JP2013015645A - Liquid crystal sealant and liquid crystal display cell using the same - Google Patents
Liquid crystal sealant and liquid crystal display cell using the same Download PDFInfo
- Publication number
- JP2013015645A JP2013015645A JP2011147813A JP2011147813A JP2013015645A JP 2013015645 A JP2013015645 A JP 2013015645A JP 2011147813 A JP2011147813 A JP 2011147813A JP 2011147813 A JP2011147813 A JP 2011147813A JP 2013015645 A JP2013015645 A JP 2013015645A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- epoxy resin
- meth
- component
- crystal sealant
- 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
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 177
- 239000000565 sealant Substances 0.000 title claims abstract description 76
- 239000003822 epoxy resin Substances 0.000 claims abstract description 104
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 104
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 17
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 23
- 238000011109 contamination Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 30
- -1 acryl Chemical group 0.000 description 24
- 210000004027 cell Anatomy 0.000 description 20
- 238000001723 curing Methods 0.000 description 19
- 239000000758 substrate Substances 0.000 description 19
- 229920003986 novolac Polymers 0.000 description 15
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007983 Tris buffer Substances 0.000 description 9
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000003780 insertion Methods 0.000 description 7
- 230000037431 insertion Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 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 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 5
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000009257 reactivity Effects 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
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-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
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 125000001931 aliphatic 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
- 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
- 210000002858 crystal cell Anatomy 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 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 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229940091173 hydantoin Drugs 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-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
- 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
- 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
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 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
- 230000008859 change Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 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
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- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- 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
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- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LGWROMGRXCZCLA-UHFFFAOYSA-N 2-hydroxybutanedihydrazide Chemical compound NNC(=O)CC(O)C(=O)NN LGWROMGRXCZCLA-UHFFFAOYSA-N 0.000 description 1
- TZMACLAARXHRRZ-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarbohydrazide Chemical compound NNC(=O)CC(O)(C(=O)NN)CC(=O)NN TZMACLAARXHRRZ-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- OFLXLNCGODUUOT-UHFFFAOYSA-N acetohydrazide Chemical compound C\C(O)=N\N OFLXLNCGODUUOT-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- UHVCSNKHFBQKBO-UHFFFAOYSA-N benzyl-ethenyl-[2-(3-trimethoxysilylpropylamino)ethyl]azanium;chloride Chemical compound Cl.CO[Si](OC)(OC)CCCNCCN(C=C)CC1=CC=CC=C1 UHVCSNKHFBQKBO-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- HJMZMZRCABDKKV-UHFFFAOYSA-N carbonocyanidic acid Chemical compound OC(=O)C#N HJMZMZRCABDKKV-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- FOAFCAUCIZMBJM-UHFFFAOYSA-N cyclohexane-1,1,2-tricarbohydrazide Chemical compound NNC(=O)C1CCCCC1(C(=O)NN)C(=O)NN FOAFCAUCIZMBJM-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DKKXSNXGIOPYGQ-UHFFFAOYSA-N diphenylphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C1=CC=CC=C1 DKKXSNXGIOPYGQ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- OXAGUPFRAIIDLT-UHFFFAOYSA-N heptanedihydrazide Chemical compound NNC(=O)CCCCCC(=O)NN OXAGUPFRAIIDLT-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 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
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 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
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 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
- 230000000704 physical 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 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
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 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
- 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 compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4035—Hydrazines; Hydrazides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、熱による硬化性が良好である液晶シール剤に関する。より詳細には、熱による良好な硬化性を有し、かつ保存安定性にも優れ、更に硬化物の耐湿性等にも優れる液晶シール剤、及びその硬化物でシールされた液晶表示セルに関する。 The present invention relates to a liquid crystal sealing agent having good curability by heat. More specifically, the present invention relates to a liquid crystal sealing agent having good curability by heat, excellent storage stability, and excellent moisture resistance of a cured product, and a liquid crystal display cell sealed with the cured product.
近年の液晶表示セルの大型化に伴い、液晶表示セルの製造法として、より量産性の高い、いわゆる液晶滴下工法が提案されている（特許文献１、特許文献２参照）。具体的には、一方の基板に形成された液晶シール剤の堰の内側に液晶を滴下した後、もう一方の基板を貼り合わせることにより液晶が封止される液晶表示セルの製造方法である。 With the recent increase in size of liquid crystal display cells, a so-called liquid crystal dropping method with higher mass productivity has been proposed as a method for manufacturing liquid crystal display cells (see Patent Document 1 and Patent Document 2). Specifically, it is a method of manufacturing a liquid crystal display cell in which liquid crystal is sealed by dropping a liquid crystal inside a weir of a liquid crystal sealant formed on one substrate and then bonding the other substrate.
しかし、液晶滴下工法は、未硬化の状態の液晶シール剤が液晶に接触するため、その際に液晶シール剤の成分が液晶に溶解（溶出）して液晶の抵抗値を低下させ、シール近傍の表示不良を発生させるという問題点がある。 However, in the liquid crystal dropping method, the liquid crystal sealant in an uncured state comes into contact with the liquid crystal. At that time, the components of the liquid crystal sealant are dissolved (eluting) in the liquid crystal to reduce the resistance value of the liquid crystal, There is a problem that a display defect occurs.
この課題を解決する為、現在は液晶滴下工法用の液晶シール剤として光熱併用型のものが用いられ、実用化されている（特許文献３、４）。この液晶シール剤を使用した液晶滴下工法では、基板に挟まれた液晶シール剤に光を照射して一次硬化させた後、加熱して二次硬化させることを特徴とする。この方法によれば、未硬化の液晶シール剤を光によって速やかに硬化でき、液晶シール剤成分の液晶への溶解（溶出）を抑えることが可能である。さらに、光硬化のみでは光硬化時の硬化収縮等による接着強度不足という問題も発生するが、光熱併用型であれば加熱による二次硬化によって、そういった問題も解消できるという利点を有する。 In order to solve this problem, a photothermal combination type liquid crystal sealant for a liquid crystal dropping method is currently used and put into practical use (Patent Documents 3 and 4). The liquid crystal dropping method using the liquid crystal sealant is characterized in that the liquid crystal sealant sandwiched between the substrates is irradiated with light to be primarily cured and then heated to be secondarily cured. According to this method, the uncured liquid crystal sealant can be quickly cured by light, and dissolution (elution) of the liquid crystal sealant component into the liquid crystal can be suppressed. Furthermore, the problem of insufficient adhesive strength due to curing shrinkage at the time of photocuring occurs only by photocuring, but the photothermal combination type has an advantage that such problems can be solved by secondary curing by heating.
しかしながら、近年では、液晶表示素子の小型化に伴い、液晶表示素子のアレイ基板のメタル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、シール近傍の表示不良を引き起こす。 However, in recent years, with the miniaturization of the liquid crystal display element, a light shielding portion where the liquid crystal sealant is not exposed to light is generated by the metal wiring part of the array substrate of the liquid crystal display element and the black matrix part of the color filter substrate. The defect problem 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, the dissolution of the uncured component into the liquid crystal is accelerated by the heat, resulting in a display defect near the seal.
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５、６では、熱ラジカル開始剤を用いる方法が開示されている。また、特許文献７〜９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 5 and 6 disclose a method using a thermal radical initiator. Patent Documents 7 to 9 disclose a method using a polyvalent carboxylic acid as a curing accelerator.
しかし、一般に、熱ラジカル開始剤は常温においても少しずつラジカルが発生する為、液晶シール剤の保存安定性や作業安定性が悪いという問題を抱えている。また、多価カルボン酸のような硬化促進剤は、触媒として作用する為、それ自体が反応し、硬化物中に化学的結合によって取り込まれることが無い為、液晶中に溶解し、表示不良を引き起こすといった問題がある。 However, in general, a thermal radical initiator generates radicals little by little even at room temperature, and thus has a problem that the storage stability and work stability of the liquid crystal sealant are poor. In addition, since a curing accelerator such as a polyvalent carboxylic acid acts as a catalyst, it reacts with itself and is not taken into the cured product by chemical bonding, so it dissolves in the liquid crystal and causes poor display. There is a problem of causing it.
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、優れた熱反応性を有しながら、良好な保存安定性をも併せ持ち、及び低液晶汚染性を有する液晶シール剤は未だ実現していない。 As described above, the development of liquid crystal sealants has been carried out very vigorously, while having excellent thermal reactivity, it also has good storage stability and low liquid crystal contamination. A liquid crystal sealant having the above has not been realized yet.
本発明は、加熱のみ、又は光熱併用によって硬化する液晶シール剤に関するものであり、熱による反応が速い為、工程を通して液晶に対して極めて汚染性が低く、且つ保存安定性にも優れ、また耐湿信頼性等の硬化物特性にも優れる液晶滴下工法用液晶シール剤を提案するものである。 The present invention relates to a liquid crystal sealant that is cured only by heating or by combined use of light and heat, and since the reaction by heat is fast, it is extremely low in contamination with liquid crystals throughout the process, has excellent storage stability, and is resistant to moisture. The present invention proposes a liquid crystal sealant for a liquid crystal dropping method that is excellent in properties of cured products such as reliability.
本発明者らは、鋭意検討の結果、分子内に活性水素を有するエポキシ樹脂、（メタ）アクリル化エポキシ樹脂及び部分（メタ）アクリル化エポキシ樹脂から選択される１種もしくは２種以上からなる硬化性樹脂（ただし活性水素として、ヒドロキシ基に含まれる水素は除く）を含有する液晶シール剤が上記熱反応性に優れ、その結果液晶汚染性も抑える事が可能であり、更には保存安定性にも優れることを見出し、本発明を完成するに至った。
即ち本発明は、次の１）〜１３）に関するものである。なお、本明細書中、成分（ａ）について、「（ａ）分子内に活性水素を有するエポキシ樹脂、（メタ）アクリル化エポキシ樹脂及び部分（メタ）アクリル化エポキシ樹脂から選択される１種もしくは２種以上からなる硬化性樹脂」と記載する煩雑さを避ける為、「成分（ａ）硬化性樹脂」と記載する場合がある。
As a result of intensive studies, the inventors of the present invention have one or more types of curing selected from epoxy resins having active hydrogen in the molecule, (meth) acrylated epoxy resins, and partially (meth) acrylated epoxy resins. Liquid crystal sealant containing a reactive resin (excluding hydrogen contained in the hydroxy group as active hydrogen) is excellent in the above thermal reactivity, and as a result, liquid crystal contamination can be suppressed, and storage stability is further improved. Has been found to be excellent, and the present invention has been completed.
That is, the present invention relates to the following 1) to 13). In addition, in this specification, about the component (a), "(a) 1 type selected from the epoxy resin which has active hydrogen in a molecule | numerator, (meth) acrylated epoxy resin, and partial (meth) acrylated epoxy resin or In order to avoid the complexity described as “two or more curable resins”, it may be described as “component (a) curable resin”.
１）
（ａ）分子内に活性水素を有する、エポキシ樹脂、（メタ）アクリル化エポキシ樹脂及び部分（メタ）アクリル化エポキシ樹脂から選択される１種もしくは２種以上からなる硬化性樹脂（ただし活性水素として、ヒドロキシ基に含まれる水素は除く）、（ｂ）熱硬化剤を含有することを特徴とする液晶シール剤。
２）
上記成分（ａ）が分子内に活性水素を有する（メタ）アクリル化エポキシ樹脂である上記１）に記載の液晶シール剤。
３）
上記成分（ａ）が、分子内にカルボキシ基、スルファニル基又はアミノ基を有する（メタ）アクリル化エポキシ樹脂である上記１）又は２）に記載の液晶シール剤。
４）
上記成分（ａ）が分子内にカルボキシ基を有する（メタ）アクリル化エポキシ樹脂である上記１）乃至３）のいずれか一項に記載の液晶シール剤。
５）
上記成分（ａ）が分子内にカルボキシ基を有するアクリル化レゾルシノールジグリジルエーテルである上記１）乃至４）のいずれか一項に記載の液晶シール剤。
６）
更に、（ｃ）分子内に活性水素を有さないエポキシ樹脂、（メタ）アクリル化エポキシ樹脂及び部分（メタ）アクリル化エポキシ樹脂から選択される１種もしくは２種以上からなる硬化性樹脂を含有する上記１）乃至５）のいずれか一項に記載の液晶シール剤（ただし活性水素として、ヒドロキシ基に含まれる水素は除く）。
７）
上記成分（ａ）の含有量が液晶シール剤の総量を１００質量部とした場合に、５質量部〜５０質量部である上記１）乃至６）のいずれか一項に記載の液晶シール剤。
８）
上記成分（ｂ）熱硬化剤が、多価ヒドラジド化合物である上記１）乃至７）のいずれか一項に記載の液晶シール剤。
９）
上記成分（ｂ）熱硬化剤が、下記式（１）で表される１又は２以上のヒドラジド化合物である上記８）に記載の液晶シール剤。
で表される分子骨格を示す］
１０）
更に、（ｄ）シランカップリング剤を含有する、上記１）乃至９）のいずれか一項に記載の液晶シール剤。
１１）
更に、（ｅ）無機フィラーを含有する上記１）乃至１０）のいずれか一項に記載の液晶シール剤。
１２）
更に、（ｆ）光重合開始剤を含有する上記１）乃至１１）のいずれか一項に記載の液晶シール剤。
１３）
上記１）乃至１２）のいずれか一項に記載の液晶シール剤を硬化して得られる硬化物でシールされた液晶表示セル。
1)
(A) A curable resin comprising one or more selected from an epoxy resin, a (meth) acrylated epoxy resin and a partial (meth) acrylated epoxy resin having active hydrogen in the molecule (however, as active hydrogen , Excluding hydrogen contained in a hydroxy group), and (b) a liquid crystal sealant containing a thermosetting agent.
2)
The liquid crystal sealant according to 1) above, wherein the component (a) is a (meth) acrylated epoxy resin having active hydrogen in the molecule.
3)
The liquid crystal sealant according to 1) or 2) above, wherein the component (a) is a (meth) acrylated epoxy resin having a carboxy group, a sulfanyl group or an amino group in the molecule.
4)
The liquid crystal sealing agent according to any one of 1) to 3), wherein the component (a) is a (meth) acrylated epoxy resin having a carboxy group in the molecule.
5)
5. The liquid crystal sealant according to any one of 1) to 4), wherein the component (a) is an acrylated resorcinol diglycidyl ether having a carboxy group in the molecule.
6)
Further, (c) a curable resin composed of one or more selected from epoxy resins having no active hydrogen in the molecule, (meth) acrylated epoxy resins and partial (meth) acrylated epoxy resins The liquid crystal sealing agent according to any one of 1) to 5) above (however, as active hydrogen, hydrogen contained in a hydroxy group is excluded).
7)
The liquid crystal sealant according to any one of 1) to 6) above, wherein the content of the component (a) is 5 parts by mass to 50 parts by mass when the total amount of the liquid crystal sealant is 100 parts by mass.
8)
The liquid crystal sealant according to any one of 1) to 7) above, wherein the component (b) thermosetting agent is a polyhydric hydrazide compound.
9)
The liquid crystal sealing agent according to 8), wherein the component (b) thermosetting agent is one or more hydrazide compounds represented by the following formula (1).
The molecular skeleton represented by
10)
Furthermore, (d) Liquid crystal sealing agent as described in any one of said 1) thru | or 9) containing a silane coupling agent.
11)
Furthermore, (e) Liquid crystal sealing agent as described in any one of said 1) thru | or 10) containing an inorganic filler.
12)
Furthermore, (f) Liquid crystal sealing agent as described in any one of said 1) thru | or 11) containing a photoinitiator.
13)
A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent according to any one of 1) to 12) above.
本発明の液晶シール剤は、熱硬化時の反応速度が速い為、光熱併用型液晶滴下工法において、光の届き難い配線下においても充分な硬化性を有し、この為パネルの配線設計の自由度を確保でき、信頼性の高い液晶表示パネルの製造を容易にする事ができ、また更には、熱のみで液晶シール剤を硬化させる液晶滴下工法への応用も可能である。 Since the liquid crystal sealant of the present invention has a high reaction rate at the time of thermosetting, the photothermal combined liquid crystal dropping method has sufficient curability even under wiring where light does not reach easily. The liquid crystal display panel can be easily manufactured with a high degree of reliability and can be applied to a liquid crystal dropping method in which the liquid crystal sealant is cured only by heat.
本発明は成分（ａ）分子内に活性水素を有する、エポキシ樹脂、（メタ）アクリル化エポキシ樹脂及び部分（メタ）アクリル化エポキシ樹脂から選択される１種もしくは２種以上からなる硬化性樹脂を含有する。（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。）ただし、該活性水素の解釈にあたり、ヒドロキシ基に含まれる水素は除かれる。ヒドロキシ基は一般に酸解離定数（ｐＫａ）が大きく、またヒドロキシ基自体の求核性も弱い為触媒として機能し難い。実際に通常のエポキシアクリレートは、２級ヒドロキシ基を有するが、熱硬化時に反応触媒として機能しない。本発明では、該硬化性樹脂を有することによって、良好な熱反応性を実現することができる。更に、該硬化性樹脂は（メタ）アクリル基又はエポキシ基といった光又は熱によって反応する官能基を有する為、硬化物中に取り込まれ、液晶に対して溶解する量を劇的に抑えることができ、液晶表示素子の表示特性を損なわない。 The present invention provides a curable resin composed of one or more selected from an epoxy resin, a (meth) acrylated epoxy resin and a partial (meth) acrylated epoxy resin having active hydrogen in the component (a) molecule. contains. (Here, “(meth) acryl” means “acryl” and / or “methacryl”. The same shall apply hereinafter.) However, in interpreting the active hydrogen, hydrogen contained in the hydroxy group is excluded. Hydroxyl groups generally have a large acid dissociation constant (pKa), and the hydroxy group itself is weak in nucleophilicity, so it is difficult to function as a catalyst. Actually, a normal epoxy acrylate has a secondary hydroxy group, but does not function as a reaction catalyst during heat curing. In the present invention, good thermal reactivity can be realized by having the curable resin. Furthermore, since the curable resin has a functional group that reacts with light or heat such as a (meth) acrylic group or an epoxy group, the amount of the curable resin taken into the cured product and dissolved in the liquid crystal can be dramatically reduced. The display characteristics of the liquid crystal display element are not impaired.
上記活性水素としては、カルボキシ基、スルファニル基、アミノ基、スルホ基、ホスホ基等に含まれる活性水素が挙げられる。すなわち、上記成分（ａ）としては、例えば分子内にカルボキシ基、スルファニル基、アミノ基、スルホ基、ホスホ基等を有する（メタ）アクリル化エポキシ樹脂、部分（メタ）アクリル化エポキシ樹脂及び分子内にカルボキシ基、チオール基、アミノ基、スルホ基、ホスホ基等を有するエポキシ樹脂から選択される１種もしくは２種以上を含有する硬化性樹脂が挙げられる。中でも、触媒としての機能及び合成の容易さから、カルボキシ基、チオール基、アミノ基が好ましく、更にはカルボキシ基が特に好ましい。例えば、アミノ基を有するエポキシ樹脂としては、アミン変性ビスフェノールＡ型エポキシアクリレートＥＢＥＣＲＹＬ３７０３（ダイセル・サイテック株式会社製）等が市販品として容易に入手できる。 Examples of the active hydrogen include active hydrogen contained in a carboxy group, a sulfanyl group, an amino group, a sulfo group, a phospho group, and the like. That is, as the component (a), for example, a (meth) acrylated epoxy resin, a partial (meth) acrylated epoxy resin having a carboxy group, a sulfanyl group, an amino group, a sulfo group, a phospho group, etc. And curable resins containing one or more selected from epoxy resins having a carboxy group, a thiol group, an amino group, a sulfo group, a phospho group, and the like. Among these, a carboxy group, a thiol group, and an amino group are preferable, and a carboxy group is particularly preferable because of its function as a catalyst and ease of synthesis. For example, as an epoxy resin having an amino group, amine-modified bisphenol A type epoxy acrylate EBECRYL 3703 (manufactured by Daicel Cytec Co., Ltd.) and the like are easily available as commercial products.
成分（ａ）の硬化性樹脂としては、エポキシ樹脂や部分（メタ）アクリル化エポキシ樹脂よりも（メタ）アクリル化エポキシ樹脂が好ましい。（メタ）アクリル化エポキシ樹脂は、光によって速やかに反応する為、液晶への溶解をより抑えることが可能である。この硬化性樹脂としては、例えばエポキシ樹脂と（メタ）アクリル酸の周知の反応により得ることができる（メタ）アクリル化エポキシ樹脂に酸無水物、多価カルボン酸等を反応させて得ることができる。 As the curable resin of component (a), a (meth) acrylated epoxy resin is preferable to an epoxy resin or a partially (meth) acrylated epoxy resin. Since the (meth) acrylated epoxy resin reacts quickly with light, it is possible to further suppress dissolution in the liquid crystal. The curable resin can be obtained, for example, by reacting an acid anhydride, polyvalent carboxylic acid or the like with a (meth) acrylated epoxy resin that can be obtained by a known reaction of an epoxy resin and (meth) acrylic acid. .
具体的には、まずエポキシ樹脂に所定の当量比の（メタ）アクリル酸と触媒（例えば、ベンジルジメチルアミン、トリエチルアミン、ベンジルトリメチルアンモニウムクロライド、トリフェニルホスフィン、トリフェニルスチビン等）と、重合防止剤（例えば、メトキノン、ハイドロキノン、メチルハイドロキノン、フェノチアジン、ジブチルヒドロキシトルエン等）を添加して、例えば８０℃〜１１０℃でエステル化反応を行うことにより得られる。得られた（メタ）アクリル化エポキシ樹脂に、例えば特開昭４９−２６０１、特開平３−１４３９１１、特開平５−３２７４６号公報等に記載の方法で酸無水物を反応させ、分子内に活性水素を有する（メタ）アクリル化エポキシ樹脂を得ることができる。ここで原料となるエポキシ樹脂としては、特に限定されるものではないが、２官能以上のエポキシ樹脂が好ましく、例えばレゾルシノール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、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。この中でも、レゾルシノール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型エポキシ樹脂が好ましく、レゾルシノールジグリシジルエーテルが特に好ましい。 Specifically, first, epoxy resin (meth) acrylic acid and a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) and a polymerization inhibitor ( For example, methoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, and the like) are added, and the esterification reaction is performed at, for example, 80 ° C to 110 ° C. The obtained (meth) acrylated epoxy resin is reacted with an acid anhydride by the method described in, for example, JP-A-49-2601, JP-A-3-143911, JP-A-5-32746, etc. A (meth) acrylated epoxy resin having hydrogen can be obtained. The epoxy resin used as a raw material is not particularly limited, but is preferably a bifunctional or higher epoxy resin, such as resorcinol diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy. Resin, phenol novolac 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, glycidylamine type Epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, phenol novolac type epoxy resins having a triphenolmethane skeleton, and other difunctional phenols Glycidyl etherified product, bifunctional alcohols diglycidyl ethers of, and their halides, and the like hydrogenated product. Among these, resorcinol diglycidyl ether and bisphenol A type epoxy resin bisphenol F type epoxy resin are preferable, and resorcinol diglycidyl ether is particularly preferable.
成分（ａ）は、本発明の液晶シール剤の総量を１００質量部とした場合に、５質量部〜５０質量部含有することが好ましく、５質量部〜３０質量部であることが特に好ましい。成分（ａ）が少なすぎると十分な熱硬化性が得られず、逆に多すぎると液晶シール剤を高粘度化する為、その他の成分の配合に制約を生じることになる。 The component (a) is preferably contained in an amount of 5 to 50 parts by mass, particularly preferably 5 to 30 parts by mass, when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass. If the amount of the component (a) is too small, sufficient thermosetting property cannot be obtained. On the other hand, if the amount is too large, the liquid crystal sealant has a high viscosity, and thus the composition of other components is restricted.
本発明の液晶シール剤で用いられる（ｂ）成分である熱硬化剤は特に限定されるものではなく、多価アミン類、多価フェノール類、ヒドラジド化合物等を挙げる事ができるが、多価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、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、上記式（１）で表される化合物等を挙げることができる。上記（１）で表される化合物としては、例えばトリス（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（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、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が、式（１）の構造であればこれらに限定されるものではない。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（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（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。かかる（ｂ）熱硬化剤を使用する場合の使用量としては、本発明の液晶シール剤総量を１００質量部とした場合に、１質量部〜２０質量部含有する場合が好ましく、更に好ましくは２質量部〜１５質量部であり、２種以上を混合して用いても良い。 The thermosetting agent that is the component (b) used in the liquid crystal sealant of the present invention is not particularly limited, and examples thereof include polyvalent amines, polyhydric phenols, hydrazide compounds, and the like. 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 the 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, 1,4- Cyclohexane dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis (hydrazinocarbono) Hydantoin skeleton such as ethyl) -5-isopropylhydantoin, preferably valine hydantoin skeleton (carbon atom of hydantoin ring is substituted with isopropyl group) Dihydrazide compounds having a rated), can be exemplified compounds represented by the above formula (1). Examples of the compound represented by the above (1) include tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris. (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate and the like can be mentioned, but the structure of the formula (1) is not limited thereto. Preferably, from the balance of curing reactivity and latency, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris ( 2-Hydrazinocarbonylethyl) isocyanurate and tris (3-hydrazinocarbonylpropyl) isocyanurate, particularly preferably tris (2-hydrazinocarbonylethyl) isocyanurate. When (b) the thermosetting agent is used, the amount used is preferably 1 to 20 parts by mass, more preferably 2 when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass. It is a mass part-15 mass parts, and may mix and use 2 or more types.
本発明の液晶シール剤は、成分（ｃ）として、分子内に活性水素を有さないエポキシ樹脂、（メタ）アクリル化エポキシ樹脂及び部分（メタ）アクリル化エポキシ樹脂から選択される１種もしくは２種以上からなる硬化性樹脂を含有しても良い（ただし活性水素として、ヒドロキシ基に含まれる水素は除く）。例えば、エポキシ樹脂、エポキシ樹脂と（メタ）アクリル化エポキシ樹脂の混合物、（メタ）アクリル化エポキシ樹脂、部分（メタ）アクリル化エポキシ樹脂等が挙げられる。本発明で用いる成分（ｃ）は、何れも液晶に対する汚染性、溶解性が低いものが好ましく、好適なエポキシ樹脂の例としては、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、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、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が、これらに限定されるものではない。（メタ）アクリロイル化エポキシ樹脂、部分（メタ）アクリロイル化エポキシ樹脂は、エポキシ樹脂と（メタ）アクリル酸の周知の反応により得ることができる。例えば、エポキシ樹脂に所定の当量比の（メタ）アクリル酸と触媒（例えば、ベンジルジメチルアミン、トリエチルアミン、ベンジルトリメチルアンモニウムクロライド、トリフェニルホスフィン、トリフェニルスチビン等）と、重合防止剤（例えば、メトキノン、ハイドロキノン、メチルハイドロキノン、フェノチアジン、ジブチルヒドロキシトルエン等）を添加して、例えば８０℃〜１１０℃でエステル化反応を行うことにより得られる。原料となるエポキシ樹脂としては、特に限定されるものではないが、２官能以上のエポキシ樹脂が好ましく、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、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、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、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、より好ましいものはビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂である。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、工程適合性及び液晶汚染性の観点から適切に選択される。 As the component (c), the liquid crystal sealing agent of the present invention is one or two selected from an epoxy resin having no active hydrogen in the molecule, a (meth) acrylated epoxy resin, and a partially (meth) acrylated epoxy resin. A curable resin composed of more than one species may be contained (however, hydrogen contained in a hydroxy group is excluded as active hydrogen). Examples thereof include an epoxy resin, a mixture of an epoxy resin and a (meth) acrylated epoxy resin, a (meth) acrylated epoxy resin, and a partial (meth) acrylated epoxy resin. The component (c) used in the present invention preferably has low contamination and solubility in liquid crystals. Examples of suitable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy. Resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, hydantoin type epoxy Resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having triphenolmethane skeleton, other diglycidyl ethers of difunctional phenols, diglycidyl ether of difunctional alcohols Things, and their halides, but like hydrogenated product, but is not limited thereto. The (meth) acryloylated epoxy resin and the partially (meth) acryloylated epoxy resin can be obtained by a well-known reaction between an epoxy resin and (meth) acrylic acid. For example, (meth) acrylic acid in a predetermined equivalent ratio to an epoxy resin and a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) and a polymerization inhibitor (for example, methoquinone, Hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) are added, and the esterification reaction is performed at 80 ° C. to 110 ° C., for example. Although it does not specifically limit as an epoxy resin used as a raw material, An epoxy resin more than bifunctional is preferable, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin , Cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin Phenol novolac epoxy resins having a triphenolmethane skeleton, other diglycidyl ethers of difunctional phenols, diglycidyl ethers of difunctional alcohols, and Their halides, and the like hydrogenated product. Of these, bisphenol type epoxy resin and novolac type epoxy resin are more 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 and liquid crystal contamination.
本発明の液晶シール剤が成分（ｃ）を含有する場合、その使用量は、得られる液晶シール剤の作業性、物性を考慮して適宜決定される。通常、液晶シール剤総量を１００質量部とした場合に、２０質量部〜８０質量部含有する場合が好ましく、更に好ましくは３０質量部〜７０質量部である。 When the liquid-crystal sealing compound of this invention contains a component (c), the usage-amount is suitably determined in consideration of the workability | operativity and physical property of the liquid-crystal sealing compound obtained. Usually, when the total amount of the liquid crystal sealant is 100 parts by mass, the content is preferably 20 parts by mass to 80 parts by mass, and more preferably 30 parts by mass to 70 parts by mass.
本発明の液晶シール剤では成分（ｄ）シランカップリング剤を用いて、接着強度向上や耐湿信頼性向上を図ることができる。シランカップリング剤としては、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メトキシシラン、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。シランカップリング剤（ｄ）の液晶シール剤に占める含有量は、本発明の液晶シール剤の総量を１００質量部とした場合、０．０５質量部〜３質量部が好適である。 In the liquid crystal sealing agent of the present invention, the component (d) silane coupling agent can be used to improve the adhesive strength and improve the moisture resistance reliability. Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3 -Black Propyl methyl dimethoxy silane, 3-chloropropyl trimethoxy silane, and the like. The content of the silane coupling agent (d) in the liquid crystal sealant is preferably 0.05 parts by mass to 3 parts by mass when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass.
本発明の液晶シール剤では成分（ｅ）無機フィラーを用いて、接着強度向上や耐湿信頼性向上を図ることができる。この（ｅ）無機フィラーとしては、溶融シリカ、結晶シリカ、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、珪酸アルミニウムであり、更に好ましくは溶融シリカ、結晶シリカ、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。その平均粒径は、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、３μｍ以下が適当であり、好ましくは２μｍ以下である。粒径はレーザー回折・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）により測定した。 In the liquid crystal sealant of the present invention, the component (e) inorganic filler can be used to improve adhesive strength and moisture resistance reliability. As this (e) inorganic filler, fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, 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, nitriding Silicon, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, more preferably fused silica, crystalline silica, aluminum Mina, is a talc. These inorganic fillers may be used in combination of two or more. If the average particle size is too large, it becomes a cause of defects such as failure to form a gap when laminating the upper and lower glass substrates when manufacturing a narrow gap liquid crystal cell, and therefore 3 μm or less is appropriate, and preferably 2 μm or less. The particle size was measured with a laser diffraction / scattering type particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
本発明の液晶シール剤で使用しうる無機フィラー（ｅ）の液晶シール剤中の含有量は、本発明の液晶シール剤の総量を１００質量部とした場合、通常３〜６０質量部、好ましくは５〜５０質量部である。無機フィラーの含有量が少なすぎる場合、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多すぎると、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。 The content of the inorganic filler (e) that can be used in the liquid crystal sealant of the present invention in the liquid crystal sealant is usually 3 to 60 parts by mass, preferably 100 parts by mass when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass, preferably 5 to 50 parts by mass. When there is too little content of an inorganic filler, since the adhesive strength with respect to a glass substrate falls and moisture resistance reliability is also inferior, the fall of the adhesive strength after moisture absorption may also become large. Moreover, when there is too much content of an inorganic filler, it may become difficult to collapse and it will become impossible to form the gap of a liquid crystal cell.
本発明の液晶シール剤は、光熱併用硬化型の液晶シール剤とする為に、成分（ｆ）光ラジカル重合開始剤を含有しても良い。光ラジカル重合開始剤は、ＵＶや可視光の照射によって、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、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フィンオキサイド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ＷＯ２００６／０２７９８２号記載の方法にて製造して得ることができる。 The liquid crystal sealant of the present invention may contain a component (f) photo radical polymerization initiator in order to obtain a photothermal combined curing liquid crystal sealant. The photo radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by UV or visible light irradiation and initiates a chain polymerization reaction. For example, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, Benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine An oxide etc. can be mentioned. Moreover, it is preferable to use what has a (meth) acryl group in a molecule | numerator from a liquid crystal contamination viewpoint, for example, 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl]- The reaction product with 2-hydroxy-2methyl-1-propan-1-one is preferably used. This compound can be obtained by the method described in International Publication WO2006 / 027982.
本発明の液晶シール剤で使用しうる成分（ｆ）光重合開始剤の液晶シール剤中の含有量は、本発明の液晶シール剤の総量を１００質量部とした場合、通常０．５質量部〜２０質量部、好ましくは１質量部〜１５質量部である。 The content of the component (f) photopolymerization initiator that can be used in the liquid crystal sealant of the present invention in the liquid crystal sealant is usually 0.5 parts by mass when the total amount of the liquid crystal sealant of the present invention is 100 parts by mass. -20 parts by mass, preferably 1-15 parts by mass.
本発明の液晶シール剤には、さらに必要に応じて、（メタ）アクリル酸エステルのモノマー及び／又はオリゴマーを使用しても良い。そのようなモノマー、オリゴマーとしては、例えば、ジペンタエリスリトールと（メタ）アクリル酸の反応物、ジペンタエリスリトール・カプロラクトンと（メタ）アクリル酸の反応物等が挙げられるが、液晶に対する汚染性が低いものならば特に制限されるものではない。 In the liquid crystal sealant of the present invention, a monomer and / or oligomer of (meth) acrylic acid ester may be used as necessary. Examples of such a monomer or oligomer include a reaction product of dipentaerythritol and (meth) acrylic acid, a reaction product of dipentaerythritol / caprolactone and (meth) acrylic acid, and the like, but has low contamination with liquid crystals. If it is a thing, it will not restrict | limit in particular.
本発明の液晶シール剤には、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、有機フィラーならびに顔料、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 liquid crystal sealing agent of the present invention may further contain additives such as curing accelerators such as organic acids and imidazoles, organic fillers, pigments, leveling agents, antifoaming agents, and solvents.
本発明の液晶シール剤を得る方法の一例としては、次に示す方法がある。まず、（ａ）成分に必要に応じ、（ｃ）成分、（ｆ）成分を加熱溶解する。次いで室温まで冷却後、（ｂ）成分を添加し、必要に応じて（ｄ）成分、（ｅ）成分、並びに有機フィラー、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 liquid crystal sealant of the present invention is the following method. First, the component (c) and the component (f) are heated and dissolved in the component (a) as necessary. Next, after cooling to room temperature, component (b) is added, and if necessary, component (d), component (e), organic filler, antifoaming agent, leveling agent, solvent, etc. are added, 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５００ｍＪ／ｃｍ２〜６０００ｍＪ／ｃｍ２、より好ましくは１０００ｍＪ／ｃｍ２〜４０００ｍＪ／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２μｍ〜８μｍ、好ましくは４μｍ〜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質量部〜４質量部、好ましくは０．５質量部〜２質量部、更に、好ましくは０．９質量部〜１．５質量部程度である。 The liquid crystal display cell of the present invention is a cell in which a pair of substrates having predetermined electrodes formed on a substrate are arranged opposite to each other at a predetermined interval, the periphery is sealed with the liquid crystal sealant of the present invention, and the liquid crystal is sealed in the gap. is there. 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 of the present invention, the liquid crystal sealant is applied to one of the pair of substrates using a dispenser or a screen printing device. Then, if necessary, temporary curing is performed at 80 ° C 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 ° C. to 130 ° C. for 1 hour 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. Ultraviolet irradiation amount is preferably 500mJ / cm 2 ~6000mJ / cm 2 , more preferably the dose of 1000mJ / cm 2 ~4000mJ / cm 2 is preferred. Then, if necessary, the liquid crystal display cell of the present invention can be obtained by curing at 90 ° C. 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 μm to 8 μm, preferably 4 μm 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 0.9 to 1 part by weight, based on 100 parts by weight of the liquid crystal sealant of the present invention. About 5 parts by mass.
本発明の液晶シール剤は、熱硬化性が非常に良好であり、液晶滴下工法における加熱工程において速やかに硬化する。従って、構成成分の液晶への溶出も極めて少なく、液晶表示セルの表示不良を低減することが可能である。また、保存安定性にも優れる為、液晶表示セルの製造に適している。更に、その硬化物は接着強度、耐熱性、耐湿性等の各種硬化物特性にも優れる為、本発明の液晶シール剤を用いることにより、信頼性に優れる液晶表示セルを作成することが可能である。また、本発明の液晶シール剤を用いて作成した液晶表示セルは、電圧保持率が高く、イオン密度が低いという液晶表示セルとして必要な特性も充足される。 The liquid crystal sealing agent of the present invention has a very good thermosetting property, and quickly cures in the heating step in the liquid crystal dropping method. Therefore, the elution of the constituent components into the liquid crystal is extremely small, and display defects of the liquid crystal display cell can be reduced. Moreover, since it is excellent also in storage stability, it is suitable for manufacture of a liquid crystal display cell. Furthermore, since the cured product is excellent in various cured product characteristics such as adhesive strength, heat resistance, and moisture resistance, it is possible to produce a liquid crystal display cell with excellent reliability by using the liquid crystal sealant of the present invention. is there. In addition, the liquid crystal display cell prepared using the liquid crystal sealant of the present invention satisfies the characteristics required for a liquid crystal display cell having a high voltage holding ratio and a low ion density.
以下合成例、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, the present invention will be described in more detail with reference to synthesis examples and 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型エポキシ樹脂のエポキシアクリレートの合成
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（アクリル化ビスフェノールＡ型エポキシ樹脂）３９５ｇを得た（ＫＡＹＡＲＡＤＲＴＭＲ−９３１００）。
[Synthesis Example 1]
Synthesis of epoxy acrylate 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.) was dissolved in 266.8 g of toluene, and dibutylhydroxytoluene as a polymerization inhibitor. 0.8g was added and it heated up to 60 degreeC. Thereafter, 117.5 g of acrylic acid with 100% equivalent of epoxy group was added and 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. The reaction solution was washed with water and toluene was distilled off to obtain 395 g of the desired bisphenol A type epoxy acrylate (acrylated bisphenol A type epoxy resin) (KAYARAD RTM R-93100).
［合成例２］
ビスフェノールＡ型エポキシアクリレートの酸無水物付加物の合成
合成例１で得られたビスフェノールＡ型エポキシアクリレート４．８４ｇ、４−ジメチルアミノピリジン０．０４９ｇ、トリエチルアミン６．０７ｇ、塩化メチレン１０００ｍｌを加え、室温にて撹拌して溶解させた後、テトラヒドロ無水フタル酸１８．３ｇを加え室温で３時間撹拌した。得られた反応液を６回水洗した後、塩化メチレンを留去することにより分子内にカルボキシ基を有するビスフェノールＡ型エポキシアクリレート７ｇを得た。ＬＣ ＭＳ（ｍ／ｚ）＝７８７（Ｍ−Ｈ）、ＩＲ １７０９ｃｍ−１（ＣＯＯＨ）。
[Synthesis Example 2]
Synthesis of acid anhydride adduct of bisphenol A type epoxy acrylate 4.84 g of bisphenol A type epoxy acrylate obtained in Synthesis Example 1, 0.049 g of 4-dimethylaminopyridine, 6.07 g of triethylamine, and 1000 ml of methylene chloride were added at room temperature. Then, 18.3 g of tetrahydrophthalic anhydride was added and stirred at room temperature for 3 hours. The obtained reaction solution was washed 6 times with water, and then methylene chloride was distilled off to obtain 7 g of a bisphenol A type epoxy acrylate having a carboxy group in the molecule. LC MS (m / z) = 787 (M-H), IR 1709 cm < -1 > (COOH).
［合成例３］
アクリル化レゾルシンジグリシジルエーテルの合成
レゾルシンジグリシジルエーテル１８１．２ｇ（ナガセケムテックス株式会社）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、目的とするレゾルシンジグリシジルエーテルのエポキシアクリレート（アクリル化レゾルシンジグリシジルエーテル）２５３ｇを得た。
［合成例４］
アクリル化レゾルシンジグリシジルエーテルの酸無水物付加物の合成
合成例３で得られたレゾルシンジグリシジルエーテルのエポキシアクリレート３．６６ｇ、４−ジメチルアミノピリジン０．０４９ｇ、トリエチルアミン６．０７ｇ、塩化メチレン１０００ｍｌを加え、室温にて撹拌して溶解させた後、無水マレイン酸１１．８ｇを加え室温で２時間撹拌した。得られた反応液を６回水洗した後、塩化メチレンを留去することにより分子内にカルボキシ基を有するアクリル化レゾルシノールジグリシジルエーテル５ｇを得た。ＬＣ ＭＳ（ｍ／ｚ）＝５６１（Ｍ−Ｈ）、ＩＲ １７０５ｃｍ−１（ＣＯＯＨ）。
[Synthesis Example 3]
Synthesis of acrylated resorcin diglycidyl ether Resorcin diglycidyl ether 181.2g (Nagase ChemteX Corporation) was dissolved in 266.8g of toluene, and 0.8g of dibutylhydroxytoluene was added to this as a polymerization inhibitor, and the temperature was raised to 60 ° C. Warm up. Thereafter, 117.5 g of acrylic acid with 100% equivalent of epoxy group was added and 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 253 g of a desired resorcin diglycidyl ether epoxy acrylate (acrylated resorcin diglycidyl ether).
[Synthesis Example 4]
Synthesis of acid anhydride adduct of acrylated resorcin diglycidyl ether 3.66 g of resorcin diglycidyl ether epoxy acrylate obtained in Synthesis Example 3, 0.049 g of 4-dimethylaminopyridine, 6.07 g of triethylamine, and 1000 ml of methylene chloride. The mixture was stirred and dissolved at room temperature, 11.8 g of maleic anhydride was added, and the mixture was stirred at room temperature for 2 hours. The obtained reaction solution was washed with water six times, and then methylene chloride was distilled off to obtain 5 g of acrylated resorcinol diglycidyl ether having a carboxy group in the molecule. LC MS (m / z) = 561 (M-H), IR 1705 cm < -1 > (COOH).
[実施例１〜３、比較例１〜４]
下記表１に示す割合で各硬化性樹脂成分（成分（ａ）、（ｃ））を混合攪拌した後、９０℃で加熱溶解した。そこへ、光ラジカル重合開始剤（成分（ｆ））を加熱溶解させた後、室温まで冷却し、シランカップリング剤（成分（ｄ））、無機フィラー（成分（ｅ））、熱硬化剤（成分（ｂ））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、液晶滴下工法用シール剤実施例１〜３を調製した。
また、同様に下記表１に示す割合で硬化性樹脂成分（成分（ｃ））を９０℃で加熱した。そこへ、光ラジカル重合開始剤（成分（ｆ））を加熱溶解させた後、室温まで冷却し、シランカップリング剤（成分（ｄ））、無機フィラー（成分（ｅ））、熱硬化剤（成分（ｂ））、硬化促進剤を添加し、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、液晶滴下工法用シール剤比較例１〜４を調製した。
[Examples 1 to 3, Comparative Examples 1 to 4]
Each curable resin component (components (a) and (c)) was mixed and stirred at the ratio shown in Table 1 below, and then heated and dissolved at 90 ° C. The photo radical polymerization initiator (component (f)) was heated and dissolved therein, and then cooled to room temperature. A silane coupling agent (component (d)), an inorganic filler (component (e)), a thermosetting agent ( Component (b)) was added and stirred, and then dispersed by a three-roll mill and filtered through a metal mesh (635 mesh) to prepare liquid crystal dropping method sealing agents Examples 1 to 3.
Similarly, the curable resin component (component (c)) was heated at 90 ° C. at the ratio shown in Table 1 below. The photo radical polymerization initiator (component (f)) was heated and dissolved therein, and then cooled to room temperature. A silane coupling agent (component (d)), an inorganic filler (component (e)), a thermosetting agent ( Component (b)) and a curing accelerator were added and stirred, and then dispersed by a three-roll mill and filtered through a metal mesh (635 mesh) to prepare sealant comparative examples 1 to 4 for a liquid crystal dropping method.
評価試験は下記の方法で実施した。 The evaluation test was carried out by the following method.
（接着強度測定）
得られた液晶シール剤１００ｇにスペーサとして５μｍのグラスファイバー１ｇを添加して混合撹拌を行う。この液晶シール剤を５０ｍｍ×５０ｍｍのガラス基板上に塗布し、その液晶シール剤上に１．５ｍｍ×１．５ｍｍのガラス片を貼り合わせＵＶ照射機により３０００ｍＪ／ｃｍ２の紫外線を照射後、オーブンに投入して１２０℃１時間熱硬化させた。ガラス片のせん断接着強度をボンドテスター（ＳＳ−３０ＷＤ：西進商事株式会社製）にて測定した。結果を表１に示す。
(Adhesive strength measurement)
To 100 g of the obtained liquid crystal sealant, 1 g of 5 μm glass fiber is added as a spacer and mixed and stirred. This liquid crystal sealant is applied onto a 50 mm × 50 mm glass substrate, a 1.5 mm × 1.5 mm glass piece is bonded onto the liquid crystal sealant, and an ultraviolet ray of 3000 mJ / cm 2 is irradiated by a UV irradiator. And then heat-cured at 120 ° C. for 1 hour. The shear adhesive strength of the glass pieces was measured with a bond tester (SS-30WD: manufactured by Seishin Shoji Co., Ltd.). The results are shown in Table 1.
（耐湿接着強度測定）
上記の液晶シール剤接着強度テストと同一の測定サンプルを作成する。その測定サンプルを１２１℃、２気圧、湿度１００％の条件で、プレッシャークッカー試験機（ＴＰＣ−４１１：タバイエスペック株式会社製）に１２時間投入したサンプルを上記ボンドテスターにて測定した。その結果を表１に示す。
(Moisture resistance measurement)
The same measurement sample as the above liquid crystal sealant adhesive strength test is prepared. The sample that was put into a pressure cooker tester (TPC-411: manufactured by Tabay Espec Co., Ltd.) for 12 hours under the conditions of 121 ° C., 2 atm, and humidity 100% was measured with the above bond tester. The results are shown in Table 1.
（吸湿率測定）
得られた液晶シール剤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ＵＶ照射機により３０００ｍＪ／ｃｍ２の紫外線を照射後、オーブンに投入して１２０℃１時間熱硬化させ、硬化後ＰＥＴフィルムを剥がしてサンプルとした。サンプルの重量を測定した後、６０℃９０％ＲＨの環境下に１２時間放置し、再度重量測定をする。初期重量に対する重量変化率（％）を表１に示す。
(Measurement of moisture absorption rate)
The obtained liquid crystal sealant was sandwiched between polyethylene terephthalate (PET) films to form a thin film having a thickness of 100 μm, irradiated with 3000 mJ / cm 2 of ultraviolet rays by a UV irradiator, and then put into an oven and thermally cured at 120 ° C. for 1 hour, After curing, the PET film was peeled off to prepare a sample. After the weight of the sample is measured, the sample is left in an environment of 60 ° C. and 90% RH for 12 hours, and the weight is measured again. Table 1 shows the weight change rate (%) with respect to the initial weight.
（ポットライフ測定）
得られた液晶シール剤の２５℃における粘度変化を測定した。２５℃５０ＲＨ％の条件下で７２時間放置した後の粘度測定を行い、初期粘度に対する粘度増加率（％）を表１に示す。
(Pot life measurement)
The viscosity change at 25 ° C. of the obtained liquid crystal sealant was measured. Viscosity measurement was performed after standing for 72 hours at 25 ° C. and 50 RH%, and Table 1 shows the rate of increase in viscosity (%) relative to the initial viscosity.
（評価用液晶セルの作成）
透明電極付き基板に配向膜液（ＰＩＡ−５５４０−０５Ａ；チッソ株式会社製）を塗布、焼成し、ラビング処理を施した。この基板に得られた液晶シール剤を貼り合せ後の線幅が１ｍｍとなるようにメインシールおよびダミーシールをディスペンスし、次いで液晶（ＪＣ−５０１５ＬＡ;チッソ株式会社製）の微小滴をシールパターンの枠内に滴下した。更にもう一枚のラビング処理済み基板に面内スペーサ（ナトコスペーサＫＳＥＢ−５２５Ｆ；ナトコ株式会社製；貼り合せ後のギャップ幅５μｍ）を散布、熱固着し、貼り合せ装置を用いて真空中で先の液晶滴下済み基板と貼り合せた。大気開放してギャップ形成した後、シールパターン枠内のみマスクをしてＵＶ照射機により５０ｍＪ／ｃｍ２の紫外線を照射後、オーブンに投入して１２０℃１時間熱硬化させ評価用液晶テストセルを作成した。
(Creation of liquid crystal cell for evaluation)
An alignment film solution (PIA-5540-05A; manufactured by Chisso Corporation) was applied to a substrate with a transparent electrode, baked, and rubbed. The main seal and the dummy seal are dispensed so that the line width after bonding the obtained liquid crystal sealant to the substrate is 1 mm, and then fine droplets of liquid crystal (JC-5015LA; manufactured by Chisso Corporation) are applied to the seal pattern. It was dripped in the frame. Furthermore, an in-plane spacer (NATOCO SPACER KSEB-525F; manufactured by NATCO; gap width of 5 μm after bonding) is sprayed and thermally fixed on another rubbing-treated substrate, and the substrate is first vacuumed using a bonding apparatus. It was bonded to a liquid crystal dripped substrate. After forming the gap by opening to the atmosphere, masking only the inside of the seal pattern frame and irradiating with 50 mJ / cm 2 of ultraviolet rays with a UV irradiator, putting it in an oven and thermosetting it at 120 ° C. for 1 hour to make a liquid crystal test cell for evaluation Created.
作成した評価用液晶セルのシールの耐差込み性およびシール近傍の液晶配向乱れを偏光顕微鏡にて観察し、耐差込み性及びシール近傍の液晶配向について以下に示す基準に従って評価を行った。結果を表１に示す。 The insertion resistance of the seal of the prepared liquid crystal cell for evaluation and liquid crystal alignment disorder in the vicinity of the seal were observed with a polarizing microscope, and the evaluation of the insertion resistance and liquid crystal alignment in the vicinity of the seal was performed according to the following criteria. The results are shown in Table 1.
（耐差込み性の評価）
◎：シールへの液晶の差込みが０．２ｍｍ未満であり、液晶の封止には問題が無いレベルである。
○：シールへの液晶の差込みが０．２ｍｍ以上０．４ｍｍ未満であり、液晶の封止には問題が無いレベルである。
△：シールへの液晶の差込みが０．４ｍｍ以上０．６ｍｍ未満であり、液晶の封止には問題が無いレベルである。
×：シールへの液晶の差込みが０．６ｍｍ以上１．０ｍｍ未満であり、液晶の封止には問題が無いレベルである。
××：シールが決壊しセルが形成できない。
(Evaluation of insertion resistance)
A: The insertion of the liquid crystal into the seal is less than 0.2 mm, and there is no problem in sealing the liquid crystal.
○: The insertion of the liquid crystal into the seal is 0.2 mm or more and less than 0.4 mm, and there is no problem in sealing the liquid crystal.
(Triangle | delta): The insertion of the liquid crystal to a seal | sticker is 0.4 mm or more and less than 0.6 mm, and is a level which does not have a problem in sealing of a liquid crystal.
X: The insertion of the liquid crystal into the seal is 0.6 mm or more and less than 1.0 mm, and there is no problem in sealing the liquid crystal.
XX: The seal is broken and a cell cannot be formed.
（シール近傍の液晶配向の評価）
◎：液晶の配向乱れがシールから０．２ｍｍ未満である。
○：液晶の配向乱れがシールから０．２ｍｍ以上０．４ｍｍ未満である。
△：液晶の配向乱れがシールから０．４ｍｍ以上０．６ｍｍ未満である。
×：液晶の配向乱れがシールから０．６ｍｍ以上１．０ｍｍ未満である。
××：シールが決壊しセルが形成出来ない。
(Evaluation of liquid crystal alignment near the seal)
A: The alignment disorder of the liquid crystal is less than 0.2 mm from the seal.
○: The alignment disorder of the liquid crystal is 0.2 mm or more and less than 0.4 mm from the seal.
Δ: The alignment disorder of the liquid crystal is 0.4 mm or more and less than 0.6 mm from the seal.
X: The alignment disorder of the liquid crystal is 0.6 mm or more and less than 1.0 mm from the seal.
XX: The seal is broken and a cell cannot be formed.
（硬化速度測定）
得られた液晶シール剤を動的粘弾性率測定装置（Ｒｈｅｏｓｏｌ−Ｇ５０００、株式会社ユービーエム製）にて複素粘性率を測定した。動的粘弾性率測定装置の設定は、以下のとおりである。コーン：直径２０ｍｍのパラレルコーン、周波数：１Ｈｚ、歪み角度：３ｄｅｇ．、測定温度３０℃から１２０℃まで１８℃／分の速度で昇温させ、その後１２０℃を維持させた。粘度が１００００Ｐａ・ｓに到達したときの時間を表１に示す。
(Curing rate measurement)
The complex viscosity of the obtained liquid crystal sealant was measured with a dynamic viscoelasticity measuring device (Rhesol-G5000, manufactured by UBM Co., Ltd.). The setting of the dynamic viscoelasticity measuring apparatus is as follows. Cone: Parallel cone with a diameter of 20 mm, frequency: 1 Hz, distortion angle: 3 deg. The measurement temperature was raised from 30 ° C. to 120 ° C. at a rate of 18 ° C./min, and then maintained at 120 ° C. Table 1 shows the time when the viscosity reached 10,000 Pa · s.
表１の結果より、硬化促進剤成分を含有しない比較例１は硬化性に劣り、その結果パネル表示特性において配向不良を生じている。また、硬化促進剤としてＣＩＣ酸やドデカン二酸、熱ラジカル開始剤を用いたものは、硬化性の向上は達成しているものの、液晶汚染性や耐湿接着性に不具合を生じている。これに対し、本願発明に係る実施例１〜３については、硬化性向上を実現しながら、他の特性も使用可能レベルであることが確認される。特に実施例１、２においては全ての特性において非常に優れた結果を示している。この結果より、本願発明の液晶シール剤は、保存安定性、硬化性に優れることから作業性に優れることが言え、また液晶汚染性、耐湿接着性、パネル表示特性に優れることから、液晶表示セルの高信頼性を実現できることが言える。 From the results shown in Table 1, Comparative Example 1 containing no curing accelerator component is inferior in curability, and as a result, orientation failure occurs in the panel display characteristics. In addition, those using CIC acid, dodecanedioic acid, or a thermal radical initiator as a curing accelerator have improved the curability, but have problems with liquid crystal contamination and moisture-resistant adhesion. On the other hand, about Examples 1-3 which concern on this invention, it is confirmed that another characteristic is also a usable level, implement | achieving sclerosis | hardenability improvement. In particular, Examples 1 and 2 show very excellent results in all characteristics. From this result, it can be said that the liquid crystal sealant of the present invention is excellent in workability because of its excellent storage stability and curability, and is excellent in liquid crystal contamination, moisture-resistant adhesion, and panel display characteristics. It can be said that high reliability can be realized.
本願発明の液晶シール剤は、作業性に優れる為、液晶表示セルの安定生産を可能とし、さらには液晶表示セルの長期信頼性確保にも貢献するものである。 Since the liquid crystal sealant of the present invention is excellent in workability, it enables stable production of the liquid crystal display cell and further contributes to ensuring long-term reliability of the liquid crystal display cell.
Claims (13)
で表される分子骨格を示す］ The liquid crystal sealant according to claim 8, wherein the component (b) thermosetting agent is one or more hydrazide compounds represented by the following formula (1).
The molecular skeleton represented by
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| JP2011147813A JP5748273B2 (en) | 2011-07-03 | 2011-07-03 | Liquid crystal sealant and liquid crystal display cell using the same |
| CN201280032956.9A CN103649824B (en) | 2011-07-03 | 2012-06-29 | Liquid crystal sealing agent and use its liquid crystal display |
| TW101123489A TW201319109A (en) | 2011-07-03 | 2012-06-29 | Liquid crystal sealing material and liquid crystal display cell using same |
| PCT/JP2012/066792 WO2013005692A1 (en) | 2011-07-03 | 2012-06-29 | Liquid crystal sealing material and liquid crystal display cell using same |
| KR1020147001603A KR20140039314A (en) | 2011-07-03 | 2012-06-29 | Liquid crystal sealing material and liquid crystal display cell using same |
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| JP2011147813A JP5748273B2 (en) | 2011-07-03 | 2011-07-03 | Liquid crystal sealant and liquid crystal display cell using the same |
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| JP5748273B2 JP5748273B2 (en) | 2015-07-15 |
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| JP (1) | JP5748273B2 (en) |
| KR (1) | KR20140039314A (en) |
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| JP3240487B2 (en) | 1992-12-14 | 2001-12-17 | 澄夫 増澤 | Drawing spraying method |
| JP6373181B2 (en) * | 2014-12-10 | 2018-08-15 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
| KR102149717B1 (en) * | 2016-11-21 | 2020-08-31 | 교리쯔 가가꾸 산교 가부시키가이샤 | Resin composition for electronic device |
| WO2018201428A1 (en) * | 2017-05-05 | 2018-11-08 | Henkel Ag & Co. Kgaa | Thermally curable sealant composition and use thereof |
| CN116217892B (en) * | 2022-12-22 | 2025-10-03 | 南京思远光电科技有限公司 | A curable resin and liquid crystal sealant prepared therefrom |
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| JP2006039096A (en) * | 2004-07-26 | 2006-02-09 | Three Bond Co Ltd | Composition for liquid crystal display device |
| WO2009001689A1 (en) * | 2007-06-25 | 2008-12-31 | Nippon Kayaku Kabushiki Kaisha | Sealing material for liquid crystal and liquid-crystal display cell made with the same |
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| AU2003264513A1 (en) * | 2002-09-19 | 2004-04-08 | Mitsui Chemicals, Inc. | Sealing composition for liquid crystal displays and process for production of liquid crystal display panels |
| JP4802461B2 (en) * | 2004-07-22 | 2011-10-26 | 株式会社スリーボンド | Photopolymerization initiator and photocurable material using the same |
| JP5153123B2 (en) * | 2006-11-20 | 2013-02-27 | 三井化学株式会社 | SEALING AGENT FOR LIQUID CRYSTAL DROPING METHOD, LIQUID CRYSTAL DISPLAY PANEL MANUFACTURING METHOD USING SAME, AND LIQUID CRYSTAL DISPLAY PANEL |
| JP2010014771A (en) * | 2008-07-01 | 2010-01-21 | Nippon Kayaku Co Ltd | Thermosetting liquid crystal sealing material for liquid crystal dropping method and liquid crystal display cell using the same |
| JP5008682B2 (en) * | 2009-01-21 | 2012-08-22 | 株式会社Ａｄｅｋａ | Sealant for liquid crystal dropping method containing photo-curing resin and thermosetting resin |
| JP5152868B2 (en) * | 2009-06-11 | 2013-02-27 | 日本化薬株式会社 | Visible light curable liquid crystal sealant and liquid crystal display cell using the same |
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- 2012-06-29 KR KR1020147001603A patent/KR20140039314A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006039096A (en) * | 2004-07-26 | 2006-02-09 | Three Bond Co Ltd | Composition for liquid crystal display device |
| WO2009001689A1 (en) * | 2007-06-25 | 2008-12-31 | Nippon Kayaku Kabushiki Kaisha | Sealing material for liquid crystal and liquid-crystal display cell made with the same |
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| TW201319109A (en) | 2013-05-16 |
| CN103649824B (en) | 2016-09-07 |
| CN103649824A (en) | 2014-03-19 |
| KR20140039314A (en) | 2014-04-01 |
| WO2013005692A1 (en) | 2013-01-10 |
| JP5748273B2 (en) | 2015-07-15 |
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