B2 JP6979326B2 JP2017203288A JP2017203288A JP6979326B2 JP 6979326 B2 JP6979326 B2 JP 6979326B2 JP 2017203288 A JP2017203288 A JP 2017203288A JP 2017203288 A JP2017203288 A JP 2017203288A JP 6979326 B2 JP6979326 B2 JP 6979326B2
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- resin composition
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- liquid crystal
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 76
- 239000000853 adhesive Substances 0.000 title description 24
- 230000001070 adhesive effect Effects 0.000 title description 24
- 150000001875 compounds Chemical class 0.000 claims description 60
- -1 styrene olefin Chemical class 0.000 claims description 54
- 239000004973 liquid crystal related substance Substances 0.000 claims description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 36
- 239000000565 sealant Substances 0.000 claims description 32
- 239000004593 Epoxy Substances 0.000 claims description 29
- 239000010419 fine particle Substances 0.000 claims description 25
- 125000003700 epoxy group Chemical group 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000005062 Polybutadiene Substances 0.000 claims description 14
- 229920002857 polybutadiene Polymers 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 239000012766 organic filler Substances 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- 239000007870 radical polymerization initiator Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- ZJWLBMNXCXSHBD-UHFFFAOYSA-N trimethyl(1,1,2,2-tetraphenylethoxy)silane Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O[Si](C)(C)C)C(C=1C=CC=CC=1)C1=CC=CC=C1 ZJWLBMNXCXSHBD-UHFFFAOYSA-N 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 40
- 229920000647 polyepoxide Polymers 0.000 description 26
- 239000003822 epoxy resin Substances 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 18
- 230000035699 permeability Effects 0.000 description 16
- 239000007983 Tris buffer Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- 229920003986 novolac Polymers 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical class CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 5
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- CSFWPUWCSPOLJW-UHFFFAOYSA-N lawsone Chemical compound C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 3
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 3
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229930192627 Naphthoquinone Natural products 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 229910052570 clay Inorganic materials 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 150000002791 naphthoquinones Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- OVJHMJJVXOJMBB-UHFFFAOYSA-N 2-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)ethyl prop-2-enoate Chemical compound C1CCCC2C(=O)N(CCOC(=O)C=C)C(=O)C21 OVJHMJJVXOJMBB-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 2
- OBGBGHKYJAOXRR-UHFFFAOYSA-N 2-methoxy-1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C(OC)=CC(=O)C2=C1 OBGBGHKYJAOXRR-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 229920006397 acrylic thermoplastic Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000004956 cell adhesive effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- ZASZWSTYEJKHIN-UHFFFAOYSA-N tripropylazanium;hydroxide Chemical compound [OH-].CCC[NH+](CCC)CCC ZASZWSTYEJKHIN-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- ROFVGYAMRSGUSQ-UHFFFAOYSA-N 1-(2-bromoethyl)piperazine;hydrobromide Chemical compound Br.BrCCN1CCNCC1 ROFVGYAMRSGUSQ-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- XRNSUHLEVOUTDT-UHFFFAOYSA-N 10-hydrazinyl-10-oxodecanoic acid Chemical compound NNC(=O)CCCCCCCCC(O)=O XRNSUHLEVOUTDT-UHFFFAOYSA-N 0.000 description 1
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- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- IFZUFHWISBKFJP-UHFFFAOYSA-N n'-[4-[dimethoxy(methyl)silyl]oxybutyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)OCCCCNCCN IFZUFHWISBKFJP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- DDOVHJODVHQLCS-UHFFFAOYSA-N pyridine-2,6-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=N1 DDOVHJODVHQLCS-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WTKVMIIQXATOJO-UHFFFAOYSA-N trimethyl-(1,1,2,2-tetraphenyl-2-trimethylsilyloxyethoxy)silane Chemical compound C=1C=CC=CC=1C(C(O[Si](C)(C)C)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O[Si](C)(C)C)C1=CC=CC=C1 WTKVMIIQXATOJO-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、フレキシブルディスプレイや湾曲形状のディスプレイにも適用できる電子部品用接着剤に使用される樹脂組成物に関する。より詳細には、分子内に特定の構造を有する化合物を含有する樹脂組成物に関する。この樹脂組成物は、柔軟性と低透湿性を両立できるものである為、電子部品用接着剤、特にディスプレイ用封止剤として有用である。 The present invention relates to a resin composition used as an adhesive for electronic components, which can also be applied to flexible displays and curved displays. More specifically, the present invention relates to a resin composition containing a compound having a specific structure in the molecule. Since this resin composition has both flexibility and low moisture permeability, it is useful as an adhesive for electronic parts, particularly as a sealing agent for displays.
樹脂組成物は、ディスプレイ用封止剤、太陽電池用封止剤、半導体封止剤等の電子部品用接着剤用途で広く用いられている。ディスプレイ用封止剤とは、例えば液晶用シール剤、有機ＥＬディスプレイ用封止剤やタッチパネル用接着剤等を挙げることができる。これらの材料として共通していることは、優れた硬化性を有しながら、アウトガスが少なく、表示素子にダメージを与えないという特性が要求される点である。
また最近では、ディスプレイ分野等で湾曲した形状のものや、フレキシブル性に富んだものが開発され製品化されている。こういったディスプレイ等に使用される基板は、従来のガラスのような剛直なものに代わって、プラスチックフィルムのような柔軟なものが使用されている（特許文献１）。
こういった背景から、樹脂組成物には基板等のたわみに追従するような、すなわち硬化後においても柔軟であるという性質が要求されつつある。
Resin compositions are widely used in adhesives for electronic components such as sealants for displays, sealants for solar cells, and semiconductor sealants. Examples of the sealant for a display include a sealant for a liquid crystal display, a sealant for an organic EL display, an adhesive for a touch panel, and the like. What these materials have in common is that they are required to have excellent curability, low outgas, and no damage to the display element.
Recently, curved shapes and highly flexible ones have been developed and commercialized in the display field and the like. As the substrate used for such a display or the like, a flexible one such as a plastic film is used instead of a rigid one such as conventional glass (Patent Document 1).
From such a background, the resin composition is required to have a property of following the deflection of the substrate or the like, that is, being flexible even after curing.
一方、硬化物の柔軟性を高めるためには、硬化物の架橋密度を下げることが有効な手段である。しかし、架橋密度が下がると透湿性を悪化させるのが通常である。これはネットワークの緩い部分から水分が浸入する為であると考えられる。従って、低透湿性を担保する為には、架橋密度を下げずに柔軟性を高めるか、架橋密度は下げるが透湿性を悪化させないという相反する特性の実現が必要となる。 On the other hand, in order to increase the flexibility of the cured product, it is an effective means to reduce the cross-linking density of the cured product. However, when the crosslink density decreases, the moisture permeability usually deteriorates. It is considered that this is because water infiltrates from the loose part of the network. Therefore, in order to ensure low moisture permeability, it is necessary to increase the flexibility without lowering the crosslink density, or to realize the contradictory characteristics that the crosslink density is lowered but the moisture permeability is not deteriorated.
従来、接着強度向上の観点から、柔軟性を有する表示素子用接着剤の開発は行われてきた（特許文献２）。しかし、上記の柔軟な基板に適応するための十分な性能を備えたものは未だ実現していない。 Conventionally, from the viewpoint of improving the adhesive strength, a flexible adhesive for a display element has been developed (Patent Document 2). However, a device having sufficient performance for adapting to the above-mentioned flexible substrate has not yet been realized.
本発明は、フレキシブルディスプレイや湾曲形状のディスプレイ用の電子部品にも適用でき、更には低透湿性にも優れる樹脂組成物を提案するものである。当該樹脂組成物は、柔軟性と低透湿性を両立できるものである為、電子部品用接着剤、特にディスプレイ用封止剤として有用である。 The present invention proposes a resin composition that can be applied to electronic components for flexible displays and curved displays, and also has excellent low moisture permeability. Since the resin composition can achieve both flexibility and low moisture permeability, it is useful as an adhesive for electronic parts, particularly as a sealing agent for displays.
本発明者らは、鋭意検討の結果、分子内にエポキシ基を有するポリブタジエン化合物を含有する樹脂組成物が、柔軟性と低透湿性に非常に優れることを見出し、本発明に至った。
なお、本明細書中、「（メタ）アクリル」とは「アクリル及び／又はメタクリル」を意味し、「（メタ）アクリロイル基」とは「アクリロイル基及び／又はメタクリロイル基」を意味する。また、「液晶滴下工法用液晶シール剤」を単に「液晶シール剤」又は「シール剤」と記載する場合もある。
As a result of diligent studies, the present inventors have found that a resin composition containing a polybutadiene compound having an epoxy group in the molecule is extremely excellent in flexibility and low moisture permeability, and have reached the present invention.
In the present specification, "(meth) acrylic" means "acrylic and / or methacrylic", and "(meth) acryloyl group" means "acryloyl group and / or methacrylic group". Further, the "liquid crystal sealant for the liquid crystal dropping method" may be simply described as "liquid crystal sealant" or "sealant".
即ち本発明は、
［１］成分（Ａ）：分子内にエポキシ基を有するポリブタジエン化合物、を含有する樹脂組成物、
［２］前記成分（Ａ）が、分子内に、更に反応性二重結合を有する化合物である前項［１］に記載の樹脂組成物、
［３］前記成分（Ａ）の数平均分子量が、５００以上１００００以下である前項［１］又は［２］に記載の樹脂組成物、
［４］前記成分（Ａ）が３個以上のヒドロキシ基を有さない前項［１］乃至［３］のいずれか一項に記載の樹脂組成物、
［５］更に、成分（Ｂ）硬化性化合物を含有する前項［１］乃至［４］４のいずれか一項に記載の樹脂組成物、
［６］前記成分（Ｂ）が、成分（Ｂ−１）（メタ）アクリル化合物である前項［５］に記載の樹脂組成物、
［７］前記成分（Ｂ）が、成分（Ｂ−１）（メタ）アクリル化合物と成分（Ｂ−２）エポキシ化合物の混合物である前項［５］に記載の樹脂組成物、
［８］前記成分（Ｂ−１）が、エポキシ（メタ）アクリレートである前項［６］又は［７］に記載の樹脂組成物、
［９］更に、成分（Ｃ）チオール化合物を含有する前項［１］乃至［８］のいずれか一項に記載の樹脂組成物、
［１０］更に、成分（Ｄ）有機フィラーを含有する前項［１］及至［９］のいずれか一項に記載の樹脂組成物、
［１１］前記成分（Ｄ）が、ウレタン微粒子、アクリル微粒子、スチレン微粒子、スチレンオレフィン微粒子、及びシリコーン微粒子からなる群より選択される１又は２以上の有機フィラーである前項［１０］に記載の樹脂組成物、
［１２］更に、成分（Ｅ）無機フィラーを含有する前項［１］及至［１１］のいずれか一項に記載の樹脂組成物、
［１３］更に、成分（Ｆ）シランカップリング剤を含有する前項［１］及至［１２］のいずれか一項に記載の樹脂組成物、
［１４］更に、成分（Ｇ）熱硬化剤を含有する前項［１］及至［１３］いずれか一項に記載の樹脂組成物、
［１５］前記成分（Ｇ）が有機酸ヒドラジド化合物である前項［１４］に記載の樹脂組成物、
［１６］更に、成分（Ｈ）光ラジカル重合開始剤を含有する前項［１］及至［１５］のいずれか一項に記載の樹脂組成物、
［１７］更に、成分（Ｉ）熱ラジカル重合開始剤を含有する前項［１］及至［１６］のいずれか一項に記載の樹脂組成物、
［１８］前項［１］乃至［１７］のいずれか一項に記載の樹脂組成物を用いた電子部品用接着剤、
［１９］前項［１７］に記載の電子部品用接着剤を硬化して得られる硬化物で接着された電子部品、
［２０］前項［１］乃至［１７］のいずれか一項に記載の樹脂組成物を用いた液晶表示セル用接着剤、
［２１］前項［１］乃至［１７］のいずれか一項に記載の樹脂組成物を用いた液晶シール剤、
［２２］前項［２０］又は［２１］に記載の液晶表示セル用接着剤又は液晶シール剤を用いて接着された液晶表示セル、
に関するものである。
That is, the present invention
[1] A resin composition containing a component (A): a polybutadiene compound having an epoxy group in the molecule.
[2] The resin composition according to the preceding item [1], wherein the component (A) is a compound having a reactive double bond in the molecule.
[3] The resin composition according to the preceding item [1] or [2], wherein the number average molecular weight of the component (A) is 500 or more and 10,000 or less.
[4] The resin composition according to any one of the above items [1] to [3], wherein the component (A) does not have three or more hydroxy groups.
[5] The resin composition according to any one of [1] to [4] 4 above, which further contains the component (B) a curable compound.
[6] The resin composition according to the preceding item [5], wherein the component (B) is a component (B-1) (meth) acrylic compound.
[7] The resin composition according to the preceding item [5], wherein the component (B) is a mixture of the component (B-1) (meth) acrylic compound and the component (B-2) epoxy compound.
[8] The resin composition according to the above item [6] or [7], wherein the component (B-1) is an epoxy (meth) acrylate.
[9] The resin composition according to any one of the preceding items [1] to [8], which further contains the component (C) thiol compound.
[10] The resin composition according to any one of the above items [1] and [9], which further contains the component (D) organic filler.
[11] The resin according to the preceding item [10], wherein the component (D) is one or more organic fillers selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. Composition,
[12] The resin composition according to any one of the above items [1] and [11], which further contains the component (E) an inorganic filler.
[13] The resin composition according to any one of the above items [1] and [12], which further contains the component (F) silane coupling agent.
[14] The resin composition according to any one of the above items [1] and [13], which further contains the component (G) thermosetting agent.
[15] The resin composition according to the preceding item [14], wherein the component (G) is an organic acid hydrazide compound.
[16] The resin composition according to any one of the above items [1] and [15], which further contains the component (H) photoradical polymerization initiator.
[17] The resin composition according to any one of the above items [1] and [16], which further contains the component (I) thermal radical polymerization initiator.
[18] An adhesive for electronic components using the resin composition according to any one of the preceding items [1] to [17].
[19] An electronic component bonded with a cured product obtained by curing the adhesive for electronic components according to the preceding item [17].
[20] An adhesive for a liquid crystal display cell using the resin composition according to any one of the preceding items [1] to [17].
[21] A liquid crystal sealant using the resin composition according to any one of the preceding items [1] to [17].
[22] A liquid crystal display cell bonded using the liquid crystal display cell adhesive or liquid crystal sealant according to the preceding item [20] or [21].
It is about.
本発明の樹脂組成物は、柔軟性と低透湿性を両立できるものである為、電子部品用接着剤、特にディスプレイ用封止剤として有用である。 Since the resin composition of the present invention can achieve both flexibility and low moisture permeability, it is useful as an adhesive for electronic parts, particularly as a sealing agent for displays.
［（Ａ）分子内にエポキシ基を有するポリブタジエン化合物］
本発明の樹脂組成物は、成分（Ａ）：分子内にエポキシ基を有するポリブタジエン化合物（以下、単に「成分（Ａ）」ともいう。）を含有する。この化合物は、柔軟性を有しながら、エポキシ基の開環反応により低透湿性を実現できる。従来、ポリブタジエンやポリイソプレンは末端二重結合を用いて反応させるものが主であるが、ラジカル反応では反応性が速い一方で、十分な架橋が得られず、透湿を悪化させるものと考えられる。
[(A) Polybutadiene compound having an epoxy group in the molecule]
The resin composition of the present invention contains a component (A): a polybutadiene compound having an epoxy group in the molecule (hereinafter, also simply referred to as “component (A)”). This compound can realize low moisture permeability by the ring-opening reaction of the epoxy group while having flexibility. Conventionally, polybutadiene and polyisoprene are mainly reacted using a terminal double bond, but it is considered that while the radical reaction has a high reactivity, sufficient cross-linking cannot be obtained and the moisture permeability is deteriorated. ..
前記エポキシ基を有するポリブタジエン化合物とは、ブタジエン骨格に含まれる炭素−炭素二重結合の少なくとも一部がエポキシ化されることによって、分子内にエポキシ基が導入された化合物である。エポキシ化ポリブタジエン化合物は、特に制限されないが、主鎖の両末端に、水素原子、ヒドロキシ基、カルボキシ基、シアノ基、ヒドロキシエチル基などのヒドロキシアルキル基を有しているものが挙げられる。
成分（Ａ）としては、分子内に更に反応性二重結合を有する化合物が好ましい。上記ラジカル硬化の速反応性のメリットも生かしながら、硬化物特性はエポキシ基の開環反応によって得るという設計となり、より有益である。
The polybutadiene compound having an epoxy group is a compound in which an epoxy group is introduced into the molecule by epoxidizing at least a part of carbon-carbon double bonds contained in the butadiene skeleton. The epoxidized polybutadiene compound is not particularly limited, and examples thereof include those having a hydroxyalkyl group such as a hydrogen atom, a hydroxy group, a carboxy group, a cyano group, and a hydroxyethyl group at both ends of the main chain.
As the component (A), a compound having a reactive double bond in the molecule is preferable. While taking advantage of the rapid reactivity of radical curing, the cured product property is designed to be obtained by the ring-opening reaction of the epoxy group, which is more useful.
エポキシ化ポリブタジエン化合物としては、下記式（１）で示される繰り返し単位と、下記式（２）で示される繰り返し単位を有する化合物、あるいは下記式（３）で示される繰り返し単位又は下記式（４）で示される繰り返し単位を有する化合物が挙げられる。 The epoxidized polybutadiene compound includes a compound having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), or the following formula (4). Examples thereof include compounds having a repeating unit indicated by.
エポキシ化ポリブタジエン化合物としては、下記式（５）で示される化合物又は下記式（６）で示される化合物が好ましい。 As the epoxidized polybutadiene compound, a compound represented by the following formula (5) or a compound represented by the following formula (6) is preferable.
エポキシ基を有するポリブタジエン化合物は、ポリブタジエン樹脂にエポキシ化剤を反応させることによって得ることができる。原料であるポリブタジエン樹脂において、二重結合部位の立体構造は、シス−１，４、トランス−１，４、トランス−１，２、シス−１，２のいずれであってもよい。また、それらの比率は任意でよい。エポキシ化剤としては、過酢酸、過ギ酸、過安息香酸、トリフルオロ過酢酸、過プロピオン酸などの有機過酸類、過酸化水素、ｔ−ブチルヒドロパーオキサイド、クメンヒドロパーオキサイドなどの有機ヒドロパーオキサイド類などを使用できる。有機過酸としては、目的物のオキシラン酸素濃度を高めるため、実質的に水を含まないもの（例えば、水分含有量で０．８重量％以下）が好ましい。上記エポキシ化剤の中でも、工業的に安価に入手でき、且つ安定度の高い点から、過酢酸が特に好ましい。 A polybutadiene compound having an epoxy group can be obtained by reacting a polybutadiene resin with an epoxidizing agent. In the raw material polybutadiene resin, the three-dimensional structure of the double bond site may be any of cis-1,4, trans-1,4, trans-1,2, and cis-1,2. Moreover, those ratios may be arbitrary. Examples of the epoxidizing agent include organic peracetic acids such as peracetic acid, performic acid, perbenzoic acid, trifluoroperacetic acid and perpropionic acid, and organic hydropers such as hydrogen peroxide, t-butylhydroperoxide and cumenehydroperoxide. Oxides and the like can be used. The organic peracid preferably contains substantially no water (for example, 0.8% by weight or less in terms of water content) in order to increase the oxygen concentration of oxylane of the target substance. Among the above epoxidizing agents, peracetic acid is particularly preferable because it can be obtained industrially at low cost and has high stability.
また、 前記エポキシ化ポリジエン樹脂の数平均分子量は、樹脂組成物からの発ガスや、液晶周辺材料、例えば液晶シール剤として用いる場合の液晶汚染性低減の観点から、成分下限は５００が好ましく、更に好ましくは７５０、特に好ましくは１０００である。
また、ハンドリング性の観点から、成分（Ａ）の数平均分子量の上限は１００００が好ましく、更に好ましくは８０００、特に好ましくは６０００である。
The number average molecular weight of the epoxidized polydiene resin is preferably 500 at the lower limit of the component from the viewpoint of gas generation from the resin composition and reduction of liquid crystal contamination when used as a liquid crystal peripheral material, for example, a liquid crystal sealant. It is preferably 750, particularly preferably 1000.
Further, from the viewpoint of handleability, the upper limit of the number average molecular weight of the component (A) is preferably 10000, more preferably 8000, and particularly preferably 6000.
前記エポキシ基を有するポリブタジエン化合物は市販品を用いることができる。市販品としては、例えばＪＰ−１００、ＪＰ−２００、ＪＰ−４００（いずれも日本曹達株式会社（製））、エポリード ＰＢ３６００、エポリード ＰＢ４７００（いずれも株式会社ダイセル（製））、ＢＦ−１０００（株式会社ＡＤＥＫＡ（製））、Ｒｉｃｏｎ６５７（クレイバレー社（製））として市場から入手することができる。 As the polybutadiene compound having an epoxy group, a commercially available product can be used. Commercially available products include, for example, JP-100, JP-200, JP-400 (all manufactured by Nippon Soda Corporation), Epolide PB3600, Epolide PB4700 (all manufactured by Daicel Corporation), and BF-1000 (stocks). It can be obtained from the market as companies ADEKA (manufactured) and Rikon 657 (Clay Valley (manufactured)).
［（Ｂ）硬化性化合物］
本発明の樹脂組成物は、成分（Ｂ）硬化性化合物（以下、単に「成分（Ｂ）」ともいう。）を含有する場合が好ましい。
[(B) Curable compound]
The resin composition of the present invention preferably contains a component (B) curable compound (hereinafter, also simply referred to as “component (B)”).
［（Ｂ−１）（メタ）アクリル化合物］
成分（Ｂ）としては、光や熱等によって硬化する化合物であれば特に限定されないが、成分（Ｂ−１）（メタ）アクリル化合物（以下、単に成分（Ｂ−２）ともいう。）である場合が好ましい。ここで「（メタ）アクリル」とは「アクリル」及び／又は「メタクリル」を意味する。（以下同様。）成分（Ｂ−１）としては、例えば、（メタ）アクリルエステル化合物、エポキシ（メタ）アクリレート化合物等が挙げられる。このうち、好ましくはエポキシ（メタ）アクリレート化合物である。
（メタ）アクリルエステル化合物の具体例としては、Ｎ−アクリロイルオキシエチルヘキサヒドロフタルイミド、アクリロイルモルホリン、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、シクロヘキサン−１，４−ジメタノールモノ（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェニルポリエトキシ（メタ）アクリレート、２−ヒドロキシ−３−フェニルオキシプロピル（メタ）アクリレート、ｏ−フェニルフェノールモノエトキシ（メタ）アクリレート、ｏ−フェニルフェノールポリエトキシ（メタ）アクリレート、ｐ−クミルフェノキシエチル（メタ）アクリレート、イソボニル（メタ）アクリレート、トリブロモフェニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、トリシクロデカンジメタノール（メタ）アクリレート、ビスフェノールＡポリエトキシジ（メタ）アクリレート、ビスフェノールＡポリプロポキシジ（メタ）アクリレート、ビスフェノールＦポリエトキシジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ネオペンチルグリコールとヒドロキシピバリン酸のエステルジアクリレートやネオペンチルグリコールとヒドロキシピバリン酸のエステルのε−カプロラクトン付加物のジアクリレート等のモノマー類を挙げることができる。好ましくは、Ｎ−アクリロイルオキシエチルヘキサヒドロフタルイミド、フェノキシエチル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレートを挙げることができる。
エポキシ（メタ）アクリレート化合物は、エポキシ化合物と（メタ）アクリル酸との反応により公知の方法で得られる。原料となるエポキシ化合物としては、特に限定されるものではないが、２官能以上のエポキシ化合物が好ましく、例えば、レゾルシンジグリシジルエーテル、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールＳ型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビスフェノールＡノボラック型エポキシ化合物、ビスフェノールＦノボラック型エポキシ化合物、脂環式エポキシ化合物、脂肪族鎖状エポキシ化合物、グリシジルエステル型エポキシ化合物、グリシジルアミン型エポキシ化合物、ヒダントイン型エポキシ化合物、イソシアヌレート型エポキシ化合物、トリフェノールメタン骨格を有するフェノールノボラック型エポキシ化合物、その他、カテコール、レゾルシノール等の二官能フェノール類のジグリシジルエーテル化物、二官能アルコール類のジグリシジルエーテル化物、およびそれらのハロゲン化物、水素添加物などが挙げられる。これらのうち液晶汚染性の観点から、ビスフェノールＡ型エポキシ化合物やレゾルシンジグリシジルエーテルが好ましい。また、エポキシ基と（メタ）アクリロイル基との比率は限定されるものではなく、工程適合性の観点から適切に選択される。
成分（Ｂ）は単独で用いても良いし、２種類以上を混合しても良い。本発明の樹脂組成物において、成分（Ｂ）を使用する場合には、樹脂組成物の総量中、通常１０〜８０質量％、好ましくは２０〜７０質量％である。
[(B-1) (meth) acrylic compound]
The component (B) is not particularly limited as long as it is a compound that is cured by light, heat, or the like, but is a component (B-1) (meth) acrylic compound (hereinafter, also simply referred to as a component (B-2)). The case is preferable. Here, "(meth) acrylic" means "acrylic" and / or "methacryl". (The same shall apply hereinafter.) Examples of the component (B-1) include (meth) acrylic ester compounds and epoxy (meth) acrylate compounds. Of these, an epoxy (meth) acrylate compound is preferable.
Specific examples of the (meth) acrylic ester compound include N-acryloyloxyethyl hexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and cyclohexane-1,4-dimethanol. Mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenylpolyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy ( Meta) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobonyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (Meta) acrylate, tricyclodecanedimethanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene Glycoldi (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate , Tripentaerythritol Penta (meth) acrylate, Trimethylolpropantri (meth) acrylate, Trimethylolpropanepolyethoxytri (meth) acrylate, Ditrimethylolpropanetetra (meth) acrylate, Neopentyl glycol and hydroxypivalic acid ester diacrylate And monomers such as diacrylates of ε-caprolactone adducts of neopentyl glycol and hydroxypivalic acid esters. Preferred examples include N-acryloyloxyethyl hexahydrophthalimide, phenoxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
The epoxy (meth) acrylate compound is obtained by a known method by reacting the epoxy compound with (meth) acrylic acid. The epoxy compound as a raw material is not particularly limited, but a bifunctional or higher functional epoxy compound is preferable, and for example, resorcindiglycidyl ether, bisphenol A type epoxy compound, bisphenol F type epoxy compound, and bisphenol S type epoxy compound. , Phenol novolak type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolak type epoxy compound, bisphenol F novolak type epoxy compound, alicyclic epoxy compound, aliphatic chain epoxy compound, glycidyl ester type epoxy compound, glycidylamine type epoxy Compounds, hydride-in type epoxy compounds, isocyanurate type epoxy compounds, phenol novolac type epoxy compounds having a triphenol methane skeleton, diglycidyl ethers of bifunctional phenols such as catechol and resorcinol, diglycidyl ethers of bifunctional alcohols Examples include compounds, their halides, hydrogen additives and the like. Of these, bisphenol A type epoxy compounds and resorcinol diglycidyl ethers are preferable from the viewpoint of liquid crystal contamination. Further, the ratio of the epoxy group to the (meth) acryloyl group is not limited, and is appropriately selected from the viewpoint of process compatibility.
The component (B) may be used alone or in combination of two or more. When the component (B) is used in the resin composition of the present invention, it is usually 10 to 80% by mass, preferably 20 to 70% by mass, based on the total amount of the resin composition.
［（Ｂ−２）エポキシ化合物］
本発明の態様として、上記成分（Ｂ）中に、さらに成分（Ｂ−２）エポキシ化合物（以下、単に成分（Ｂ−２）ともいう。）が含有される場合がさらに好ましい。
エポキシ化合物としては特に限定されるものではないが、２官能以上のエポキシ化合物が好ましく、例えば、レゾルシンジグリシジルエーテル、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂、トリフェノールメタン骨格を有するフェノールノボラック型エポキシ樹脂、その他、カテコール、レゾルシノール等の二官能フェノール類のジグリシジルエーテル化物、二官能アルコール類のジグリシジルエーテル化物、およびそれらのハロゲン化物、水素添加物などが挙げられる。これらのうち液晶汚染性の観点から、ビスフェノールＡ型エポキシ樹脂やレゾルシンジグリシジルエーテルが好ましい。
成分（Ｂ−２）は単独で用いても良いし、２種類以上を混合しても良い。本発明の樹脂組成物において、成分（Ｂ−２）を使用する場合には、樹脂組成物総量中、通常５〜５０質量％、好ましくは５〜３０質量％である。
[(B-2) Epoxy compound]
As an aspect of the present invention, it is more preferable that the component (B) further contains the component (B-2) epoxy compound (hereinafter, also simply referred to as the component (B-2)).
The epoxy compound is not particularly limited, but a bifunctional or higher functional epoxy compound is preferable, and for example, resorcindiglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and phenol novolak type. Epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hidden in type Epoxy resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having a triphenol methane skeleton, diglycidyl etherified products of bifunctional phenols such as catechol and resorcinol, diglycidyl etherified products of bifunctional alcohols, and them. Examples thereof include epoxies and hydrogen additives. Of these, bisphenol A type epoxy resin and resorcinol diglycidyl ether are preferable from the viewpoint of liquid crystal contamination.
The component (B-2) may be used alone or in combination of two or more. When the component (B-2) is used in the resin composition of the present invention, it is usually 5 to 50% by mass, preferably 5 to 30% by mass, based on the total amount of the resin composition.
［（Ｃ）チオール化合物］
本発明の樹脂組成物は、成分（Ｃ）チオール化合物（以下、単に成分（Ｃ）ともいう。）を含有しても良い。成分（Ｃ）は成分（Ａ）のエポキシ基とも、反応性二重結合とも反応する為、添加することが非常に有用である。
成分（Ｃ）としては、分子内にチオール基を有する化合物であれが特に限定されるものではないが、保存安定性と反応性の観点から２級チオール基を有するチオール化合物が好ましい。
また、チオール基の数は、分子内に２以上有するもの（多官能チオール化合物）が好ましく、更に好ましくは３官能又は４官能である。
本発明の樹脂組成物を電子部品用封止剤として用いる場合、発ガスの抑制等の観点から、チオール化合物のチオール当量は８０以上が好ましく、更に好ましくは１００以上である。また、分子量は、好ましくは２５０以上であり、更に好ましくは５００以上である。
成分（Ｃ）は単独で用いても良いし、２種類以上を混合しても良い。本発明の樹脂組成物において、成分（Ｃ）を使用する場合には、樹脂組成物総量中、通常０．５〜３０質量％、好ましくは０．５〜２０質量％である。
[(C) Thiol compound]
The resin composition of the present invention may contain a component (C) thiol compound (hereinafter, also simply referred to as a component (C)). Since the component (C) reacts with both the epoxy group of the component (A) and the reactive double bond, it is very useful to add the component (C).
The component (C) is not particularly limited as long as it is a compound having a thiol group in the molecule, but a thiol compound having a secondary thiol group is preferable from the viewpoint of storage stability and reactivity.
The number of thiol groups is preferably two or more in the molecule (polyfunctional thiol compound), and more preferably trifunctional or tetrafunctional.
When the resin composition of the present invention is used as a sealing agent for electronic components, the thiol equivalent of the thiol compound is preferably 80 or more, more preferably 100 or more, from the viewpoint of suppressing gas generation. The molecular weight is preferably 250 or more, and more preferably 500 or more.
The component (C) may be used alone or in combination of two or more. When the component (C) is used in the resin composition of the present invention, it is usually 0.5 to 30% by mass, preferably 0.5 to 20% by mass, based on the total amount of the resin composition.
［（Ｄ）有機フィラー］
本発明の樹脂組成物は、成分（Ｄ）有機フィラー（以下、単に成分（Ｄ）ともいう。）を含有しても良い。上記有機フィラーとしては、例えばウレタン微粒子、アクリル微粒子、スチレン微粒子、スチレンオレフィン微粒子及びシリコーン微粒子が挙げられる。なおシリコーン微粒子としてはＫＭＰ−５９４、ＫＭＰ−５９７、ＫＭＰ−５９８（信越化学工業製）、トレフィルＲＴＭＥ−５５００、９７０１、ＥＰ−２００１（東レダウコーニング社製）が好ましく、ウレタン微粒子としてはＪＢ−８００Ｔ、ＨＢ−８００ＢＫ（根上工業株式会社）、スチレン微粒子としてはラバロンＲＴＭＴ３２０Ｃ、Ｔ３３１Ｃ、ＳＪ４４００、ＳＪ５４００、ＳＪ６４００、ＳＪ４３００Ｃ、ＳＪ５３００Ｃ、ＳＪ６３００Ｃ（三菱化学製）が好ましく、スチレンオレフィン微粒子としてはセプトンＲＴＭＳＥＰＳ２００４、ＳＥＰＳ２０６３が好ましい。
これら有機フィラーは単独で用いても良いし、２種類以上を併用しても良い。また２種以上を用いてコアシェル構造としても良い。これらのうち、好ましくは、アクリル微粒子、シリコーン微粒子である。
上記アクリル微粒子を使用する場合、２種類のアクリルゴムからなるコアシェル構造のアクリルゴムである場合が好ましく、特に好ましくはコア層がｎ−ブチルアクリレートであり、シェル層がメチルメタクリレートであるものが好ましい。これはゼフィアックＲＴＭＦ−３５１としてアイカ工業株式会社から販売されている。
また、上記シリコーン微粒子としては、オルガノポリシロキサン架橋物粉体、直鎖のジメチルポリシロキサン架橋物粉体等があげられる。また、複合シリコーンゴムとしては、上記シリコーンゴムの表面にシリコーン樹脂（例えば、ポリオルガノシルセスキオキサン樹脂）を被覆したものがあげられる。これらの微粒子のうち、特に好ましいのは、直鎖のジメチルポリシロキサン架橋粉末のシリコーンゴム又はシリコーン樹脂被覆直鎖ジメチルポリシロキサン架橋粉末の複合シリコーンゴム微粒子である。これらのものは、単独で用いても良いし、２種類以上を併用しても良い。また、好ましくは、ゴム粉末の形状は、添加後の粘度の増粘が少ない球状が良い。本発明の樹脂組成物において、成分（Ｄ）を使用する場合には、樹脂組成物の総量中、通常５〜５０質量％、好ましくは５〜４０質量％である。
[(D) Organic filler]
The resin composition of the present invention may contain a component (D) organic filler (hereinafter, also simply referred to as a component (D)). Examples of the organic filler include urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. The silicone fine particles are preferably KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil RTM E-5500, 9701, EP-2001 (manufactured by Toray Dow Corning), and the urethane fine particles are JB-. 800T, HB-800BK (Negami Kogyo Co., Ltd.), Lavalon RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (manufactured by Mitsubishi Chemical) are preferable as styrene fine particles, and Septon RTM SEPS2004, as styrene olefin fine particles. SEPS2063 is preferable.
These organic fillers may be used alone or in combination of two or more. Further, a core shell structure may be formed by using two or more kinds. Of these, acrylic fine particles and silicone fine particles are preferable.
When the acrylic fine particles are used, it is preferable that the acrylic rubber has a core-shell structure composed of two types of acrylic rubber, and it is particularly preferable that the core layer is n-butyl acrylate and the shell layer is methyl methacrylate. It is sold by Aica Kogyo Co., Ltd. as Zephyac RTM F-351.
Examples of the silicone fine particles include organopolysiloxane crosslinked powder and linear dimethylpolysiloxane crosslinked powder. Further, examples of the composite silicone rubber include those in which the surface of the silicone rubber is coated with a silicone resin (for example, polyorganosylsesquioxane resin). Of these fine particles, particularly preferable are silicone rubber of straight-chain dimethylpolysiloxane cross-linked powder or composite silicone rubber fine particles of silicone resin-coated linear dimethylpolysiloxane cross-linked powder. These may be used alone or in combination of two or more. Further, preferably, the shape of the rubber powder is a spherical shape with less viscosity increase after addition. When the component (D) is used in the resin composition of the present invention, it is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the resin composition.
［（Ｅ）無機フィラー］
本発明の樹脂組成物は、成分（Ｅ）無機フィラー（以下、単に「成分（Ｅ）」ともいう。）を含有しても良い。本発明で含有する無機フィラーとしては、シリカ、シリコンカーバイド、窒化珪素、窒化ホウ素、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、硫酸カルシウム、マイカ、タルク、クレー、アルミナ、酸化マグネシウム、酸化ジルコニウム、水酸化アルミニウム、水酸化マグネシウム、珪酸カルシウム、珪酸アルミニウム、珪酸リチウムアルミニウム、珪酸ジルコニウム、チタン酸バリウム、硝子繊維、炭素繊維、二硫化モリブデン、アスベスト等が挙げられ、好ましくは溶融シリカ、結晶シリカ、窒化珪素、窒化ホウ素、炭酸カルシウム、硫酸バリウム、硫酸カルシウム、マイカ、タルク、クレー、アルミナ、水酸化アルミニウム、珪酸カルシウム、珪酸アルミニウムが挙げられるが、好ましくはシリカ、アルミナ、タルクである。これら無機フィラーは２種類以上を混合して用いても良い。
無機フィラーの平均粒子径は、大きすぎると狭ギャップの液晶セル製造時に上下ガラス基板の貼り合わせ時のギャップ形成がうまくできない等の不良要因となるため、２０００ｎｍ以下が適当であり、好ましくは１０００ｎｍ以下、さらに好ましくは３００ｎｍ以下である。また好ましい下限は１０ｎｍ程度であり、さらに好ましくは１００ｎｍ程度である。粒子径はレーザー回折・散乱式粒度分布測定器（乾式）（株式会社セイシン企業製；ＬＭＳ−３０）により測定することができる。
本発明の樹脂組成物において、無機フィラーを使用する場合には、液晶シール剤の総量中、通常５〜５０質量％、好ましくは５〜４０質量％である。
[(E) Inorganic filler]
The resin composition of the present invention may contain a component (E) inorganic filler (hereinafter, also simply referred to as “component (E)”). Examples of the inorganic filler contained in the present invention include silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, and aluminum hydroxide. , Magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably molten silica, crystalline silica, silicon nitride, nitrided Examples thereof include boron, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate and aluminum silicate, with preference given to silica, alumina and talc. Two or more kinds of these inorganic fillers may be mixed and used.
If the average particle size of the inorganic filler is too large, it may cause defects such as poor formation of gaps when the upper and lower glass substrates are bonded when manufacturing a liquid crystal cell with a narrow gap. Therefore, 2000 nm or less is appropriate, and preferably 1000 nm or less. , More preferably 300 nm or less. The lower limit is preferably about 10 nm, and more preferably about 100 nm. The particle size can be measured by a laser diffraction / scattering type particle size distribution measuring device (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
When the inorganic filler is used in the resin composition of the present invention, it is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the liquid crystal sealant.
［（Ｆ）シランカップリング剤］
本発明の樹脂組成物は、成分（Ｆ）シランカップリング剤（以下、単に成分（Ｆ）ともいう。）を添加して、接着強度や耐湿性の向上を図ることができる。
成分（Ｆ）としては、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルメチルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、ビニルトリメトキシシラン、Ｎ−（２−（ビニルベンジルアミノ）エチル）３−アミノプロピルトリメトキシシラン塩酸塩、３−メタクリロキシプロピルトリメトキシシラン、３−クロロプロピルメチルジメトキシシラン、３−クロロプロピルトリメトキシシラン等が挙げられる。これらのシランカップリング剤はＫＢＭシリーズ、ＫＢＥシリーズ等として信越化学工業株式会社等によって販売されている為、市場から容易に入手可能である。本発明の樹脂組成物において、成分（Ｆ）を使用する場合には、樹脂組成物総量中、０．０５〜３質量％が好適である。
[(F) Silane coupling agent]
In the resin composition of the present invention, the component (F) silane coupling agent (hereinafter, also simply referred to as the component (F)) can be added to improve the adhesive strength and the moisture resistance.
The component (F) includes 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltri. Methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, Examples thereof include 3-chloropropylmethyldimethoxysilane and 3-chloropropyltrimethoxysilane. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. as KBM series, KBE series, etc., they are easily available from the market. When the component (F) is used in the resin composition of the present invention, 0.05 to 3% by mass is preferable in the total amount of the resin composition.
［（Ｇ）熱硬化剤］
本発明の樹脂組成物は、成分（Ｇ）熱硬化剤（以下、単に成分（Ｇ）ともいう。）を含有しても良い。成分（Ｇ）は非共有電子対や分子内のアニオンによって、求核的に反応するものであって、例えば多価アミン類、多価フェノール類、有機酸ヒドラジド化合物等を挙げる事ができる。ただしこれらに限定されるものではない。これらのうち有機酸ヒドラジド化合物が特に好適に用いられる。例えば、芳香族ヒドラジドであるテレフタル酸ジヒドラジド、イソフタル酸ジヒドラジド、２，６−ナフトエ酸ジヒドラジド、２，６−ピリジンジヒドラジド、１，２，４−ベンゼントリヒドラジド、１，４，５，８−ナフトエ酸テトラヒドラジド、ピロメリット酸テトラヒドラジド等をあげることが出来る。また、脂肪族ヒドラジド化合物であれば、例えば、ホルムヒドラジド、アセトヒドラジド、プロピオン酸ヒドラジド、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジド、ピメリン酸ジヒドラジド、セバシン酸ジヒドラジド、１，４−シクロヘキサンジヒドラジド、酒石酸ジヒドラジド、リンゴ酸ジヒドラジド、イミノジ酢酸ジヒドラジド、Ｎ，Ｎ’−ヘキサメチレンビスセミカルバジド、クエン酸トリヒドラジド、ニトリロ酢酸トリヒドラジド、シクロヘキサントリカルボン酸トリヒドラジド、１，３−ビス（ヒドラジノカルボノエチル）−５−イソプロピルヒダントイン等のヒダントイン骨格、好ましくはバリンヒダントイン骨格（ヒダントイン環の炭素原子がイソプロピル基で置換された骨格）を有するジヒドラジド化合物、トリス（１−ヒドラジノカルボニルメチル）イソシアヌレート、トリス（２−ヒドラジノカルボニルエチル）イソシアヌレート、トリス（１−ヒドラジノカルボニルエチル）イソシアヌレート、トリス（３−ヒドラジノカルボニルプロピル）イソシアヌレート、ビス（２−ヒドラジノカルボニルエチル）イソシアヌレート等をあげることができる。硬化反応性と潜在性のバランスから好ましくは、イソフタル酸ジヒドラジド、マロン酸ジヒドラジド、アジピン酸ジヒドラジド、トリス（１−ヒドラジノカルボニルメチル）イソシアヌレート、トリス（１−ヒドラジノカルボニルエチル）イソシアヌレート、トリス（２−ヒドラジノカルボニルエチル）イソシアヌレート、トリス（３−ヒドラジノカルボニルプロピル）イソシアヌレートであり、特に好ましくはトリス（２−ヒドラジノカルボニルエチル）イソシアヌレートである。
成分（Ｇ）は単独で用いても良いし、２種類以上を混合しても良い。本発明の樹脂組成物において、成分（Ｇ）を使用する場合には、樹脂組成物総量中、通常０．１〜１０質量％、好ましくは１〜５質量％である。
[(G) Thermosetting agent]
The resin composition of the present invention may contain a component (G) thermosetting agent (hereinafter, also simply referred to as a component (G)). The component (G) reacts nucleophilically with an unshared electron pair or an anion in the molecule, and examples thereof include polyvalent amines, polyphenols, and organic acid hydrazide compounds. However, it is not limited to these. Of these, organic acid hydrazide compounds are particularly preferably used. For example, aromatic hydrazides terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzenetrihydrazide, 1,4,5,8-naphthoic acid. Examples thereof include tetrahydrazide and tetrameritzic acid tetrahydrazide. In the case of an aliphatic hydrazide compound, for example, formhydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutarate dihydrazide, adipate dihydrazide, pimelliate dihydrazide, sebacic acid hydrazide. 1,4-Cyclohexanedihydrazide, tartrate dihydrazide, malonic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebis semi-hydrazide, citrate trihydrazide, nitriloacetate trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis ( A dihydrazide compound having a hydrandin skeleton such as hydrazinocarbonoethyl) -5-isopropylhydrantin, preferably a valine hydrandin skeleton (a skeleton in which the carbon atom of the hydrandin ring is replaced with an isopropyl group), tris (1-hydrazinocarbonylmethyl). Isocyanurate, Tris (2-hydrazinocarbonylethyl) isocyanurate, Tris (1-hydrazinocarbonylethyl) isocyanurate, Tris (3-hydrazinocarbonylpropyl) isocyanurate, Bis (2-hydrazinocarbonylethyl) isocyanurate And so on. From the balance of curing reactivity and latentness, preferably isophthalic acid dihydrazide, malonic acid dihydrazide, adipate dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate 2-Hydradinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, and particularly preferably tris (2-hydrazinocarbonylethyl) isocyanurate.
The component (G) may be used alone or in combination of two or more. When the component (G) is used in the resin composition of the present invention, it is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the resin composition.
［（Ｈ）光ラジカル重合開始剤］
本発明の樹脂組成物は、成分（Ｈ）光ラジカル重合開始剤（以下、単に「成分（Ｈ）」ともいう。）を含有しても良い。光ラジカル重合開始剤としては、紫外線や可視光の照射によって、ラジカルや酸を発生し、連鎖重合反応を開始させる化合物であれば特に限定されないが、例えば、ベンジルジメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、ジエチルチオキサントン、ベンゾフェノン、２−エチルアンスラキノン、２−ヒドロキシ−２−メチルプロピオフェノン、２−メチル−〔４−（メチルチオ）フェニル〕−２−モルフォリノ−１−プロパン、２，４，６−トリメチルベンゾイルジフェニルホスヒンオキサイド、カンファーキノン、９−フルオレノン、ジフェニルジスルヒド等を挙げることができる。具体的には、ＩＲＧＡＣＵＲＥＲＴＭ ６５１、１８４、２９５９、１２７、９０７、３６９、３７９ＥＧ、８１９、７８４、７５４、５００、ＯＸＥ０１、ＯＸＥ０２、ＤＡＲＯＣＵＲＥＲＴＭ１１７３、ＬＵＣＩＲＩＮＲＴＭ ＴＰＯ（いずれもＢＡＳＦ社製）、セイクオールＲＴＭＺ、ＢＺ、ＢＥＥ、ＢＩＰ、ＢＢＩ（いずれも精工化学株式会社製）等を挙げることができる。
また、液晶汚染性の観点から、分子内に（メタ）アクリル基を有するものを使用する事が好ましく、例えば２−メタクリロイルオキシエチルイソシアネートと１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２メチル−１−プロパン−１−オンとの反応生成物が好適に用いられる。この化合物は国際公開第２００６／０２７９８２号記載の方法にて製造して得ることができる。
本発明の樹脂組成物において、成分（Ｈ）を使用する場合には、樹脂組成物総量中、通常０．００１〜３質量％、好ましくは０．００２〜２質量％である。
[(H) Photoradical Polymerization Initiator]
The resin composition of the present invention may contain a component (H) photoradical polymerization initiator (hereinafter, also simply referred to as “component (H)”). The photoradical polymerization initiator is not particularly limited as long as it is a compound that generates radicals or acids by irradiation with ultraviolet rays or visible light to initiate a chain polymerization reaction, and is not particularly limited, but for example, benzyldimethylketal and 1-hydroxycyclohexylphenylketone. , Diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6- Examples thereof include trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyldisulfide and the like. Specifically, IRGACURE RTM 651, 184, 2959, 127, 907, 369, 379EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE RTM 1173, LUCIRIN RTM TPO (all manufactured by BASF), Sequol RTM. Z, BZ, BEE, BIP, BBI (all manufactured by Seiko Kagaku Co., Ltd.) and the like can be mentioned.
Further, from the viewpoint of liquid crystal contamination, it is preferable to use one having a (meth) acrylic group in the molecule, for example, 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl]-. Reaction products with 2-hydroxy-2methyl-1-propane-1-one are preferably used. This compound can be produced and obtained by the method described in International Publication No. 2006/027982.
When the component (H) is used in the resin composition of the present invention, it is usually 0.001 to 3% by mass, preferably 0.002 to 2% by mass, based on the total amount of the resin composition.
［（Ｉ）熱ラジカル重合開始剤］
本発明の液樹脂組成物は、成分（Ｉ）熱ラジカル重合開始剤（以下、単に「成分（Ｉ）」ともいう。）を含有して、硬化速度、硬化性を向上することができる。
熱ラジカル重合開始剤は、加熱によりラジカルを生じ、連鎖重合反応を開始させる化合物であれば特に限定されないが、有機過酸化物、アゾ化合物、ベンゾイン化合物、ベンゾインエーテル化合物、アセトフェノン化合物、ベンゾピナコール等が挙げられ、ベンゾピナコールが好適に用いられる。例えば、有機過酸化物としては、カヤメックＲＴＭＡ、Ｍ、Ｒ、Ｌ、ＬＨ、ＳＰ−３０Ｃ、パーカドックスＣＨ−５０Ｌ、ＢＣ−ＦＦ、カドックスＢ−４０ＥＳ、パーカドックス１４、トリゴノックスＲＴＭ２２−７０Ｅ、２３−Ｃ７０、１２１、１２１−５０Ｅ、１２１−ＬＳ５０Ｅ、２１−ＬＳ５０Ｅ、４２、４２ＬＳ、カヤエステルＲＴＭＰ−７０、ＴＭＰＯ−７０、ＣＮＤ−Ｃ７０、ＯＯ−５０Ｅ、ＡＮ、カヤブチルＲＴＭＢ、パーカドックス１６、カヤカルボンＲＴＭＢＩＣ−７５、ＡＩＣ−７５（化薬アクゾ株式会社製）、パーメックＲＴＭＮ、Ｈ、Ｓ、Ｆ、Ｄ、Ｇ、パーヘキサＲＴＭＨ、ＨＣ、ＴＭＨ、Ｃ、Ｖ、２２、ＭＣ、パーキュアーＲＴＭＡＨ、ＡＬ、ＨＢ、パーブチルＲＴＭＨ、Ｃ、ＮＤ、Ｌ、パークミルＲＴＭＨ、Ｄ、パーロイルＲＴＭＩＢ、ＩＰＰ、パーオクタＲＴＭＮＤ（日油株式会社製）などが市販品として入手可能である。
[(I) Thermal radical polymerization initiator]
The liquid resin composition of the present invention contains the component (I) thermal radical polymerization initiator (hereinafter, also simply referred to as “component (I)”), and can improve the curing rate and curability.
The thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction, but organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzopinacol and the like can be used. Benzopinacol is preferably used. For example, as organic peroxides, Kayamec RTM A, M, R, L, LH, SP-30C, Parkadocs CH-50L, BC-FF, Cadox B-40ES, Parkadocs 14, Trigonox RTM 22-70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl RTM B, Percadox 16 , Kayacarbonate RTM BIC-75, AIC-75 (manufactured by Kayaku Akzo Corporation), Permec RTM N, H, S, F, D, G, Perhexa RTM H, HC, TMH, C, V, 22, MC, Percure RTM AH, AL, HB, Perbutyl RTM H, C, ND, L , Percumyl RTM H, D, PEROYL RTM IB, IPP, Perocta RTM ND (manufactured by NOF Corporation) and the like are commercially available.
また、アゾ化合物としては、ＶＡ−０４４、０８６、Ｖ−０７０、ＶＰＥ−０２０１、ＶＳＰ−１００１（和光純薬工業株式会社製）等が市販品として入手可能である。 As the azo compound, VA-044, 086, V-070, VPE-0201, VSS-1001 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like are available as commercial products.
成分（Ｉ）の含有量としては、樹脂組成物の総量中、０．０００１〜１０質量％であることが好ましく、さらに好ましくは０．０００５〜５質量％であり、０．００１〜３質量％が特に好ましい。 The content of the component (I) is preferably 0.0001 to 10% by mass, more preferably 0.0005 to 5% by mass, and 0.001 to 3% by mass in the total amount of the resin composition. Is particularly preferable.
［その他成分］
本発明の樹脂組成物には、さらに必要に応じて、有機酸やイミダゾール等の硬化促進剤、ラジカル重合防止剤、顔料、レベリング剤、消泡剤、溶剤などの添加剤を配合することができる。
[Other ingredients]
If necessary, the resin composition of the present invention may further contain additives such as a curing accelerator such as an organic acid or imidazole, a radical polymerization inhibitor, a pigment, a leveling agent, a defoaming agent, and a solvent. ..
［硬化促進剤］
上記硬化促進剤としては、有機酸やイミダゾール等を挙げることができる。
有機酸としては、有機カルボン酸や有機リン酸等が挙げられるが、有機カルボン酸である場合が好ましい。具体的には、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、フランジカルボン酸等の芳香族カルボン酸、コハク酸、アジピン酸、ドデカン二酸、セバシン酸、チオジプロピオン酸、シクロヘキサンジカルボン酸、トリス（２−カルボキシメチル）イソシアヌレート、トリス（２−カルボキシエチル）イソシアヌレート、トリス（２−カルボキシプロピル）イソシアヌレート、ビス（２−カルボキシエチル）イソシアヌレート等を挙げることができる。
また、イミダゾール化合物としては、２−メチルイミダゾール、２−フェニルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、２，４−ジアミノ−６（２’−メチルイミダゾール（１’））エチル−ｓ−トリアジン、２，４−ジアミノ−６（２’−ウンデシルイミダゾール（１’））エチル−ｓ−トリアジン、２，４−ジアミノ−６（２’−エチル−４−メチルイミダゾール（１’））エチル−ｓ−トリアジン、２，４−ジアミノ−６（２’−メチルイミダゾール（１’））エチル−ｓ−トリアジン・イソシアヌル酸付加物、２−メチルイミダゾールイソシアヌル酸の２：３付加物、２−フェニルイミダゾールイソシアヌル酸付加物、２−フェニル−３，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−ヒドロキシメチル−５−メチルイミダゾール、１−シアノエチル−２−フェニル−３，５−ジシアノエトキシメチルイミダゾール等が挙げられる。
本発明の樹脂組成物において、硬化促進剤を使用する場合には、樹脂組成物の総量中、通常０．１〜１０質量％、好ましくは１〜５質量％である。
[Curing accelerator]
Examples of the curing accelerator include organic acids and imidazoles.
Examples of the organic acid include an organic carboxylic acid and an organic phosphoric acid, but an organic carboxylic acid is preferable. Specifically, aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenonetetracarboxylic acid and frangylcarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid and thiodipropionic acid. , Cyclohexanedicarboxylic acid, Tris (2-carboxymethyl) isocyanurate, Tris (2-carboxyethyl) isocyanurate, Tris (2-carboxypropyl) isocyanurate, Bis (2-carboxyethyl) isocyanurate and the like. ..
Examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl. -2-Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1') )) Ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl-4-methylimidazole) (1')) Ethyl-s-triazine, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 Additives, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5- Examples thereof include dicyanoethoxymethylimidazole.
When the curing accelerator is used in the resin composition of the present invention, it is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the resin composition.
［ラジカル重合防止剤］
上記ラジカル重合防止剤としては、光ラジカル重合開始剤や熱ラジカル重合開始剤等から発生するラジカルと反応して重合を防止する化合物であれば特に限定されるものではなく、キノン系、ピペリジン系、ヒンダードフェノール系、ニトロソ系等を用いることができる。具体的には、ナフトキノン、２−ヒドロキシナフトキノン、２−メチルナフトキノン、２−メトキシナフトキノン、２，２，６，６−テトラメチルピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−ヒドロキシピペリジン−１−オキシル、２，２，６，６，−テトラメチル−４−メトキシピペリジン−１−オキシル、２，２，６，６−テトラメチル−４−フェノキシピペリジン−１−オキシル、ハイドロキノン、２−メチルハイドロキノン、２−メトキシハイドロキノン、パラベンゾキノン、ブチル化ヒドロキシアニソール、２，６−ジ−ｔ−ブチル−４−エチルフェノール、２，６−ジ−ｔ−ブチルクレゾール、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４’−チオビス−３−メチル−６−ｔ−ブチルフェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、３，９−ビス［１，１−ジメチル−２−［β―（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］エチル］、２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、テトラキス−［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニルプロピオネート）］メタン、１，３，５−トリス（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシベンジル）−ｓｅｃ−トリアジン−２，４，６−（１Ｈ，３Ｈ，５Ｈ）トリオン、パラメトキシフェノール、４−メトキシ−１−ナフトール、チオジフェニルアミン、Ｎ−ニトロソフェニルヒドロキシアミンのアルミニウム塩、商品名アデカスタブＬＡ−８１、商品名アデカスタブＬＡ−８２（株式会社アデカ製）等が挙げられるが、これらに限定されるものではない。これらのうちナフトキノン系、ハイドロキノン系、ニトロソ系ピペラジン系のラジカル重合防止剤が好ましく、ナフトキノン、２−ヒドロキシナフトキノン、ハイドロキノン、２，６−ジ−ｔ−ブチル−Ｐ−クレゾール、ポリストップ７３００Ｐ（伯東株式会社製）が更に好ましく、ポリストップ７３００Ｐ（伯東株式会社製）が最も好ましい。
ラジカル重合防止剤の含有量としては本発明の樹脂組成物総量中、０．０００１〜１質量％が好ましく、０．００１〜０．５質量％が更に好ましく、０．０１〜０．２質量％が特に好ましい。
[Radical polymerization inhibitor]
The radical polymerization inhibitor is not particularly limited as long as it is a compound that reacts with radicals generated from a photoradical polymerization initiator, a thermal radical polymerization initiator, or the like to prevent polymerization, and is not particularly limited. A hindered radical type, a nitroso type, or the like can be used. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethyl-4. -Hydroxypiperidine-1-oxyl, 2,2,6,6, -tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxyl, hydroquinone , 2-Methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearyl β- (3) , 5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis-3-methyl-6-t-butylphenol ), 4,4'-Butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-) Methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis- [methylene-3- (3', 5'-di-t-butyl-4'- Hydroxyphenylpropionate)] Methyl, 1,3,5-tris (3', 5'-di-t-butyl-4'-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) Trion, paramethoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, aluminum salt of N-nitrosophenylhydroxyamine, trade name Adecastab LA-81, trade name Adecastab LA-82 (manufactured by Adeca Co., Ltd.), etc. However, it is not limited to these. Of these, naphthoquinone-based, hydroquinone-based, and nitroso-based piperazine-based radical polymerization inhibitors are preferable, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-t-butyl-P-cresol, and Polystop 7300P (Hakuto Co., Ltd.) (Manufactured by the company) is more preferable, and Polystop 7300P (manufactured by Hakuto Co., Ltd.) is the most preferable.
The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and 0.01 to 0.2% by mass in the total amount of the resin composition of the present invention. Is particularly preferable.
本発明の樹脂組成物を得る方法の一例としては、次に示す方法がある。まず、成分（Ｂ）（成分（Ｂ−１）と（Ｂ−２）を用いる場合には、その混合物）に、成分（Ａ）及び必要に応じて成分（Ｈ）を加熱溶解する。次いで室温まで冷却後、必要に応じて成分（Ｃ）、成分（Ｄ）、成分（Ｅ）、成分（Ｆ）、成分（Ｇ）、成分（Ｉ）、消泡剤、及びレベリング剤、溶剤等を添加し、公知の混合装置、例えば３本ロール、サンドミル、ボールミル等により均一に混合し、金属メッシュにて濾過することにより本発明の液晶シール剤を製造することができる。 As an example of the method for obtaining the resin composition of the present invention, there is the following method. First, the component (A) and, if necessary, the component (H) are heat-dissolved in the component (B) (a mixture thereof when the components (B-1) and (B-2) are used). Then, after cooling to room temperature, the component (C), the component (D), the component (E), the component (F), the component (G), the component (I), the defoaming agent, the leveling agent, the solvent, etc. The liquid crystal sealant of the present invention can be produced by adding the above, uniformly mixing with a known mixing device, for example, a three-roll, sand mill, ball mill or the like, and filtering with a metal mesh.
本発明の樹脂組成物は電子部品用封止剤や電子部品用接着剤として非常に有用である。電子部品用封止剤、接着剤としては、フレキシブルプリント配線板用接着剤、ＴＡＢ用接着剤、半導体用接着剤、各種ディスプレイ用接着剤等が挙げられるが、これらに限定されるものではない。 The resin composition of the present invention is very useful as a sealing agent for electronic parts and an adhesive for electronic parts. Examples of the sealant and the adhesive for electronic parts include, but are not limited to, an adhesive for a flexible printed wiring board, an adhesive for a TAB, an adhesive for a semiconductor, and an adhesive for various displays.
また、本発明の樹脂組成物は、液晶表示セル用接着剤として、特に液晶シール剤として非常に有用である。本発明の樹脂組成物を液晶シール剤として用いた場合の、液晶表示セルについて、以下に例を示す。 Further, the resin composition of the present invention is very useful as an adhesive for a liquid crystal display cell, particularly as a liquid crystal sealant. An example of a liquid crystal display cell when the resin composition of the present invention is used as a liquid crystal sealant is shown below.
本発明の液晶表示セル用接着剤を用いて製造される液晶表示セルは、基板に所定の電極を形成した一対の基板を所定の間隔に対向配置し、周囲を本発明の液晶シール剤でシールし、その間隙に液晶が封入されたものである。封入される液晶の種類は特に限定されない。ここで、基板とはガラス、石英、プラスチック、シリコン等からなる少なくとも一方に光透過性がある組み合わせの基板から構成される。その製法としては、本発明の液晶シール剤に、グラスファイバー等のスペーサ（間隙制御材）を添加後、該一対の基板の一方にディスペンサー、またはスクリーン印刷装置等を用いて該液晶シール剤を塗布した後、必要に応じて、８０〜１２０℃で仮硬化を行う。その後、該液晶シール剤の堰の内側に液晶を滴下し、真空中にてもう一方のガラス基板を重ね合わせ、ギャップ出しを行う。ギャップ形成後、９０〜１３０℃で３０分〜２時間硬化することにより本発明の液晶表示セルを得ることができる。また光熱併用型として使用する場合は、紫外線照射機により液晶シール剤部に紫外線を照射させて光硬化させる。紫外線照射量は、好ましくは５００〜６０００ｍＪ／ｃｍ２、より好ましくは１０００〜４０００ｍＪ／ｃｍ２の照射量が好ましい。その後必要に応じて、９０〜１３０℃で３０分〜２時間硬化することにより本発明の液晶表示セルを得ることができる。このようにして得られた本発明の液晶表示セルは、液晶汚染による表示不良が無く、接着性、耐湿信頼性に優れたものである。スペーサとしては、例えばグラスファイバー、シリカビーズ、ポリマービーズ等があげられる。その直径は、目的に応じ異なるが、通常２〜８μｍ、好ましくは４〜７μｍである。その使用量は、本発明の液晶シール剤１００質量部に対し通常０．１〜４質量部、好ましくは０．５〜２質量部、更に、好ましくは０．９〜１．５質量部程度である。 In a liquid crystal display cell manufactured by using the liquid crystal display cell adhesive of the present invention, a pair of substrates having predetermined electrodes formed on the substrates are arranged facing each other at predetermined intervals, and the periphery thereof is sealed with the liquid crystal sealant of the present invention. However, the liquid crystal is enclosed in the gap. The type of liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a combination of substrates made of glass, quartz, plastic, silicon, etc., which has light transmission in at least one of them. As the manufacturing method, after adding a spacer (gap control material) such as glass fiber to the liquid crystal sealant of the present invention, the liquid crystal sealant is applied to one of the pair of substrates using a dispenser, a screen printing device or the like. Then, if necessary, temporary curing is performed at 80 to 120 ° C. After that, the liquid crystal is dropped on the inside of the weir of the liquid crystal sealant, and the other glass substrate is overlapped in a vacuum to create a gap. After forming the gap, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 30 minutes to 2 hours. When used as a photo-heat combined type, the liquid crystal sealant portion is irradiated with ultraviolet rays by an ultraviolet irradiator to be photo-cured. UV irradiation dose is preferably 500~6000mJ / cm 2, more preferably the dose of 1000~4000mJ / cm 2 is preferred. Then, if necessary, the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 30 minutes to 2 hours. The liquid crystal display cell of the present invention thus obtained is excellent in adhesiveness and moisture resistance and reliability without display defects due to liquid crystal contamination. Examples of the spacer include glass fiber, silica beads, polymer beads and the like. Its diameter varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount used is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, and more preferably about 0.9 to 1.5 parts by mass with respect to 100 parts by mass of the liquid crystal sealant of the present invention. be.
本発明の樹脂組成物は、柔軟性と低透湿性を両立するものである為、フレキシブル基板等が用いられ、かつ耐湿信頼性の要求される分野の接着剤用途の使用に非常に適するものである。例えば液晶シール剤、有機ＥＬ用封止剤、タッチパネル用接着剤である。 Since the resin composition of the present invention has both flexibility and low moisture permeability, it is very suitable for use in adhesive applications in fields where flexible substrates and the like are used and moisture resistance and reliability are required. be. For example, a liquid crystal sealant, an organic EL sealant, and a touch panel adhesive.
以下、実施例により本発明を更に詳細に説明するが、本発明は実施例に限定されるものではない。尚、特別の記載のない限り、本文中「部」及び「％」とあるのは質量基準である。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. Unless otherwise specified, "part" and "%" in the text are based on mass.
［合成例１：ビスフェノールＡ型エポキシ樹脂の全アクリル化物の合成］
ビスフェノールＡ型エポキシ樹脂２８２．５ｇ（製品名：ＹＤ−８１２５、新日鉄化学株式会社製）をトルエン２６６．８ｇに溶解し、これに重合禁止剤としてジブチルヒドロキシトルエン０．８ｇを加え、６０℃まで昇温した。その後、エポキシ基の１００％当量のアクリル酸１１７．５ｇを加え更に８０℃まで昇温し、これに反応触媒であるトリメチルアンモニウムクロライド０．６ｇを添加して、９８℃で約３０時間攪拌し、反応液を得た。この反応液を水洗し、トルエンを留去することにより、目的とするビスフェノールＡ型のエポキシアクリレート３９５ｇを得た。
[Synthesis Example 1: Synthesis of all acrylics of bisphenol A type epoxy resin]
282.5 g of bisphenol A type epoxy resin (product name: YD-8125, manufactured by Nippon Steel Chemical Co., Ltd.) is dissolved in 266.8 g of toluene, 0.8 g of dibutylhydroxytoluene is added as a polymerization inhibitor, and the temperature rises to 60 ° C. It was warm. Then, 117.5 g of acrylic acid equivalent to 100% of the epoxy group was added, the temperature was further raised to 80 ° C., 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C. for about 30 hours. A reaction solution was obtained. This reaction solution was washed with water and toluene was distilled off to obtain 395 g of the desired bisphenol A type epoxy acrylate.
［合成例２：ビスフェノールＡ型エポキシ樹脂の全メタクリル化物の合成］
ビスフェノールＡ型エポキシ樹脂２８２．５ｇ（製品名：ＹＤ−８１２５、新日鉄化学株式会社製）をトルエン２６６．８ｇに溶解し、これに重合禁止剤としてジブチルヒドロキシトルエン０．８ｇを加え、６０℃まで昇温した。その後、エポキシ基の１００％当量のメタクリル酸１４０．６ｇを加え更に８０℃まで昇温し、これに反応触媒であるトリメチルアンモニウムクロライド０．６ｇを添加して、９８℃で約３０時間攪拌し、反応液を得た。この反応液を水洗し、トルエンを留去することにより、目的とするビスフェノールＡ型のエポキシメタクリレート４１７ｇを得た。
[Synthesis Example 2: Synthesis of all methacrylates of bisphenol A type epoxy resin]
282.5 g of bisphenol A type epoxy resin (product name: YD-8125, manufactured by Nippon Steel Chemical Co., Ltd.) is dissolved in 266.8 g of toluene, 0.8 g of dibutylhydroxytoluene is added as a polymerization inhibitor, and the temperature rises to 60 ° C. It was warm. Then, 140.6 g of methacrylic acid equivalent to 100% of the epoxy group was added, the temperature was further raised to 80 ° C., 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C. for about 30 hours. A reaction solution was obtained. This reaction solution was washed with water and toluene was distilled off to obtain 417 g of the desired bisphenol A type epoxy methacrylate.
［合成例３：ビスフェノールＡ型エポキシ樹脂の部分メタクリル化物の合成］
ビスフェノールＡ型エポキシ樹脂８３６ｇ（日本化薬株式会社製ＲＥ−３１０Ｓ）をトルエン１０００ｇに溶解し、これに重合禁止剤としてジブチルヒドロキシトルエン３ｇを加え、６０℃まで昇温した。その後、エポキシ基の５０％当量のメタクリル酸１９７ｇと反応触媒であるトリプロピルアンモニウムヒドロキシドの４０％水溶液５ｇを添加して、９８℃で約１０時間攪拌し、反応液を得た。この反応液を水洗し、トルエンを留去することにより、目的とする部分メタクリル化ビスフェノールＡ型エポキシ樹脂１０２７ｇを得た。
[Synthesis Example 3: Synthesis of Partial Methacrylate of Bisphenol A Type Epoxy Resin]
836 g of bisphenol A type epoxy resin (RE-310S manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 1000 g of toluene, 3 g of dibutylhydroxytoluene was added as a polymerization inhibitor, and the temperature was raised to 60 ° C. Then, 197 g of methacrylic acid equivalent to 50% of the epoxy group and 5 g of a 40% aqueous solution of tripropylammonium hydroxide as a reaction catalyst were added, and the mixture was stirred at 98 ° C. for about 10 hours to obtain a reaction solution. This reaction solution was washed with water and toluene was distilled off to obtain 1027 g of the desired partially methacrylated bisphenol A type epoxy resin.
［合成例４：ビスフェノールＡ型エポキシ樹脂の部分アクリル化物の合成］
ビスフェノールＡ型エポキシ樹脂８３６ｇ（日本化薬株式会社製ＲＥ−３１０Ｓ）をトルエン１０００ｇに溶解し、これに重合禁止剤としてジブチルヒドロキシトルエン３ｇを加え、６０℃まで昇温した。その後、エポキシ基の５０％当量のアクリル酸１６５ｇ（株式会社日本触媒製）と反応触媒であるトリプロピルアンモニウムヒドロキシドの４０％水溶液５ｇを添加して、９８℃で約１０時間攪拌し、反応液を得た。この反応液を水洗し、トルエンを留去することにより、目的とする部分アクリル化ビスフェノールＡ型エポキシ樹脂９９５ｇを得た。
[Synthesis Example 4: Synthesis of partial acrylics of bisphenol A type epoxy resin]
836 g of bisphenol A type epoxy resin (RE-310S manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 1000 g of toluene, 3 g of dibutylhydroxytoluene was added as a polymerization inhibitor, and the temperature was raised to 60 ° C. Then, 165 g of acrylic acid having a 50% equivalent of an epoxy group (manufactured by Nippon Shokubai Co., Ltd.) and 5 g of a 40% aqueous solution of tripropylammonium hydroxide as a reaction catalyst were added, and the mixture was stirred at 98 ° C. for about 10 hours to prepare a reaction solution. Got This reaction solution was washed with water and toluene was distilled off to obtain 995 g of the target partially acrylicized bisphenol A type epoxy resin.
［合成例５：１，２−ビス（トリメチルシロキシ）−１，１，２，２−テトラフェニルエタンの合成］
市販ベンゾピナコール（東京化成製）１００部（０．２８モル）をジメチルホルムアルデヒド３５０部に溶解させた。これに塩基触媒としてピリジン３２部（０．４モル）、シリル化剤としてＢＳＴＦＡ（信越化学工業製）１５０部（０．５８モル）を加え７０℃まで昇温し、２時間攪拌した。得られた反応液を冷却し、攪拌しながら、水２００部を入れ、生成物を沈殿させると共に未反応シリル化剤を失活させた。沈殿した生成物をろ別分離した後十分に水洗した。次いで得られた生成物をアセトンに溶解し、水を加えて再結晶させ、精製した。目的の１，２−ビス（トリメチルシロキシ）−１，１，２，２−テトラフェニルエタンを１０５．６部（収率８８．３％）得た。
[Synthesis Example 5: Synthesis of 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane]
100 parts (0.28 mol) of commercially available benzopinacol (manufactured by Tokyo Kasei) was dissolved in 350 parts of dimethyl formaldehyde. To this, 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of BSTFA (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silylating agent were added, the temperature was raised to 70 ° C., and the mixture was stirred for 2 hours. The obtained reaction solution was cooled and stirred with 200 parts of water to precipitate the product and inactivate the unreacted silylating agent. The precipitated product was separated by filtration and washed thoroughly with water. The resulting product was then dissolved in acetone, water was added to recrystallize and purify. The desired 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane was obtained in 105.6 parts (yield 88.3%).
［実施例１〜１２、比較例１、２］
下記表１に示す割合で成分（Ｂ）（成分（Ｂ−１）と（Ｂ−２）を用いる場合には、その混合物）に、成分（Ａ）、成分（Ｈ）を９０℃で加熱溶解させた後、室温まで冷却し、成分（Ｃ）、成分（Ｄ）、成分（Ｅ）、成分（Ｆ）、成分（Ｇ）、成分（Ｉ）を添加し、攪拌した後、３本ロールミルにて分散させ、金属メッシュ（６３５メッシュ）で濾過し、実施例１〜１２を調製した。また、成分（Ａ）を除いて、比較例１、２を調製した。
[Examples 1 to 12, Comparative Examples 1 and 2]
The component (A) and the component (H) are dissolved by heating at 90 ° C. in the component (B) (a mixture thereof when the components (B-1) and (B-2) are used) in the ratio shown in Table 1 below. After allowing to cool to room temperature, the component (C), the component (D), the component (E), the component (F), the component (G), and the component (I) are added, stirred, and then put into a three-roll mill. And filtered through a metal mesh (635 mesh) to prepare Examples 1-12. Further, Comparative Examples 1 and 2 were prepared except for the component (A).
［透湿度］
実施例及び比較例で製造した液晶シール剤について、ポリエチレンテレフタレート（ＰＥＴ）フィルムに挟み、厚み１００μｍの薄膜としたものに、メタルハライドランプ（ウシオ電機株式会社製）にて３０００ｍＪ／ｃｍ２（１００ｍＷ／ｃｍ２で３０秒）の紫外線を照射して硬化させた後、１２０℃のオーブンに４０分間投入して硬化させた。その後、ＰＥＴフィルムをはがしサンプルとした。サンプルの６０℃９０％での透湿度を透湿度測定機（Ｌｅｓｓｙ社製：Ｌ８０−５０００）にて測定した。結果を表１と表２に示す。
[Humidity permeability]
The liquid crystal sealant produced in Examples and Comparative Examples was sandwiched between polyethylene terephthalate (PET) films to form a thin film with a thickness of 100 μm, and then used with a metal halide lamp (manufactured by Ushio, Inc.) at 3000 mJ / cm 2 (100 mW / cm). After irradiating with ultraviolet rays (2 for 30 seconds) to cure, the film was placed in an oven at 120 ° C. for 40 minutes to cure. Then, the PET film was peeled off and used as a sample. The moisture permeability of the sample at 60 ° C. and 90% was measured with a moisture permeability measuring machine (Lessy Co., Ltd .: L80-5000). The results are shown in Tables 1 and 2.
［屈曲性］
実施例及び比較例で製造した液晶シール剤について、ポリエチレンテレフタレート（ＰＥＴ）フィルムに挟み、厚み１００μｍの薄膜としたものに、メタルハライドランプ（ウシオ電機株式会社製）にて３０００ｍＪ／ｃｍ２（１００ｍＷ／ｃｍ２で３０秒）の紫外線を照射して硬化させた後、１２０℃のオーブンに４０分間投入して硬化させた。その後、ＰＥＴフィルムをはがしシール剤硬化膜を５０ｍｍ×５ｍｍの短冊状にカットしサンプル片とした。得られたサンプルを２ｍｍΦの棒に巻き付け、１０秒間固定した。試験片が割れていないものを○、試験片が割れたものを×として評価した。結果を表１と表２に示す。
[Flexibility]
The liquid crystal sealant produced in Examples and Comparative Examples was sandwiched between polyethylene terephthalate (PET) films to form a thin film with a thickness of 100 μm, and then used with a metal halide lamp (manufactured by Ushio, Inc.) at 3000 mJ / cm 2 (100 mW / cm). After irradiating with ultraviolet rays (2 for 30 seconds) to cure, the film was placed in an oven at 120 ° C. for 40 minutes to cure. Then, the PET film was peeled off and the sealant cured film was cut into strips of 50 mm × 5 mm to obtain sample pieces. The obtained sample was wound around a 2 mmΦ rod and fixed for 10 seconds. Those in which the test piece was not cracked were evaluated as ◯, and those in which the test piece was broken were evaluated as x. The results are shown in Tables 1 and 2.
［ガラス転移温度（Ｔｇ）］
実施例及び比較例で製造した液晶シール剤について、ポリエチレンテレフタレート（ＰＥＴ）フィルムに挟み、厚み１００μｍの薄膜としたものに、メタルハライドランプ（ウシオ電機株式会社製）にて３０００ｍＪ／ｃｍ２（１００ｍＷ／ｃｍ２で３０秒）の紫外線を照射して硬化させた後、１２０℃のオーブンに４０分間投入して硬化させた。その後、ＰＥＴフィルムをはがしシール剤硬化膜を５０ｍｍ×５ｍｍの短冊状にカットしサンプル片とした。このサンプル片を動的粘弾性測定装置（ＤＭＳ−６１００：エスアイアイ・ナノテクノロジー社製）の引っ張りモードにて周波数１０Ｈｚ、昇温温度２℃／分の条件で測定を行った。損失弾性率と貯蔵弾性率との比（ＪＩＳ Ｋ ７２４４−１）から損失係数Ｔａｎδが得られ、得られた損失係数Ｔａｎδが最大値となる温度をガラス転移温度（Ｔｇ）とした。結果を表１と表２に示す。
[Glass transition temperature (Tg)]
The liquid crystal sealant produced in Examples and Comparative Examples was sandwiched between polyethylene terephthalate (PET) films to form a thin film with a thickness of 100 μm, and then used with a metal halide lamp (manufactured by Ushio, Inc.) at 3000 mJ / cm 2 (100 mW / cm). After irradiating with ultraviolet rays (2 for 30 seconds) to cure, the film was placed in an oven at 120 ° C. for 40 minutes to cure. Then, the PET film was peeled off and the sealant cured film was cut into strips of 50 mm × 5 mm to obtain sample pieces. This sample piece was measured in a tensile mode of a dynamic viscoelasticity measuring device (DMS-6100: manufactured by SII Nanotechnology) under the conditions of a frequency of 10 Hz and a temperature rise temperature of 2 ° C./min. The loss coefficient Tan δ was obtained from the ratio of the loss elastic modulus to the storage elastic modulus (JIS K 7424-1), and the temperature at which the obtained loss coefficient Tan δ became the maximum value was defined as the glass transition temperature (Tg). The results are shown in Tables 1 and 2.
表１、表２に示されるように、実施例１〜１２の樹脂組成物は、柔軟性が高く、それでいて透湿度も低い値を示している。従って、本発明の樹脂組成物は、フレキシブル基板等に使用される接着剤として、優れた特性を有することが確認された。 As shown in Tables 1 and 2, the resin compositions of Examples 1 to 12 show high flexibility and low moisture permeability. Therefore, it was confirmed that the resin composition of the present invention has excellent properties as an adhesive used for flexible substrates and the like.
本発明の樹脂組成物は、柔軟性と低透湿性を両立できるものである為、電子部品用接着剤、特にディスプレイ用封止剤として有用である。
Since the resin composition of the present invention can achieve both flexibility and low moisture permeability, it is useful as an adhesive for electronic parts, particularly as a sealing agent for displays.
Claims (9)
成分（Ｂ）硬化性化合物、
成分（Ｄ）有機フィラー、
成分（Ｉ）熱ラジカル重合開始剤、
を含有する樹脂組成物であって、前記成分（Ａ）は更に反応性二重結合を有し、数平均分子量は５００以上１３００以下であり、前記成分（Ｂ）としてエポキシ（メタ）アクリレートを含有し、前記成分（Ｄ）としてウレタン微粒子、アクリル微粒子、スチレン微粒子、スチレンオレフィン微粒子、及びシリコーン微粒子からなる群より選択される１又は２以上の有機フィラーを含有し、前記成分（Ｉ）として１，２−ビス（トリメチルシロキシ）−１，１，２，２−テトラフェニルエタンを含有する樹脂組成物。 Component (A): Polybutadiene compound having an epoxy group in the molecule,
Ingredient (B) curable compound,
Ingredient (D) Organic filler,
Ingredient (I) Thermal Radical Polymerization Initiator,
The component (A) further has a reactive double bond, the number average molecular weight is 500 or more and 1300 or less, and the component (B) contains an epoxy (meth) acrylate. The component (D) contains one or more organic fillers selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles, and the component (I) is 1, A resin composition containing 2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane.
A liquid crystal display cell adhered using the liquid crystal sealant according to claim 8 .
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