JP2018104668A - Photocurable resin composition and electronic component sealant - Google Patents
Photocurable resin composition and electronic component sealant Download PDFInfo
- Publication number
- JP2018104668A JP2018104668A JP2017129657A JP2017129657A JP2018104668A JP 2018104668 A JP2018104668 A JP 2018104668A JP 2017129657 A JP2017129657 A JP 2017129657A JP 2017129657 A JP2017129657 A JP 2017129657A JP 2018104668 A JP2018104668 A JP 2018104668A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- component
- photocurable resin
- compound
- liquid crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 87
- 239000000565 sealant Substances 0.000 title claims description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- -1 oxime compound Chemical class 0.000 claims abstract description 53
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004973 liquid crystal related substance Substances 0.000 claims description 53
- 239000004593 Epoxy Substances 0.000 claims description 27
- 239000010419 fine particle Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000007789 sealing Methods 0.000 claims description 16
- 239000007870 radical polymerization initiator Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 10
- 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
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 206010034960 Photophobia Diseases 0.000 abstract 1
- 208000013469 light sensitivity Diseases 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 35
- 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 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000003822 epoxy resin Substances 0.000 description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 15
- 229920000647 polyepoxide Polymers 0.000 description 15
- 239000000758 substrate Substances 0.000 description 14
- 239000007983 Tris buffer Substances 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 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
- 238000000034 method Methods 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
- 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 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 125000003118 aryl group Chemical group 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
- 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
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical group C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 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
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229930192627 Naphthoquinone Natural products 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 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
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002791 naphthoquinones Chemical class 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical class 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 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
- 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
- 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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 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
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-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
- 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
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229940091173 hydantoin Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000005985 organic acids Nutrition 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[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
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
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- 230000000630 rising effect Effects 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 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
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 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
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- MDJZGXRFYKPSIM-JCYAYHJZSA-N (2r,3r)-2,3-dihydroxybutanedihydrazide Chemical compound NNC(=O)[C@H](O)[C@@H](O)C(=O)NN MDJZGXRFYKPSIM-JCYAYHJZSA-N 0.000 description 1
- 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
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 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
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- 239000005457 ice water Substances 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 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
- 238000005121 nitriding Methods 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-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
- 238000010943 off-gassing Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000003544 oxime group Chemical group 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
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 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
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
- 230000007017 scission Effects 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
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 230000014616 translation Effects 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
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 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 compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
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- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/04—Non-macromolecular additives inorganic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
Description
本発明は、電子部品用封止剤に使用される光硬化性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光硬化性樹脂組成物に関する。この光硬化性樹脂組成物は、低エネルギー光に対しても好感度であり、更にはアウトガスも少ない為、電子部品用封止剤として極めて有用であり、特に表示ディスプレイ用封止剤として有用である。 The present invention relates to a photocurable resin composition used for an electronic component sealant. More specifically, the present invention relates to a photocurable resin composition containing a compound having a specific structure in the molecule. This photo-curable resin composition has good sensitivity to low energy light, and also has little outgas, so it is extremely useful as a sealant for electronic parts, and particularly useful as a sealant for display displays. is there.
光硬化性樹脂組成物は、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封止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、アウトガスの発生が少なく、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。
しかし、光硬化性樹脂組成物の欠点は、光の届かない部分で硬化反応が進行しないことであり、使用できる部分に制限があることである。
Photocurable resin compositions are widely used in electronic component sealants such as display sealants, solar cell sealants, and semiconductor sealants. Examples of the display sealing agent include a liquid crystal sealing agent, an organic EL display sealing agent, and a touch panel adhesive. What is common as these materials is that they have excellent curability but require little outgassing and no damage to the display element.
However, a drawback of the photocurable resin composition is that the curing reaction does not proceed in a portion where light does not reach, and there are limitations on the portion that can be used.
特に液晶滴下工法用液晶シール剤（以下、「シール剤」と表記する。）においては、液晶表示素子のアレイ基板の配線部分やカラーフィルター基板のブラックマトリックス部分により液晶シール剤に光が当たらない遮光部が生じ、シール部近傍の表示不良の問題が以前よりも深刻なものとなっている。すなわち、遮光部の存在によって上記光による一次硬化が不十分となり、液晶シール剤中に未硬化成分が多量に残存する。この状態で熱による二次硬化工程に進んだ場合、当該未硬化成分の液晶への溶解は、熱によって促進されてしまうという結果をもたらし、シール部近傍の表示不良を引き起こすという問題がある。 In particular, in a liquid crystal sealing agent for liquid crystal dropping method (hereinafter referred to as “sealing agent”), light is not applied to the liquid crystal sealing agent by the wiring portion of the array substrate of the liquid crystal display element or the black matrix portion of the color filter substrate. The problem of display failure near the seal portion is more serious than before. That is, the primary curing by the light becomes insufficient due to the presence of the light shielding part, and a large amount of uncured components remain in the liquid crystal sealant. When the process proceeds to the secondary curing step by heat in this state, dissolution of the uncured component into the liquid crystal is accelerated by heat, and there is a problem in that display failure near the seal portion is caused.
この課題を解決する為、熱反応性を改良する様々な検討がなされている。上記遮光部において、光によって十分に硬化していない液晶シール剤を、低温から速やかに反応させ、液晶汚染を抑えようという試みである。例えば、特許文献１、２では、熱ラジカル重合開始剤を用いる方法が開示されている。また、特許文献３〜５では、硬化促進剤として多価カルボン酸を用いる方法が開示されている。 In order to solve this problem, various studies have been made to improve thermal reactivity. It is an attempt to suppress liquid crystal contamination by reacting a liquid crystal sealant that is not sufficiently cured by light in the light shielding portion from a low temperature. For example, Patent Documents 1 and 2 disclose a method using a thermal radical polymerization initiator. Patent Documents 3 to 5 disclose a method using a polyvalent carboxylic acid as a curing accelerator.
しかし、熱ラジカル重合開始剤に効率良くラジカルを発生させる為には、ある程度分子量の小さいものである必要があるが、低分子化合物は液晶に溶解し易く、反応性には優れるものの、熱ラジカル重合開始剤自身による液晶汚染性が問題となる。
また、多価カルボン酸を用いた場合、耐湿信頼性を損なう可能性もあり、用途によっては使用できない場合もある。
However, in order to efficiently generate radicals in the thermal radical polymerization initiator, it is necessary that the molecular weight is small to some extent, but low molecular compounds are easily dissolved in liquid crystals and have excellent reactivity. Liquid crystal contamination due to the initiator itself becomes a problem.
Moreover, when a polyvalent carboxylic acid is used, there is a possibility that the moisture resistance reliability may be impaired, and it may not be used depending on the application.
以上述べたように、液晶シール剤の開発は非常に精力的に行われているにも拘わらず、優れた遮光部硬化性を有しながら、低液晶汚染性である液晶シール剤は未だ実現していない。 As described above, despite the fact that the development of liquid crystal sealants has been carried out very vigorously, liquid crystal sealants that have excellent light-shielding part curability and low liquid crystal contamination have not yet been realized. Not.
本発明は、紫外線や可視光線といった光照射によって硬化する樹脂組成物に関するものであり、光に対する感度が高く、低エネルギー光によっても十分硬化する樹脂組成物を提案するものである。当該光硬化性樹脂組成物は、光が十分に当たらない部分における硬化性も高く、また他の部材へのダメージを考慮した低エネルギーの光照射でも十分な硬化性を有する為、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 that is cured by irradiation with light such as ultraviolet rays and visible light, and proposes a resin composition that has high sensitivity to light and can be sufficiently cured even by low energy light. The photo-curable resin composition has high curability in a portion where light is not sufficiently applied, and has sufficient curability even when irradiated with low energy in consideration of damage to other members. It is useful as an agent, particularly as a sealant for a display.
本発明者らは、鋭意検討の結果、分子内にフラン構造を有するオキシム化合物を含有する光硬化性樹脂組成物が、光ラジカル重合開始剤として、非常に優れ、すなわち低エネルギーの光照射でも十分な硬化性を有することを見出し、本発明に至ったものである。
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 intensive studies, the present inventors have found that a photocurable resin composition containing an oxime compound having a furan structure in the molecule is very excellent as a radical photopolymerization initiator, that is, sufficient irradiation with low-energy light is sufficient. The present invention has been found to have excellent curability.
In the present specification, “(meth) acryl” means “acryl and / or methacryl”, and “(meth) acryloyl group” means “acryloyl group and / or methacryloyl group”. Further, “liquid crystal sealing agent for liquid crystal dropping method” may be simply referred to as “liquid crystal sealing agent” or “sealing agent”.
即ち本発明は、次の［１］〜［１９］に関するものである。
［１］成分（Ａ）分子内にフラン構造を有するオキシム化合物、成分（Ｂ）硬化性化合物を含有する光硬化性樹脂組成物。
［２］前記成分（Ａ）が、ベンゾフラン骨格を有するオキシム化合物である前項［１］に記載の光硬化性樹脂組成物。
［３］前記成分（Ａ）が、硫化ジフェニル構造を有するオキシム化合物である前項［１］又は［２］に記載の光硬化性樹脂組成物。
［４］前記成分（Ａ）が、下記式（Ａ−１）で表される化合物である前項［１］乃至［３］のいずれか一項に記載の光硬化性樹脂組成物。
That is, the present invention relates to the following [1] to [19].
[1] A photocurable resin composition containing an oxime compound having a furan structure in the component (A) molecule and a component (B) curable compound.
[2] The photocurable resin composition according to [1], wherein the component (A) is an oxime compound having a benzofuran skeleton.
[3] The photocurable resin composition according to [1] or [2] above, wherein the component (A) is an oxime compound having a diphenyl sulfide structure.
[4] The photocurable resin composition according to any one of [1] to [3], wherein the component (A) is a compound represented by the following formula (A-1).
［５］前記成分（Ｂ）が、成分（Ｂ−１）（メタ）アクリル化合物である前項［１］乃至［４］のいずれか一項に記載の光硬化性樹脂組成物。
［６］前記成分（Ｂ）が、成分（Ｂ−１）（メタ）アクリル化合物と成分（Ｂ−２）エポキシ化合物の混合物である前項［１］乃至［５］のいずれか一項に記載の光硬化性樹脂組成物。
［７］更に、成分（Ｃ）有機フィラーを含有する前項［１］及至［６］のいずれか一項に記載の光硬化性樹脂組成物。
［８］前記成分（Ｃ）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［７］に記載の光硬化性樹脂組成物。
［９］更に、成分（Ｄ）無機フィラーを含有する前項［１］及至［８］のいずれか一項に記載の光硬化性樹脂組成物。
［１０］更に、成分（Ｅ）シランカップリング剤を含有する前項［１］及至［９］のいずれか一項に記載の光硬化性樹脂組成物。
［１１］更に、成分（Ｆ）熱硬化剤を含有する前項［１］及至［１０］のいずれか一項に記載の光硬化性樹脂組成物。
［１２］前記成分（Ｆ）が有機酸ヒドラジド化合物である前項［１１］に記載の光硬化性樹脂組成物。
［１３］更に、成分（Ｇ）水素引抜型光ラジカル重合開始剤を含有する前項［１］及至［１２］のいずれか一項に記載の光硬化性樹脂組成物。
［１４］更に、成分（Ｈ）熱ラジカル重合開始剤を含有する前項［１］及至［１３］のいずれか一項に記載の光硬化性樹脂組成物。
［１５］前項［１］乃至［１４］のいずれか一項に記載の光硬化性樹脂組成物を用いた電子部品用封止剤。
［１６］前項［１５］に記載の電子部品用接着剤を硬化して得られる硬化物を用いた電子部品。
［１７］前項［１］乃至［１４］のいずれか一項に記載の光硬化性樹脂組成物を用いた液晶表示セル用封止剤。
［１８］前項［１］乃至［１４］のいずれか一項に記載の光硬化性樹脂組成物を用いた液晶シール剤。
［１９］前項［１７］又は［１８］に記載の液晶表示セル用封止剤又は液晶シール剤を用いて接着された液晶表示セル。
[5] The photocurable resin composition according to any one of [1] to [4], wherein the component (B) is a component (B-1) (meth) acrylic compound.
[6] The component (B) according to any one of [1] to [5], wherein the component (B-1) is a mixture of a (meth) acrylic compound and a component (B-2) epoxy compound. Photocurable resin composition.
[7] The photocurable resin composition according to any one of [1] to [6] above, further comprising a component (C) an organic filler.
[8] The light according to [7], wherein the component (C) 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. Curable resin composition.
[9] The photocurable resin composition according to any one of [1] to [8], which further contains a component (D) inorganic filler.
[10] The photocurable resin composition according to any one of [1] to [9], further including a component (E) a silane coupling agent.
[11] The photocurable resin composition according to any one of [1] to [10], further comprising a component (F) a thermosetting agent.
[12] The photocurable resin composition according to [11], wherein the component (F) is an organic acid hydrazide compound.
[13] The photocurable resin composition according to any one of [1] to [12], further comprising a component (G) a hydrogen abstraction type photoradical polymerization initiator.
[14] The photocurable resin composition according to any one of [1] to [13], further comprising a component (H) a thermal radical polymerization initiator.
[15] A sealant for electronic parts using the photocurable resin composition according to any one of [1] to [14].
[16] An electronic component using a cured product obtained by curing the adhesive for electronic components according to [15].
[17] A sealant for a liquid crystal display cell using the photocurable resin composition according to any one of [1] to [14].
[18] A liquid crystal sealant using the photocurable resin composition according to any one of [1] to [14].
[19] A liquid crystal display cell bonded using the liquid crystal display cell sealant or liquid crystal sealant according to [17] or [18].
本発明の光硬化性樹脂組成物は、低エネルギー光によっても十分な硬化性を示す為、遮光部分を有する電子部品や、可視光によって硬化させる必要のある電子部品用の封止剤として非常に有用である。 Since the photocurable resin composition of the present invention exhibits sufficient curability even with low energy light, it is very useful as an encapsulant for electronic components having light-shielding portions and electronic components that need to be cured by visible light. Useful.
［（Ａ）分子内にフラン構造を有するオキシム化合物］
本発明の光硬化性樹脂組成物は、（Ａ）分子内にフラン構造を有するオキシム化合物（以下、単に「成分（Ａ）」ともいう。）を含有する。この化合物は、低エネルギー光に対する感度が非常に高い、光ラジカル重合開始剤として機能する。
フラン構造はフラン環そのものであっても、他の環が縮環したものであっても良く、例えばベンゾフラン、イソベンゾフランのような骨格も含まれる。ベンゾフラン骨格を含むものが好ましい。
またフラン構造中に他の置換基を有しても良い。置換基としては、Ｃ１−Ｃ１０のアルキル基、Ｃ１−Ｃ１０のアルコキシ基、Ｃ１−Ｃ１０のアリール基、ハロゲン原子、ヒドロキシ基、カルボキシ基、ニトロ基、シアノ基等を挙げることができる。
Ｃ１−Ｃ１０のアルキル基としては、Ｃ１−Ｃ６のアルキル基が好ましく、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、へキシル基等の直鎖、分岐鎖または環状構造を有するアルキル基がより好ましく、メチル基、エチル基、ブチル基、ter-ブチル基が特に好ましい。Ｃ１−Ｃ１０のアルコキシ基としてはＣ１−Ｃ６のアルコキシ基が好ましく、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の直鎖、分岐鎖または環状構造を有するアルコキシ基がより好ましく、メトキシ基、エトキシ基、プロポキシ基が特に好ましい。Ｃ１−Ｃ１０のアリール基としてはフェニル基が好ましい。
前記フラン構造は、カルボニル基を介してフェニルスルフィド（硫化ジフェニル）構造、ジフェニルエーテル構造又はフルオレン構造と結合することが好ましい。
オキシム基に結合している有機基としては、Ｃ１−Ｃ１０のアルキル基、Ｃ１−Ｃ１０のアルコキシ基、Ｃ１−Ｃ１０のアリール基、ハロゲン原子、ヒドロキシ基、カルボキシ基、ニトロ基、シアノ基等を挙げることができ、好ましくは前述と同様である。
なお当該化合物は、特表２０１６−５３１９２６号公報に従って合成することができる。また、当該化合物は例えばＩＲＧＡＣＵＲＥ ＯＸＥ ０４として、市場からの入手も可能である。
成分（Ａ）は単独で用いても良いし、２種類以上を混合しても良い。本発明の光硬化性樹脂組成物において、成分（Ａ）の配合量は、光硬化性樹脂組成物総量中、通常０．１〜７質量％、好ましくは０．２〜５質量％であり、より好ましくは０．３〜３質量％である。
[(A) Oxime compound having furan structure in molecule]
The photocurable resin composition of the present invention contains (A) an oxime compound having a furan structure in the molecule (hereinafter also simply referred to as “component (A)”). This compound functions as a photo-radical polymerization initiator having very high sensitivity to low energy light.
The furan structure may be a furan ring itself or may be a condensed ring of another ring, and includes a skeleton such as benzofuran and isobenzofuran. Those containing a benzofuran skeleton are preferred.
Moreover, you may have another substituent in a furan structure. Examples of the substituent include a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 aryl group, a halogen atom, a hydroxy group, a carboxy group, a nitro group, and a cyano group.
As the C1-C10 alkyl group, a C1-C6 alkyl group is preferable, and an alkyl group having a linear, branched, or cyclic structure such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group. Are more preferable, and a methyl group, an ethyl group, a butyl group, and a ter-butyl group are particularly preferable. The C1-C10 alkoxy group is preferably a C1-C6 alkoxy group, more preferably an alkoxy group having a linear, branched or cyclic structure such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. And a propoxy group are particularly preferred. The C1-C10 aryl group is preferably a phenyl group.
The furan structure is preferably bonded to a phenyl sulfide (diphenyl sulfide) structure, a diphenyl ether structure or a fluorene structure via a carbonyl group.
Examples of the organic group bonded to the oxime group include a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 aryl group, a halogen atom, a hydroxy group, a carboxy group, a nitro group, and a cyano group. Preferably, as described above.
In addition, the said compound is compoundable according to Japanese translations of PCT publication No. 2006-531926. The compound can also be obtained from the market as IRGACURE OXE 04, for example.
A component (A) may be used independently and may mix 2 or more types. In the photocurable resin composition of the present invention, the compounding amount of the component (A) is usually 0.1 to 7% by mass, preferably 0.2 to 5% by mass in the total amount of the photocurable resin composition. More preferably, it is 0.3-3 mass%.
［（Ｂ）硬化性化合物］
本発明の光硬化性樹脂組成物は、成分（Ｂ）として、硬化性化合物を含有する（以下、単に「成分（Ｂ）」ともいう。）。
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、（Ｂ−１）（メタ）アクリル化合物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。
[(B) curable compound]
The photocurable resin composition of the present invention contains a curable compound as the component (B) (hereinafter, also simply referred to as “component (B)”).
Although it will not specifically limit as a component (B) if it is a compound hardened | cured with light, a heat | fever, etc., The case where it is a (B-1) (meth) acryl compound is preferable.
(Here, “(meth) acryl” means “acryl” and / or “methacryl”. The same shall apply hereinafter.) Examples of component (B-1) include (meth) acrylic ester compounds and epoxy (meth). An acrylate compound etc. are mentioned.
（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、テトラヒドロフロフリル（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。なおエポキシ基の一部をアクリルエステル化する部分エポキシ（メタ）アクリレートが好適に使用される。この場合のアクリル化の割合は、３０〜７０％程度が好ましい。
成分（Ｂ−１）は単独で用いても良いし、２種類以上を混合しても良い。本発明の光硬化性樹脂組成物において、成分（Ｂ−１）を使用する場合には、光硬化性樹脂組成物総量中、通常５〜５０質量％、好ましくは５〜３０質量％である。
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, phenyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy ( (Meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromophenol Nyloxyethyl (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 (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F Polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythris Tall tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) Acrylate, trimethylolpropane polyethoxytri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, neopentyl glycol and hydroxypivalic acid ester diacrylate and neopentyl glycol and hydroxypivalic acid ester ε-caprolactone adduct Mention may be made of monomers such as diacrylate. Preferred examples include N-acryloyloxyethyl hexahydrophthalimide, phenoxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
An epoxy (meth) acrylate compound is obtained by a well-known method by reaction with an epoxy compound and (meth) acrylic acid. Although it does not specifically limit as an epoxy compound used as a raw material, A bifunctional or more functional epoxy compound is preferable, for example, resorcin diglycidyl ether, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound , Phenol novolac type epoxy compound, cresol novolac 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, glycidyl amine type epoxy Compounds, hydantoin type epoxy compounds, isocyanurate type epoxy compounds, phenol novolac type epoxy compounds having a triphenolmethane skeleton, and others Catechol, bifunctional phenols diglycidyl ethers of resorcinol and the like, bifunctional alcohols diglycidyl ethers of, and their halides, and the like hydrogenated product. Of these, bisphenol A type epoxy compounds and resorcin diglycidyl ether are preferred from the viewpoint of liquid crystal contamination. Moreover, the ratio of an epoxy group and a (meth) acryloyl group is not limited, and is appropriately selected from the viewpoint of process compatibility. In addition, the partial epoxy (meth) acrylate which acryl-esterifies a part of epoxy group is used suitably. In this case, the proportion of acrylation is preferably about 30 to 70%.
A component (B-1) may be used independently and may mix 2 or more types. In the photocurable resin composition of this invention, when using a component (B-1), it is 5-50 mass% normally in a photocurable resin composition total amount, Preferably it is 5-30 mass%.
［（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（Ｂ−２）エポキシ化合物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。本発明の光硬化性樹脂組成物において、成分（Ｂ−２）を使用する場合には、光硬化性樹脂組成物総量中、通常５〜５０質量％、好ましくは５〜３０質量％である。
なお、本発明の光硬化性樹脂組成物において、成分（Ｂ）の配合量は、光硬化性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。成分（Ｂ−１）と成分（Ｂ−２）を混合して使用する場合の配合量も同様とする。
[(B-2) Epoxy compound]
As an aspect of the present invention, it is more preferable that the component (B) further contains (B-2) an epoxy compound.
Although it does not specifically limit as an epoxy compound, The epoxy compound more than bifunctional is preferable, for example, resorcin diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type Epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type Epoxy resin, isocyanurate type epoxy resin, phenol novolak type epoxy resin having triphenolmethane skeleton, and other bifunctional catechol, resorcinol, etc. Diglycidyl ethers of Nord acids, difunctional alcohols diglycidyl ethers of, and their halides, and the like hydrogenated product. Among these, bisphenol A type epoxy resin and resorcin diglycidyl ether are preferable from the viewpoint of liquid crystal contamination.
A component (B-2) may be used independently and may mix 2 or more types. In the photocurable resin composition of this invention, when using a component (B-2), it is 5-50 mass% normally in the photocurable resin composition total amount, Preferably it is 5-30 mass%.
In addition, in the photocurable resin composition of this invention, the compounding quantity of a component (B) is 10-80 mass% normally in the total amount of a photocurable resin composition, Preferably it is 20-70 mass%. The same applies to the blending amount when the component (B-1) and the component (B-2) are mixed and used.
［（Ｃ）有機フィラー］
本発明の光硬化性樹脂組成物は、成分（Ｃ）として有機フィラーを含有しても良い（以下、単に「成分（Ｃ）」ともいう。）。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。本発明の光硬化性樹脂組成物において、成分（Ｃ）を使用する場合には、光硬化性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。
[(C) Organic filler]
The photocurable resin composition of the present invention may contain an organic filler as the component (C) (hereinafter also simply referred to as “component (C)”). 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.), Trefill RTME-5500, 9701, EP-2001 (manufactured by Toray Dow Corning), and the urethane fine particles are preferably JB-800T. HB-800BK (Negami Kogyo Co., Ltd.), Lavalon RTMT320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (Mitsubishi Chemical) are preferred as styrene fine particles, and Septon RTMSEPS2004 and SEPS2063 are preferred as styrene olefin fine particles. .
These organic fillers may be used alone or in combination of two or more. Moreover, it is good also as a core-shell structure using 2 or more types. Of these, acrylic fine particles and silicone fine particles are preferable.
When the above acrylic fine particles are used, it is preferable that the acrylic rubber has a core-shell structure composed of two kinds of acrylic rubbers, and particularly preferably a core layer is n-butyl acrylate and a shell layer is methyl methacrylate. This is sold by Aika Industries as Zefiac RTMF-351.
Examples of the silicone fine particles include crosslinked organopolysiloxane powders and linear dimethylpolysiloxane crosslinked powders. Examples of the composite silicone rubber include those obtained by coating the surface of the silicone rubber with a silicone resin (for example, polyorganosilsesquioxane resin). Among these fine particles, a silicone rubber of a linear dimethylpolysiloxane crosslinked powder or a composite silicone rubber fine particle of a silicone resin-coated linear dimethylpolysiloxane crosslinked powder is particularly preferable. These may be used alone or in combination of two or more. Preferably, the rubber powder has a spherical shape with little viscosity increase after addition. In the photocurable resin composition of this invention, when using a component (C), it is 5-50 mass% normally in the total amount of a photocurable resin composition, Preferably it is 5-40 mass%.
［（Ｄ）無機フィラー］
本発明の光硬化性樹脂組成物は、成分（Ｄ）として、無機フィラーを含有しても良い（以下、単に成分（Ｄ）ともいう。）。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表示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。
本発明の光硬化性樹脂組成物において、無機フィラーを使用する場合には、光硬化性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。無機フィラーの含有量が５質量％より低い場合、ガラス基板に対する接着強度が低下し、また耐湿信頼性も劣るために、吸湿後の接着強度の低下も大きくなる場合がある。又、無機フィラーの含有量が５０質量％より多い場合、フィラー含有量が多すぎるため、つぶれにくく液晶セルのギャップ形成ができなくなってしまう場合がある。
[(D) Inorganic filler]
The photocurable resin composition of the present invention may contain an inorganic filler as the component (D) (hereinafter also simply referred to as the component (D)). 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 fused silica, crystalline silica, silicon nitride, nitriding Examples thereof include boron, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, and aluminum silicate, and silica, alumina, and talc are preferable. These inorganic fillers may be used in combination of two or more.
If the average particle size of the inorganic filler is too large, it becomes a cause of defects such as failure to form a gap when the upper and lower glass substrates are bonded together during the production of a narrow gap liquid crystal display cell, so 2000 nm or less is appropriate, preferably 1000 nm. Hereinafter, it is more preferably 300 nm or less. Moreover, a preferable minimum is about 10 nm, More preferably, it is about 100 nm. The particle diameter can be measured by a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
In the photocurable resin composition of this invention, when using an inorganic filler, it is 5-50 mass% normally in the total amount of a photocurable resin composition, Preferably it is 5-40 mass%. When the content of the inorganic filler is lower than 5% by mass, the adhesive strength to the glass substrate is lowered, and the moisture resistance reliability is inferior, so that the decrease in the adhesive strength after moisture absorption may be increased. Moreover, when there is more content of an inorganic filler than 50 mass%, since there is too much filler content, it may become difficult to collapse and it will become impossible to form the gap of a liquid crystal cell.
［（Ｅ）シランカップリング剤］
本発明の光硬化性樹脂組成物は、成分（Ｅ）としてシランカップリング剤を添加して、接着強度や耐湿性の向上を図ることができる（以下、単に「成分（Ｅ）」ともいう。）。
成分（Ｅ）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。本発明の光硬化性樹脂組成物において、成分（Ｅ）を使用する場合には、光硬化性樹脂組成物総量中、０．０５〜３質量％が好適である。
[(E) Silane coupling agent]
The photocurable resin composition of the present invention can be improved in adhesive strength and moisture resistance by adding a silane coupling agent as the component (E) (hereinafter also simply referred to as “component (E)”). ).
Component (E) includes 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 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, 3-chloropropyl Chill dimethoxysilane, 3-chloropropyl trimethoxy silane, and the like. 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. In the photocurable resin composition of this invention, when using a component (E), 0.05-3 mass% is suitable in the photocurable resin composition total amount.
［（Ｆ）熱硬化剤］
本発明の光硬化性樹脂組成物は、成分（Ｆ）として熱硬化剤を含有しても良い（以下、単に「成分（Ｆ）」ともいう。）。成分（Ｆ）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（Ｆ）は単独で用いても良いし、２種類以上を混合しても良い。本発明の光硬化性樹脂組成物において、成分（Ｆ）を使用する場合には、光硬化性樹脂組成物総量中、通常０．１〜１０質量％、好ましくは１〜１０質量％である。
[(F) Thermosetting agent]
The photocurable resin composition of the present invention may contain a thermosetting agent as the component (F) (hereinafter also simply referred to as “component (F)”). The component (F) reacts nucleophilically with an unshared electron pair or an anion in the molecule, and examples thereof include polyvalent amines, polyhydric phenols, and organic acid hydrazide compounds. However, it is not limited to these. Of these, organic acid hydrazide compounds are particularly preferably used. For example, the aromatic hydrazide 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 pyromellitic acid tetrahydrazide. Examples of aliphatic hydrazide compounds include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide. 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis ( Hydantoin skeleton such as hydrazinocarbonoethyl) -5-isopropylhydantoin, preferably valine hydantoin skeleton (where the carbon atom of the hydantoin ring is iso Dihydrazide compounds having a skeleton substituted with a propyl group), tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate and the like can be mentioned. Preferably, from the balance of curing reactivity and latency, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris ( 2-Hydrazinocarbonylethyl) isocyanurate and tris (3-hydrazinocarbonylpropyl) isocyanurate, particularly preferably tris (2-hydrazinocarbonylethyl) isocyanurate.
A component (F) may be used independently and may mix 2 or more types. In the photocurable resin composition of this invention, when using a component (F), it is 0.1-10 mass% normally in the photocurable resin composition total amount, Preferably it is 1-10 mass%.
［（Ｇ）水素引抜型光ラジカル重合開始剤］
本発明の光硬化性樹脂組成物は、成分（Ｇ）として水素引抜型光ラジカル重合開始剤を含有しても良い（以下、単に「成分（Ｇ）」ともいう。）。水素引抜型光ラジカル重合開始剤とは、紫外線や可視光の照射によって、他の分子の水素を引抜、ラジカルを発生させる重合開始剤であり、成分（Ａ）のような開裂型光ラジカル重合開始剤とはラジカル発生のメカニズムが異なる。本発明において、成分（Ｇ）を含有することにより、異なるメカニズムのラジカル発生を共存させ、より光反応性を高めることができる。
水素引抜型光ラジカル重合開始剤としては、特に限定されないが、例えば、ベンゾフェノン、アクリドン、２−エチルアントラキノン、２−クロロチオキサントン、２−イソプロピルアントラキノン、２，４−ジエチルチオキサントン等を挙げることができる。
また、例えば国際公開２０１２／０１１２２０記載のように分子内に反応性基を有するチオキサントン化合物も好適に用いることができる。
本発明の光硬化性樹脂組成物において、成分（Ｇ）を使用する場合には、光硬化性樹脂組成物総量中、通常０．００１〜５質量％、好ましくは０．００２〜５質量％である。
[(G) Hydrogen abstraction type photo radical polymerization initiator]
The photocurable resin composition of the present invention may contain a hydrogen abstraction type photo radical polymerization initiator as the component (G) (hereinafter also simply referred to as “component (G)”). Hydrogen abstraction type photo radical polymerization initiator is a polymerization initiator that generates radicals by extracting hydrogen of other molecules by irradiation with ultraviolet rays or visible light, and initiates cleavage type photo radical polymerization as in component (A). The mechanism of radical generation is different from the agent. In the present invention, by containing the component (G), radical generation of different mechanisms can coexist and photoreactivity can be further enhanced.
The hydrogen abstraction type photo radical polymerization initiator is not particularly limited, and examples thereof include benzophenone, acridone, 2-ethylanthraquinone, 2-chlorothioxanthone, 2-isopropylanthraquinone, and 2,4-diethylthioxanthone.
Further, for example, thioxanthone compounds having a reactive group in the molecule as described in International Publication 2012/011220 can also be suitably used.
In the photocurable resin composition of this invention, when using a component (G), it is 0.001-5 mass% normally in a photocurable resin composition total amount, Preferably it is 0.002-5 mass%. is there.
［（Ｈ）熱ラジカル重合開始剤］
本発明の光硬化性樹脂組成物は、（Ｈ）熱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、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。
[(H) Thermal radical polymerization initiator]
The photocurable resin composition of the present invention contains (H) a thermal radical polymerization initiator (hereinafter also simply referred to as “component (H)”), 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 there are organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzopinacols, and the like. And benzopinacol is preferably used. For example, examples of the organic peroxide include Kayamek RTMA, M, R, L, LH, SP-30C, Parkardox CH-50L, BC-FF, Kadox B-40ES, Parkadox 14, Trigonox RTM22-70E, 23- C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kaya ester RTMP-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl RTMB, Parka dox 16, Kayacarbon RTMBIC- 75, AIC-75 (manufactured by Kayaku Akzo Co., Ltd.), Permec RTMN, H, S, F, D, G, Perhexa RTMH, HC, TMH, C, V, 22, MC, Percure RTMAH, AL, HB, Perbutyl RTMH, C, ND, L, Parkmill RTMH, D , Parroyl RTMIB, IPP, Perocta RMTND (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 azo compounds, VA-044, 086, V-070, VPE-0201, VSP-1001 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like are commercially available.
成分（Ｈ）の含有量としては、光硬化性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。 As content of a component (H), it is preferable that it is 0.0001-10 mass% in the total amount of a photocurable resin composition, More preferably, it is 0.0005-5 mass%, 0.001- 3% by mass is particularly preferred.
本発明の光硬化性樹脂組成物には、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。 If necessary, the photo-curable resin composition of the present invention further contains additives such as curing accelerators such as organic acids and imidazoles, radical polymerization inhibitors, pigments, leveling agents, antifoaming agents, and solvents. be able to.
［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。
本発明の光硬化性樹脂組成物において、硬化促進剤を使用する場合には、光硬化性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 organic carboxylic acids and organic phosphoric acids, but organic carboxylic acids are preferred. Specifically, aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, 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 imidazole compounds 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′-me Tyrimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethyl Examples include imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole.
In the photocurable resin composition of this invention, when using a hardening accelerator, it is 0.1-10 mass% normally in the total amount of a photocurable resin composition, Preferably it is 1-5 mass%.
［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−ｔｅｒｔ−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光硬化性樹脂組成物総量中、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 prevents polymerization by reacting with radicals generated from a photo radical polymerization initiator or a thermal radical polymerization initiator, and is not limited to quinone, piperidine, A hindered phenol type, a nitroso type, etc. 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-tert-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis 4-ethyl-6-tert-butylphenol), 4,4′-thiobis-3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9 -Bis [1,1-dimethyl-2- [β- (3-tert-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) methane, 1,3,5-tris (3 ′, 5′-di-) t-butyl-4′-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, paramethoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-ni Nitroso aluminum salts of phenyl hydroxy amine, trade name ADK STAB LA-81, but such trade name ADK STAB LA-82 (manufactured by KK ADEKA) and the like, but is not limited thereto. Of these, naphthoquinone, hydroquinone, and nitroso piperazine radical polymerization inhibitors are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-P-cresol, Polystop 7300P (Hakuto Co., Ltd.) Company-made) is more preferred, and Polystop 7300P (made by Hakuto Co., Ltd.) is most preferred.
As content of a radical polymerization inhibitor, 0.0001-1 mass% is preferable in the photocurable resin composition total amount of this invention, 0.001-0.5 mass% is still more preferable, 0.01-0. 2% by mass is particularly preferred.
本発明の光硬化性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（Ｇ）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）、（Ｄ）、（Ｅ）、（Ｆ）、（Ｈ）、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。 An example of a method for obtaining the photocurable resin composition of the present invention is the following method. First, the component (A) and, if necessary, the component (G) are dissolved by heating in the component (B) (or a mixture thereof when the components (B-1) and (B-2) are used). Next, after cooling to room temperature, components (C), (D), (E), (F), (H), an antifoaming agent, a leveling agent, a solvent, etc. are added as necessary, and a known mixing device, For example, the liquid crystal sealant of the present invention can be produced by uniformly mixing with a three-roll, sand mill, ball mill or the like and filtering with a metal mesh.
本発明の光硬化性樹脂組成物は電子部品用封止剤として非常に有用である。電子部品用封止剤には、電子部品用接着剤として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含まれるが、これらに限定されるものではない。 The photocurable resin composition of the present invention is very useful as a sealant for electronic parts. Electronic component sealants include, but are not limited to, adhesives for flexible printed wiring boards, TAB adhesives, semiconductor adhesives, various display adhesives, etc. as electronic component adhesives. is not.
また、本発明の光硬化性樹脂組成物は、液晶表示セル用封止剤として、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。 Moreover, the photocurable resin composition of the present invention is very useful as a sealing agent for liquid crystal display cells, particularly as a liquid crystal sealing agent. An example is shown below about the liquid crystal display cell at the time of using the resin composition of this invention as a liquid-crystal sealing compound.
本発明の液晶表示セル用封止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、周囲を当該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、当該液晶シール剤に、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１時間〜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１〜２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。 A liquid crystal display cell manufactured using the sealant for a liquid crystal display cell of the present invention has a pair of substrates each having a predetermined electrode formed on the substrate so as to face each other at a predetermined interval, and the periphery is sealed with the liquid crystal sealant. The liquid crystal is sealed in the gap. The kind of liquid crystal to be sealed is not particularly limited. Here, the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicon, etc. and having light transmission properties. As a manufacturing method thereof, after adding a spacer (gap control material) such as glass fiber to the liquid crystal sealant, the liquid crystal sealant is applied to one of the pair of substrates using a dispenser or a screen printing apparatus. If necessary, temporary curing is performed at 80 to 120 ° C. Thereafter, a liquid crystal is dropped inside the weir of the liquid crystal sealant, and the other glass substrate is overlaid 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 1 to 2 hours. When used as a photothermal combination type, the liquid crystal sealant is irradiated with ultraviolet rays by an ultraviolet irradiator and photocured. 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 1 to 2 hours. The liquid crystal display cell of the present invention thus obtained has no display defects due to liquid crystal contamination, and has excellent adhesion and moisture resistance reliability. Examples of the spacer include glass fiber, silica beads, and polymer beads. The 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 weight, preferably 0.5 to 2 parts by weight, more preferably about 0.9 to 1.5 parts by weight with respect to 100 parts by weight of the liquid crystal sealant of the present invention. is there.
本発明の光硬化性樹脂組成物は、遮光部を有する設計の電子部品や可視光のような低エネルギー光で硬化する必要のある封止剤用途の使用に非常に適するものである。例えば配線遮光部下で用いられる液晶シール剤、有機ＥＬ用封止剤、タッチパネル用接着剤である。 The photo-curable resin composition of the present invention is very suitable for use in electronic parts designed to have a light-shielding part and for use in sealants that need to be cured with low-energy light such as visible light. For example, a liquid crystal sealant, an organic EL sealant, and a touch panel adhesive used under a wiring light shielding part.
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。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to an Example. Unless otherwise specified, “part” and “%” in the text are based on mass.
［合成例１］
特表２０１６−５３１９２６号公報に従い、成分（Ａ）として下記式（Ａ−１）で表される化合物を以下の通り合成した。
[Synthesis Example 1]
A compound represented by the following formula (A-1) as a component (A) was synthesized as follows in accordance with JP-T-2006-531926.
ジクロロメタン中の塩化アルミニウムに、硫化ジフェニルを０℃で添加した。次いで、クロロアセチルクロリドを０℃で添加し、そして室温で２時間にわたり撹拌して混合物を得た。塩化アルミニウムおよび４−メチルペンタノイルクロリドを該混合物に０℃で添加し、一晩撹拌し、反応混合物を得た。該反応混合物を氷水へと注いだ後に、有機層をジクロロメタンで抽出した。該有機層を硫酸マグネシウムにて乾燥させ、濃縮し、その残留物をカラムクロマトグラフィーによって精製し、下記式（２）の化合物を白色の粉末として得た。 To aluminum chloride in dichloromethane, diphenyl sulfide was added at 0 ° C. Chloroacetyl chloride was then added at 0 ° C. and stirred at room temperature for 2 hours to give a mixture. Aluminum chloride and 4-methylpentanoyl chloride were added to the mixture at 0 ° C. and stirred overnight to give a reaction mixture. After pouring the reaction mixture into ice water, the organic layer was extracted with dichloromethane. The organic layer was dried over magnesium sulfate and concentrated, and the residue was purified by column chromatography to obtain a compound of the following formula (2) as a white powder.
前記式（２）の化合物アセトンに添加し、さらに炭酸カリウムおよびのサリチルアルデヒドを添加し、還流下で３時間にわたり撹拌した。該反応混合物を室温にまで温め、水を添加し、ＨＣｌ溶液を添加して、酸性化させた。その沈殿物を濾過により回収し、乾燥させることで、下記式（３）の化合物を得た。 The compound of formula (2) was added to acetone, potassium carbonate and salicylaldehyde were further added, and the mixture was stirred under reflux for 3 hours. The reaction mixture was warmed to room temperature, water was added and acidified by addition of HCl solution. The precipitate was collected by filtration and dried to obtain a compound of the following formula (3).
得られた前記式（３）の化合物をの酢酸エチルに添加し、さらに塩化ヒドロキシルアンモニウムおよびピリジンを添加した。該混合物を還流下で３時間にわたり撹拌した。該反応混合物を室温にまで温め、次いで水中に注いだ。有機層を酢酸エチルで抽出し、そして硫酸マグネシウムにて乾燥させた。濃縮した後に、粗生成物をカラムクロマトグラフィーによって精製し、下記式（４）の化合物を淡黄色の固体として得た。 The obtained compound of the formula (3) was added to ethyl acetate, and hydroxylammonium chloride and pyridine were further added. The mixture was stirred at reflux for 3 hours. The reaction mixture was warmed to room temperature and then poured into water. The organic layer was extracted with ethyl acetate and dried over magnesium sulfate. After concentration, the crude product was purified by column chromatography to obtain a compound of the following formula (4) as a pale yellow solid.
前記式（４）の化合物を酢酸エチルに添加し、さらに塩化アセチルおよび１１１ｍｇのトリエチルアミンを添加し、室温で３時間撹拌した。該反応混合物を水中に注ぎ、酢酸エチルで抽出した。濃縮した後に、粗生成物を酢酸エチル／ヘキサンによって再結晶化させ、前記式（Ａ−１）の化合物を淡黄色の固体として得た。 The compound of the formula (4) was added to ethyl acetate, acetyl chloride and 111 mg of triethylamine were further added, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. After concentration, the crude product was recrystallized with ethyl acetate / hexane to obtain the compound of formula (A-1) as a pale yellow solid.
［実施例１、比較例１］
下記表１に示す割合で成分（Ｂ）２種を混合し、そこに合成例１の成分（Ａ）を９０℃で加熱溶解させた後、室温まで冷却し、成分（Ｃ）、（Ｄ）、（Ｅ）、（Ｆ）、（Ｈ）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、光硬化性樹脂組成物の実施例１、２を調製した。また、成分（Ａ）に変えて、成分（Ｏ）を用い、比較例１を調整した。
[Example 1, Comparative Example 1]
2 types of components (B) are mixed in the ratio shown in the following Table 1, and the component (A) of Synthesis Example 1 is heated and dissolved at 90 ° C., and then cooled to room temperature, and components (C) and (D) , (E), (F), (H) were added and stirred, then dispersed with a three-roll mill, filtered through a metal mesh (635 mesh), and Examples 1 and 2 of the photocurable resin composition. Was prepared. Moreover, it replaced with the component (A) and adjusted the comparative example 1 using the component (O).
［Ｔｇ（ＵＶ＋熱硬化）］
実施例１、比較例１で製造された光硬化性樹脂組成物を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）の紫外線を照射したのち１２０℃のオーブンに６０分間投入して硬化させた。硬化後ＰＥＴフィルムをはがしシール剤硬化膜を得られたのち、これを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３℃／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とした。結果を表１に示す。
[Tg (UV + thermosetting)]
The photocurable resin composition produced in Example 1 and Comparative Example 1 was sandwiched between polyethylene terephthalate (PET) films to form a thin film having a thickness of 100 μm, and 3000 mJ / cm 2 (with a metal halide lamp (manufactured by Ushio Electric Co., Ltd.)). After being irradiated with ultraviolet rays at 100 mW / cm 2 for 30 seconds, it was put into an oven at 120 ° C. for 60 minutes to be cured. After curing, the PET film was peeled off to obtain a cured sealant film, which was then cut into a 50 mm × 5 mm strip to obtain a sample piece. This sample piece was measured in a tensile mode of a dynamic viscoelasticity measuring apparatus (DMS-6100: manufactured by SII Nano Technology) under conditions of a frequency of 10 Hz and a temperature rising temperature of 3 ° C./min. The loss coefficient Tanδ was obtained from the ratio of loss elastic modulus to storage elastic modulus (JIS K 7244-1), and the temperature at which the obtained loss coefficient Tanδ was the maximum value was defined as the glass transition temperature. The results are shown in Table 1.
［Ｔｇ（Ｖｉｓ＋熱硬化）］
実施例１、比較例１で製造された光硬化性樹脂組成物を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）の可視光を照射したのち１２０℃のオーブンに６０分間投入して硬化させた。硬化後ＰＥＴフィルムをはがし硬化膜を得られたのち、これを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３℃／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とした。結果を表１に示す。
[Tg (Vis + thermosetting)]
The photocurable resin composition produced in Example 1 and Comparative Example 1 was sandwiched between polyethylene terephthalate (PET) films to form a thin film having a thickness of 100 μm, and 3000 mJ / cm 2 (with a metal halide lamp (manufactured by Ushio Electric Co., Ltd.)). After irradiation with visible light (100 mW / cm 2 for 30 seconds), it was put into an oven at 120 ° C. for 60 minutes to be cured. After curing, the PET film was peeled off to obtain a cured film, which was then cut into a 50 mm × 5 mm strip to obtain a sample piece. This sample piece was measured in a tensile mode of a dynamic viscoelasticity measuring apparatus (DMS-6100: manufactured by SII Nano Technology) under conditions of a frequency of 10 Hz and a temperature rising temperature of 3 ° C./min. The loss coefficient Tanδ was obtained from the ratio of loss elastic modulus to storage elastic modulus (JIS K 7244-1), and the temperature at which the obtained loss coefficient Tanδ was the maximum value was defined as the glass transition temperature. The results are shown in Table 1.
［Ｔｇ（ＵＶ＋熱硬化）−Ｔｇ（Ｖｉｓ＋熱硬化）］
上記測定結果から、Ｔｇ（ＵＶ＋熱硬化）−Ｔｇ（Ｖｉｓ＋熱硬化）の値を算出し、表１に示す。これによってＵＶでの硬化性と可視光での硬化性の差を確認できる。この差が小さい程、可視光でもＵＶと同程度の硬化性を実現することができることになり、可視光硬化での使用を実現できる。
[Tg (UV + thermosetting) -Tg (Vis + thermosetting)]
A value of Tg (UV + thermosetting) −Tg (Vis + thermosetting) is calculated from the measurement result, and is shown in Table 1. Thereby, the difference between the curability in UV and the curability in visible light can be confirmed. The smaller this difference is, the more the same curability as in UV can be achieved, and the use in visible light curing can be realized.
［遮光部硬化幅］
クロムをエッチングすることによって１００μｍのラインとスペースを設けたガラス基板に、４μｍのグラスファイバー（日本電気硝子（株）社製）を１質量％添加した実施例、比較例の各液晶シール剤を塗布し、対向基板としてブラックマトリクス基板を貼り合せ、ライン／スペースを設けた基板側から３０００ｍＪ／ｃｍ２（１００ｍＷ／ｃｍ２で３０秒）の紫外光を照射し、顕微鏡にて硬化幅を測定した。結果を表１に示す。
[Light-shielding part curing width]
Each liquid crystal sealant of Examples and Comparative Examples in which 1% by mass of 4 μm glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) was added to a glass substrate provided with 100 μm lines and spaces by etching chromium. Then, a black matrix substrate was bonded as the counter substrate, and 3000 mJ / cm 2 (100 mW / cm 2 for 30 seconds) of ultraviolet light was irradiated from the substrate side provided with the line / space, and the curing width was measured with a microscope. The results are shown in Table 1.
表１に示されるように、実施例１の光硬化性樹脂組成物は、比較例１の光硬化性樹脂組成物に比べて、可視光でも紫外線と同等の硬化性を有し、また遮光部における深部（低エネルギー照射部分）での硬化性も良好である。すなわち低エネルギーでの優れた硬化性を有することが確認された。 As shown in Table 1, the photocurable resin composition of Example 1 has a curability equivalent to that of ultraviolet rays even in the visible light as compared with the photocurable resin composition of Comparative Example 1, and has a light shielding portion. The curability in the deep part (low energy irradiated part) is also good. That is, it was confirmed that it has excellent curability at low energy.
本発明の光硬化性樹脂組成物は、光が十分に当たらない部分における硬化性も高く、また他の部材へのダメージを考慮した可視光照射でも十分な硬化性を有する為、電子部品用封止剤、特にディスプレイ用封止剤として有用である。
Since the photocurable resin composition of the present invention has high curability in a portion where light is not sufficiently irradiated, and has sufficient curability even when irradiated with visible light in consideration of damage to other members, it is sealed for electronic parts. It is useful as a stopper, especially as a sealant for display.
Claims (16)
A liquid crystal display cell using the liquid crystal display cell sealant or liquid crystal sealant according to claim 14 or 15.
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