JP5651177B2 - 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
- JP5651177B2 JP5651177B2 JP2012525299A JP2012525299A JP5651177B2 JP 5651177 B2 JP5651177 B2 JP 5651177B2 JP 2012525299 A JP2012525299 A JP 2012525299A JP 2012525299 A JP2012525299 A JP 2012525299A JP 5651177 B2 JP5651177 B2 JP 5651177B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- meth
- mass
- sealant
- crystal dropping
- 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.)
- Expired - Fee Related
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 213
- 239000000565 sealant Substances 0.000 title claims description 67
- -1 acryl group Chemical group 0.000 claims description 72
- 239000003795 chemical substances by application Substances 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 68
- 239000003822 epoxy resin Substances 0.000 claims description 52
- 229920000647 polyepoxide Polymers 0.000 claims description 52
- 238000007789 sealing Methods 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 28
- 229920001187 thermosetting polymer Polymers 0.000 claims description 27
- 239000003504 photosensitizing agent Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000003999 initiator Substances 0.000 claims description 20
- 239000011256 inorganic filler Substances 0.000 claims description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 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 4
- 239000003566 sealing material Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 29
- 238000001723 curing Methods 0.000 description 18
- 238000011109 contamination Methods 0.000 description 14
- 210000004027 cell Anatomy 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 239000011521 glass Substances 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 238000000016 photochemical curing Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- 230000001588 bifunctional effect Effects 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
- 239000011159 matrix material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 3
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 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
- 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
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 125000004122 cyclic group Chemical group 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 2
- 229940091173 hydantoin Drugs 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003505 polymerization initiator 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
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 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 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
- 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
- ROFVGYAMRSGUSQ-UHFFFAOYSA-N 1-(2-bromoethyl)piperazine;hydrobromide Chemical compound Br.BrCCN1CCNCC1 ROFVGYAMRSGUSQ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- 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 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
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-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
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-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
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-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
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
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- OJJNKZYYPVTTQD-UHFFFAOYSA-N CCCCOc(cc1)c(cccc2)c2c1OCC(C)OC(C=C)=O Chemical compound CCCCOc(cc1)c(cccc2)c2c1OCC(C)OC(C=C)=O OJJNKZYYPVTTQD-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- UAKWLVYMKBWHMX-UHFFFAOYSA-N SU4312 Chemical compound C1=CC(N(C)C)=CC=C1C=C1C2=CC=CC=C2NC1=O UAKWLVYMKBWHMX-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- ATJPMEDFLOEOMJ-UHFFFAOYSA-N [3,5-di(prop-2-enoyloxy)phenyl] prop-2-enoate Chemical compound C=CC(=O)OC1=CC(OC(=O)C=C)=CC(OC(=O)C=C)=C1 ATJPMEDFLOEOMJ-UHFFFAOYSA-N 0.000 description 1
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 description 1
- UKMBKKFLJMFCSA-UHFFFAOYSA-N [3-hydroxy-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)OC(=O)C(C)=C UKMBKKFLJMFCSA-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- OFLXLNCGODUUOT-UHFFFAOYSA-N acetohydrazide Chemical compound C\C(O)=N\N OFLXLNCGODUUOT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 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
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-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
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 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
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010276 construction 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
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 1
- OXAGUPFRAIIDLT-UHFFFAOYSA-N heptanedihydrazide Chemical compound NNC(=O)CCCCCC(=O)NN OXAGUPFRAIIDLT-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 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
- 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
- VMFUMDXVTKTZQY-UHFFFAOYSA-N naphthalene-1-carbohydrazide Chemical compound C1=CC=C2C(C(=O)NN)=CC=CC2=C1 VMFUMDXVTKTZQY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 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
- 229960001755 resorcinol Drugs 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
- 239000007787 solid Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000006228 supernatant 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
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0625—Polyacrylic esters or derivatives thereof
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- 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
-
- 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
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
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- Engineering & Computer Science (AREA)
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- Sealing Material Composition (AREA)
- Liquid Crystal (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、液晶パネルにおいて、配線等の影となり、直接紫外線が照射されない遮光部においても良好な硬化性を有し、また可視光等の低エネルギー光でも良好な硬化性を有し、かつ極めて液晶汚染性が低い液晶滴下工法用シール剤に関する。 In the liquid crystal panel, the present invention has good curability even in a light-shielding portion that is a shadow of wiring and is not directly irradiated with ultraviolet rays in a liquid crystal panel, has good curability even with low energy light such as visible light, and extremely The present invention relates to a sealing agent for liquid crystal dropping method with low liquid crystal contamination.
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た（特許文献１、特許文献２参照）。具体的には、該方法は、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、液晶が封止された液晶表示セルを製造する方法である。
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
しかし、液晶滴下工法は、液晶シール剤が、まず未硬化の状態で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して液晶の比抵抗を低下させ、シール近傍の表示不良が発生する問題点がある。 However, in the liquid crystal dropping method, the liquid crystal sealant first contacts the liquid crystal in an uncured state, and at that time, the components of the liquid crystal sealant dissolve in the liquid crystal, lowering the specific resistance of the liquid crystal, and displaying near the seal There is a problem that defects occur.
液晶滴下工法において、基板を貼り合わせた後の液晶シール剤の硬化方法として、熱硬化法、光硬化法、光熱硬化併用法の３つの方法が考えられている。熱硬化法では、加熱による液晶の膨張により低粘度化した硬化途中の液晶シール剤から液晶が漏れてしまうという問題と低粘度化した液晶シール剤の成分が液晶に溶解してしまうという問題があり、これらの問題は解決が困難であり、いまだ実用化されていない。 In the liquid crystal dropping method, three methods of a thermosetting method, a photocuring method, and a photothermal curing combined method are considered as a curing method of the liquid crystal sealant after the substrates are bonded together. In the thermosetting method, there is a problem that the liquid crystal leaks from the liquid crystal sealant in the middle of curing, which has been reduced in viscosity due to expansion of the liquid crystal due to heating, and a problem that the components of the liquid crystal sealant whose viscosity has been reduced dissolves in the liquid crystal. These problems are difficult to solve and have not yet been put into practical use.
一方、光硬化法に用いられる液晶シール剤としては、光重合開始剤の種類によりカチオン重合型とラジカル重合型の２種類が挙げられる。カチオン重合型の液晶シール剤（特許文献３参照）については、光硬化の際にイオンが発生するため、これを液晶滴下工法に使用した場合、接触状態の液晶中にイオン成分が溶出し、液晶の比抵抗を低下させるという問題がある。又、ラジカル重合型の液晶シール剤（特許文献４参照）については光硬化時の硬化収縮が大きいために、接着強度が十分でないという問題がある。更に、カチオン重合型とラジカル重合型の両方の光硬化法に関わる問題点として、液晶表示セル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るため、遮光部が未硬化になるという問題が生じる。 On the other hand, the liquid crystal sealant used in the photocuring method includes two types of cationic polymerization type and radical polymerization type depending on the type of photopolymerization initiator. With regard to the cationic polymerization type liquid crystal sealing agent (see Patent Document 3), ions are generated during photocuring, so when this is used in a liquid crystal dropping method, the ionic component is eluted in the liquid crystal in the contact state, and the liquid crystal There is a problem of lowering the specific resistance. Further, the radical polymerization type liquid crystal sealant (see Patent Document 4) has a problem that the adhesive strength is not sufficient because of the large shrinkage during photocuring. Furthermore, as a problem related to both cationic polymerization type and radical polymerization type photocuring methods, the light shielding part where the liquid crystal sealant is not exposed to light by the metal wiring part of the array substrate of the liquid crystal display cell and the black matrix part of the color filter substrate. Therefore, there arises a problem that the light shielding portion is uncured.
このように熱硬化法、光硬化法は様々な問題点を抱えており、現実には特許文献５に示されている様な光熱硬化併用法が最も実用的な工法と考えられている。光熱硬化併用法は、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。通常こういったシール剤には光反応性樹脂、光開始剤、熱硬化性樹脂、熱硬化剤を含有する事が一般的である。光反応性樹脂と熱硬化剤の選択の仕方によっては、光反応性樹脂を熱硬化剤で硬化させる事も可能である。例えば、特許文献６に記載の様に、光反応性樹脂にエポキシアクリレートを用い、熱硬化剤に有機酸ヒドラジドを用いると、マイケル付加反応による光反応性樹脂を熱硬化させることが可能である。この方法を用いることにより、光硬化時に未硬化となってしまう遮光部の光反応性樹脂を熱硬化時に、硬化させる事ができる。しかしながら、一般的に液晶表示セル内には遮光部と露光部が併存する為、熱硬化剤の添加量が問題となる。つまり、露光部に合わせ、熱硬化性樹脂を硬化させるだけの量の熱硬化剤を添加すると、遮光部では熱硬化剤が不足し、硬化不十分となる。また遮光部に合わせ過剰の熱硬化剤を添加すると露光部において熱硬化剤が過剰となり、未反応で残存し、硬化物の特性を落とすという結果となってしまう。従って遮光部の未硬化の光反応性樹脂を熱硬化時に一緒に硬化する方法はあまり良い方法とはいえない。
Thus, the thermosetting method and the photocuring method have various problems, and the photothermal curing combined method as shown in
また最近では、液晶滴下工法において、紫外線に代えて波長が４００ｎｍ以上の可視光を使用しようとする動きがある。可視光は紫外線と比較し、低エネルギーである為、液晶滴下工法用液晶シール剤においても、低エネルギーで硬化することが要求される。これは遮光部における硬化性の向上と類似した課題である。 Recently, in the liquid crystal dropping method, there is a movement to use visible light having a wavelength of 400 nm or more instead of ultraviolet rays. Since visible light has lower energy than ultraviolet light, it is required that the liquid crystal sealant for the liquid crystal dropping method be cured with low energy. This is a problem similar to the improvement in curability in the light shielding portion.
以上述べてきたように、液晶滴下工法用の液晶シール剤で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するものは未だ完成していない。 As described above, although development of a liquid crystal sealant for a liquid crystal dropping method has been carried out very vigorously, a product having excellent light-shielding part curability has not yet been completed.
本発明は、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て、液晶シール部に光照射後、加熱硬化で液晶表示セルが製造される液晶滴下工法に用いられる液晶シール剤に関するものであり、工程を通して液晶に対して極めて汚染性が低く、基板への塗布作業性、貼り合わせ性、接着強度に優れ、且つ遮光部硬化性が非常に優れている為、いかなる設計の液晶パネルにも適応可能である液晶シール剤を提案するものである。 In the present invention, after the liquid crystal is dropped inside the liquid crystal sealing agent weir formed on one substrate, the other substrate is bonded, the liquid crystal seal portion is irradiated with light, and then the liquid crystal display cell is manufactured by heat curing. It is related to the liquid crystal sealant used in the liquid crystal dripping method, has extremely low contamination to the liquid crystal throughout the process, has excellent workability for application to the substrate, bonding properties, and adhesive strength, and has a light-shielding part curability. This is a liquid crystal sealant that can be applied to liquid crystal panels of any design because it is very excellent.
本発明は、液晶パネルにおいて、配線等の影となり、直接紫外線が照射されない箇所においても良好な硬化性を有し、かつ極めて液晶汚染性が低い液晶シール剤及びそれを用いた液晶表示セルを提供する。 The present invention provides a liquid crystal sealant having a good curability in a liquid crystal panel which is a shadow of wiring, etc., and is not directly irradiated with ultraviolet rays, and a liquid crystal display cell using the same. To do.
本発明者らは、鋭意検討の結果、アクリル基を分子内に有する光増感剤を用いる事によって格段に光による反応性を向上し、また液晶汚染性も抑える事が可能である事を見い出し、本発明を完成するに至った。
即ち本発明は、次の（１）〜（１７）に関するものである。As a result of intensive studies, the present inventors have found that by using a photosensitizer having an acrylic group in the molecule, the reactivity by light can be remarkably improved and the liquid crystal contamination can be suppressed. The present invention has been completed.
That is, the present invention relates to the following (1) to (17).
（１） （ａ）（メタ）アクリル基を分子内に有する光増感剤および（ｂ）（メタ）アクリル基を有する硬化性樹脂を含有する液晶滴下工法用液晶シール剤。
（２）（ａ）（メタ）アクリル基を分子内に有する光増感剤がチオキサントンカルボン酸とグリシジル（メタ）アクリレート化合物との反応生成物または４−Ｃ１ーＣ４アルコキシ−１−（２−（メタ）アクリルオキシ−２−Ｒ１−エトキシ）ナフタレン（Ｒ１は水素原子またはＣ１ーＣ２アルキル基を表す）である上記（１）に記載の液晶滴下工法用液晶シール剤。
（３） 前記（ａ）（メタ）アクリル基を分子内に有する光増感剤が少なくとも下記式（１）乃至（３）で表される化合物の何れかである上記（１）に記載の液晶滴下工法用液晶シール剤。
式（１）
(2) (a) A photosensitizer having a (meth) acryl group in the molecule is a reaction product of thioxanthonecarboxylic acid and a glycidyl (meth) acrylate compound or 4-C1-C4 alkoxy-1- (2- ( meth) acryloxy -2-R 1 - ethoxy) naphthalene (R 1 is a liquid crystal dropping process for a liquid crystal sealing material according to (1) a represents a hydrogen atom or a C1 over C2 alkyl group).
(3) The liquid crystal according to (1), wherein the photosensitizer (a) having a (meth) acryl group in the molecule is at least one of compounds represented by the following formulas (1) to (3): Liquid crystal sealant for dripping method.
Formula (1)
（４） 更に（ｃ）３級アミン化合物を含有する上記（１）〜（３）の何れか一項に記載の液晶滴下工法用液晶シール剤。
（５）更に（ｄ）光重合開始剤を含有する上記（１）〜（４）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
（６） 前記光重合開始剤（ｄ）が分子内に（メタ）アクリル基を有する光重合開始剤である上記（５）に記載の液晶滴下工法用液晶シール剤。
（７） 前記硬化性樹脂（ｂ）がエポキシ（メタ）アクリレートである上記（１）〜（６）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
（８） 前記硬化性樹脂（ｂ）がレゾルシンジグリシジルエーテルとアクリル酸の反応生成物である上記（１）〜（６）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
（９） 更に（ｅ）エポキシ樹脂、（ｆ）熱硬化剤を含有する上記（１）〜（８）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
（１０） 更に（ｇ）シランカップリング剤を含む、上記（１）〜（９）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
（１１） 更に（ｈ）無機フィラーを含有する上記（１）〜（１０）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
（１２） 液晶シール剤の全体に対して、前記光増感剤（ａ）を０．０１〜５質量％および前記硬化性樹脂（ｂ）を３０〜８０質量％含む上記（１）に記載の液晶滴下工法用液晶シール剤。(4) The liquid crystal sealant for a liquid crystal dropping method according to any one of (1) to (3), further comprising (c) a tertiary amine compound.
(5) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of (1) to (4), further comprising (d) a photopolymerization initiator.
(6) The liquid crystal sealing agent for a liquid crystal dropping method according to the above (5), wherein the photopolymerization initiator (d) is a photopolymerization initiator having a (meth) acryl group in the molecule.
(7) The liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said (1)-(6) whose said curable resin (b) is epoxy (meth) acrylate.
(8) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above (1) to (6), wherein the curable resin (b) is a reaction product of resorcin diglycidyl ether and acrylic acid.
(9) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of (1) to (8), further comprising (e) an epoxy resin and (f) a thermosetting agent.
(10) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of (1) to (9), further including (g) a silane coupling agent.
(11) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of (1) to (10), further comprising (h) an inorganic filler.
(12) The liquid crystal sealant according to (1), wherein the photosensitizer (a) is 0.01 to 5% by mass and the curable resin (b) is 30 to 80% by mass with respect to the entire liquid crystal sealant. Liquid crystal sealant for liquid crystal dropping method.
（１３） 更に、（ｄ）光重合開始剤を０．０１〜５質量％含む上記（１２）に記載の液晶滴下工法用液晶シール剤。
（１４） 更に、（ｅ）エポキシ樹脂を１〜３０質量％および（ｆ）熱硬化剤をエポキシ樹脂のエポキシ基1当量に対して、０．５〜２当量含有する上記（１２）または（１３）に記載の液晶滴下工法用液晶シール剤。
（１５） 更に（ｇ）シランカップリング剤を０．０５〜３質量％および（ｈ）無機フィラーを１０〜６０質量％含有する上記（１２）〜（１４）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
（１６） 更に（ｃ）３級アミン化合物を０〜６質量％含有する上記（１２）〜（１５）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
（１７） 上記１乃至１６の何れか１項に記載の液晶滴下工法用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。(13) The liquid crystal sealing agent for a liquid crystal dropping method according to the above (12), further comprising (d) 0.01 to 5% by mass of a photopolymerization initiator.
(14) The above (12) or (13) further comprising (e) 1 to 30% by mass of an epoxy resin and (f) 0.5 to 2 equivalents of a thermosetting agent with respect to 1 equivalent of an epoxy group of the epoxy resin. Liquid crystal sealing agent for liquid crystal dropping method as described in).
(15) The liquid crystal according to any one of (12) to (14), further comprising (g) 0.05 to 3% by mass of a silane coupling agent and (h) 10 to 60% by mass of an inorganic filler. Liquid crystal sealant for dripping method.
(16) The liquid crystal sealant for a liquid crystal dropping method according to any one of (12) to (15), further containing (c) a tertiary amine compound in an amount of 0 to 6% by mass.
(17) A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent for a liquid crystal dropping method according to any one of 1 to 16 above.
本発明の液晶シール剤は、液晶汚染が少なく、かつ、可視光等の低エネルギー光でも良好な硬化性を有する。従って、直射光の届き難い配線下においても充分な硬化性を有し、直接紫外線が照射されない遮光部も広い幅で硬化でき、配線等で陰になっても、均一に硬化が可能である。この為パネルの配線設計の自由度や、可視光照射といった工程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る。
The liquid crystal sealant of the present invention has little liquid crystal contamination and has good curability even with low energy light such as visible light. Therefore, it has sufficient curability even under the wiring where direct light is difficult to reach, and the light-shielding portion that is not directly irradiated with ultraviolet rays can be cured with a wide width, and even when it is shaded by the wiring, it can be cured uniformly. For this reason, it is possible to secure the degree of freedom of the wiring design of the panel and the degree of freedom of the process of irradiation with visible light, and the manufacture of a highly reliable liquid crystal display panel can be facilitated.
図１は、遮光部硬化試験用サンプルの図であり、１−１〜１−３のそれぞれは、この試験用サンプルの硬化前の状態を上から見た図（１−１）、矢印の方向より紫外線を照射してシール剤を硬化させる時の状態の試験用サンプルを横から見た図（１−２）、および紫外線照射により液晶シール剤を硬化した後の液晶シール剤の硬化状況を示す図（１−３）である。 FIG. 1 is a view of a sample for light-shielding part curing test, and each of 1-1 to 1-3 is a view (1-1) of the state before curing of the test sample from the top (1-1), direction of an arrow Fig. 1-2 shows a side view of a test sample in a state where the sealing agent is cured by irradiating more ultraviolet rays, and shows a curing state of the liquid crystal sealing agent after curing the liquid crystal sealing agent by ultraviolet irradiation. It is a figure (1-3).
１−１ シール剤硬化前の遮光部硬化試験用サンプルを上から見た図
１ ブラックマトリックス基板
２ クロムメッキをエッチングした基板
３ エッチングした基板面上のクロムメッキ層
４ 液晶シール剤
１−２ 遮光部硬化試験用サンプルを横から見た図
１ ブラックマトリックス基板
２ クロムメッキをエッチングした基板
３ エッチングした基板上のクロムメッキ層
４ 液晶シール剤
UV 紫外線
１−３ シール剤硬化後の遮光部硬化試験用サンプルの液晶シール剤の硬化状況を示す図
５ 液晶シール剤の硬化部分
６ 液晶シール剤の未硬化部分
７ クロム層の下の遮光部において、液晶シール剤の硬化した部分1-1: Light-shielding part curing test sample before curing sealant seen from above FIG. 1
Fig. 5 shows the curing state of the liquid crystal sealant of the sample for the light-shielding part curing test after curing the UV ultraviolet ray 1-3. Cured
本発明において用いられる分子内に（メタ）アクリル基を有する光増感剤（ａ）は、（メタ）アクリル基を有し、光増感剤（ａ）として作用するものであれば何れも使用することが出来る。本発明の液晶シール剤においては、通常該光増感剤（ａ）は、後記する光重合開始剤（ｄ）と併用される。しかし、支障が無ければ、本発明の液晶シール剤は、光重合開始剤（ｄ）無しで、該光増感剤（ａ）を単独で含む液晶シール剤であってもよい。
（メタ）アクリル基を有する光増感剤（ａ）としては、例えば特開２００４−２２４９９３（ＪＰ２００４−２２４９９３ Ａ）に開示されている分子中に（メタ）アクリル基を有するチオキサントン化合物または特開２００８−１６４０（ＪＰ２００８−１６４０ Ａ）に開示されている４-アルコキシ−１−（２−（メタ）アクリルオキシアルコキシ）ナフタレン等を挙げることが出来る。
より具体的には特開２００４−２２４９９３に開示の化合物として、例えば1分子中にグリシジル基と（メタ）アクリル基の両者を有するグリシジル基含有（メタ）アクリレート化合物とチオキサントンカルボン酸の反応生成物を挙げることができる。例えば、グリシジル（メタ）アクリレートまたは２−グリシジルオキシプロピル（メタ）アクリレートとチオキサントンカルボン酸の反応生成物等を挙げることが出来る。具体的な化合物としてはチオキサントンカルボン酸の３−（メタ）アクリルオキシ−２−ヒドロキシプロピルエステルまたはチオキサントンカルボン酸の２−（３−アクリルオキシ−２−ヒドロキシプロポキシ）プロピルエステルなどを挙げることが出来る。これらの中で、チオキサントンカルボン酸の３−（メタ）アクリルオキシ−２−ヒドロキシプロピルエステルはより好ましい。
特開２００８−１６４０に開示されている４-アルコキシ−１−（２−（メタ）アクリルオキシアルコキシ）ナフタレンとしては、４−Ｃ１ーＣ４アルコキシ−１−（２−（メタ）アクリルオキシ−２−Ｒ１−エトキシ）ナフタレン（Ｒ１は水素原子またはＣ１−Ｃ２アルキル基を表す）が好ましい。
なお、本明細書に置いて、「（メタ）アクリル」の用語は「アクリル」（ＣＨ２＝ＣＨ２ＣＯ−）及び／又は「メタクリル」（ＣＨ（ＣＨ３）＝ＣＨ２ＣＯ−）を意味する。Any photosensitizer (a) having a (meth) acryl group in the molecule used in the present invention may be used as long as it has a (meth) acryl group and acts as a photosensitizer (a). I can do it. In the liquid crystal sealing agent of the present invention, the photosensitizer (a) is usually used in combination with a photopolymerization initiator (d) described later. However, if there is no hindrance, the liquid crystal sealant of the present invention may be a liquid crystal sealant containing the photosensitizer (a) alone without the photopolymerization initiator (d).
As the photosensitizer (a) having a (meth) acryl group, for example, a thioxanthone compound having a (meth) acryl group in a molecule disclosed in JP-A-2004-224993 (JP 2004-224993 A) or JP-A-2008 4-alkoxy-1- (2- (meth) acryloxyalkoxy) naphthalene and the like disclosed in -1640 (JP2008-1640 A).
More specifically, as a compound disclosed in JP-A-2004-224993, for example, a reaction product of a glycidyl group-containing (meth) acrylate compound having both a glycidyl group and a (meth) acryl group in one molecule and a thioxanthone carboxylic acid. Can be mentioned. For example, a reaction product of glycidyl (meth) acrylate or 2-glycidyloxypropyl (meth) acrylate and thioxanthonecarboxylic acid can be used. Specific examples of the compound include 3- (meth) acryloxy-2-hydroxypropyl ester of thioxanthone carboxylic acid or 2- (3-acryloxy-2-hydroxypropoxy) propyl ester of thioxanthone carboxylic acid. Of these, 3- (meth) acryloxy-2-hydroxypropyl ester of thioxanthonecarboxylic acid is more preferable.
As 4-alkoxy-1- (2- (meth) acryloxyalkoxy) naphthalene disclosed in JP-A-2008-1640, 4-C1-C4 alkoxy-1- (2- (meth) acryloxy-2- R 1 - ethoxy) naphthalene (R 1 represents a hydrogen atom or a C1-C2 alkyl group).
In the present specification, the term “(meth) acryl” means “acryl” (CH 2 ═CH 2 CO—) and / or “methacryl” (CH (CH 3 ) ═CH 2 CO—). To do.
（メタ）アクリル基を有する光増感剤（ａ）としてより好ましい化合物としては、例えば下記式（１）、（２）、（３）で表される化合物等が挙げられる。
なお、上記式（１）で表される化合物は、特開２００４−２２４９９３公報に記載の方法にて製造して得ることができる。また、上記式（２）、（３）で表される化合物は、特開２００８−１６４０公報に記載の方法で製造することができる。
通常、光増感剤は低エネルギーの光であっても有効に、光重合開始剤のラジカルの発生を助ける事ができる。しかし、通常の光増感剤は液晶に対して汚染性を有し、液晶シール剤を構成する成分としては使用困難である。しかしながら、本発明においては、分子内に光反応性基、特に（メタ）アクリル基を有する光増感剤を使用することによって、液晶汚染を防止する事ができることを見出したもので、該（メタ）アクリル基を有する光増感剤は硬化物に取り込まれることにより液晶汚染を防止する事ができると考えられる。
この分子内に（メタ）アクリル基を有する光増感剤（ａ）の含有量としては本発明の液晶シール剤の全体を１００質量％とした場合、０．０１質量％から５質量％が好ましく、より好ましくは０．１質量％から３質量％であり、更に好ましくは０．７〜３質量％である。In addition, the compound represented by the said Formula (1) can be manufactured and obtained by the method of Unexamined-Japanese-Patent No. 2004-224993. Moreover, the compounds represented by the above formulas (2) and (3) can be produced by the method described in JP-A-2008-1640.
Usually, the photosensitizer can effectively assist the generation of radicals of the photopolymerization initiator, even with low energy light. However, ordinary photosensitizers are contaminated with liquid crystals and are difficult to use as components constituting liquid crystal sealants. However, in the present invention, it has been found that liquid crystal contamination can be prevented by using a photosensitizer having a photoreactive group, particularly a (meth) acryl group, in the molecule. ) It is considered that the photosensitizer having an acrylic group can prevent liquid crystal contamination by being taken into the cured product.
The content of the photosensitizer (a) having a (meth) acryl group in the molecule is preferably 0.01% by mass to 5% by mass when the entire liquid crystal sealant of the present invention is 100% by mass. More preferably, the content is from 0.1% by mass to 3% by mass, and even more preferably from 0.7 to 3% by mass.
また、本発明で用いられる光重合開始剤（ｄ）は、ラジカル型重合開始剤であれば特に限定されない。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、または国際公開ＷＯ２００６／０２７９８２パンフレット記載の下記式（Ａ）で表される（メタ）アクリル基を有する光重合開始剤を挙げることができる。
式（Ａ）
上記Ｒ１またはＲ２としてはＣ１−Ｃ４アルキレン基が好ましい。 Moreover, the photoinitiator (d) used by this invention will not be specifically limited if it is a radical type polymerization initiator. For example, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2- Examples include morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or a photopolymerization initiator having a (meth) acrylic group represented by the following formula (A) described in International Publication WO2006 / 027982. be able to.
Formula (A)
R 1 or R 2 is preferably a C1-C4 alkylene group.
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光重合開始剤を使用する事が好ましい。例えば好ましい光重合開始剤として、下記式（Ａ’）で表されるものを挙げることが出来る。
この化合物は国際公開ＷＯ２００６／０２７９８２パンフレット記載の方法にて製造することができる。上記式（Ａ’）で表される好ましい化合物としては、上記式において、Ｒがメチル基、Ｘ及びＹが酸素原子、Ｚがヒドロキシ基である化合物を挙げることができる。該化合物は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−オンとの反応で得ることができる。From the viewpoint of liquid crystal contamination, it is preferable to use a photopolymerization initiator having a (meth) acryl group in the molecule. For example, preferable photopolymerization initiators include those represented by the following formula (A ′).
This compound can be produced by the method described in International Publication WO2006 / 027982 Pamphlet. Preferable compounds represented by the above formula (A ′) include compounds in which R is a methyl group, X and Y are oxygen atoms, and Z is a hydroxy group in the above formula. The compound can be obtained by reaction of 2-methacryloyloxyethyl isocyanate with 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one.
光重合開始剤（ｄ）の含有量としては本発明の液晶シール剤の全体を１００質量％とした場合、０．０１質量％から５質量％が好ましく、好ましくは０．１質量％から３質量％より好ましくは０．７〜３質量％である。少な過ぎると充分な硬化性を得る事ができず、また多過ぎると液晶に対する該開始剤での汚染が問題となることがある。 The content of the photopolymerization initiator (d) is preferably 0.01% by mass to 5% by mass, preferably 0.1% by mass to 3% by mass, when the total liquid crystal sealant of the present invention is 100% by mass. % Is more preferably 0.7 to 3% by mass. If the amount is too small, sufficient curability cannot be obtained. If the amount is too large, contamination of the liquid crystal with the initiator may be a problem.
本発明の液晶シール剤は（メタ）アクリル基を有する硬化性樹脂（ｂ）を含有する。例えば（メタ）アクリルエステル、エポキシ（メタ）アクリレート等が挙げられる。（メタ）アクリルエステルとしては、ベンジルメタクリレート、シクロヘキシルメタクリレート、グリセロールジメタクリレート、グリセロールトリアクリレート、ＥＯ変性グリセロールトリアクリレート、ペンタエリスリトールアクリレート、トリメチロールプロパントリアクリレート、トリス（アクリロキシエチル）イソシアヌレート、ジペンタエリスリトールヘキサアクリレート、フロログリシノールトリアクリレート等が挙げられる。エポキシ（メタ）アクリレートは、エポキシ樹脂と（メタ）アクリル酸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、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、より好ましいものはレゾルシンジグリシジルエーテルである。また、エポキシ基と（メタ）アクリ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。
また、（メタ）アクリル基を有する硬化性樹脂（ｂ）の液晶シール剤中に占める含有率は、通常３０〜８０質量％程度であり、好ましくは４０〜７０質量％程度である。The liquid crystal sealing agent of the present invention contains a curable resin (b) having a (meth) acryl group. For example, (meth) acrylic ester, epoxy (meth) acrylate, etc. are mentioned. (Meth) acrylic esters include benzyl methacrylate, cyclohexyl methacrylate, glycerol dimethacrylate, glycerol triacrylate, EO-modified glycerol triacrylate, pentaerythritol acrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol. Examples include hexaacrylate and phloroglucinol triacrylate. Epoxy (meth) acrylate is obtained by a known method by reaction of an epoxy resin and (meth) acrylic acid. 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 novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin , Isocyanurate type epoxy resins, phenol novolac type epoxy resins having a triphenolmethane skeleton, and other difunctional phenolic diglycidyl esters such as catechol and resorcinol Ether compound, bi-functional alcohol diglycidyl ethers of, and their halides, and the like hydrogenated product. Among these, from the viewpoint of liquid crystal contamination, more preferred is resorcin diglycidyl ether. Moreover, the ratio of an epoxy group and a (meth) acryl group is not limited, and is appropriately selected from the viewpoint of process compatibility and liquid crystal contamination.
Moreover, the content rate which occupies in the liquid-crystal sealing compound of the curable resin (b) which has a (meth) acryl group is about 30-80 mass% normally, Preferably it is about 40-70 mass%.
本発明の液晶シール剤は、成分（ｃ）３級アミン化合物を含んでも良く、該３級アミン化合物を含むことにより遮光部の硬化性の更なる向上を図ることができる。
ここで３級アミン化合物とは、アンモニアの水素原子が３つとも炭化水素基で置換された化合物であり、例えば下記式（４）に例示する化合物が挙げられる。
式（４）中、Ｚ1〜Ｚ3はそれぞれ独立に、Ｃ１−Ｃ４アルキル基、ヒドロキシＣ１−Ｃ４アルキル基、ヒドロキシＣ１−Ｃ４アルコキシＣ１−Ｃ４アルキル基、グリシジル基、アクリルオキシＣ１〜Ｃ４アルキル基、または、置換基としてＣ１〜Ｃ６アルコキシカルボニル基またはＣ１〜Ｃ３アルキル基を有してもよい芳香環基（好ましくはＣ６〜Ｃ１０芳香環基、更に好ましくはフェニル基）を表わす。
上記Ｃ１−Ｃ４アルキル基の例としては、メチル、エチル等が挙げられる。同様に、上記ヒドロキシＣ１−Ｃ４アルキル基の例としては、ヒドロキシメチル、ヒドロキシエチル、３−ヒドロキシプロピル、２−ヒドロキシプロピル、４−ヒドロキシブチル、３−ヒドロキシブチル、２−ヒドロキシブチル等が挙げられる。同様に、上記ヒドロキシＣ１−Ｃ４アルコキシＣ１−Ｃ４アルキル基の例としては、ヒドロキシエトキシメチル、２−ヒドロキシエトキシエチル、３−（ヒドロキシエトキシ）プロピル、３−（ヒドロキシエトキシ）ブチル、２−（ヒドロキシエトキシ）ブチル等が挙げられる。上記の芳香環基としては、ナフチル基、フェニル基、Ｃ１−Ｃ３アルキル置換フェニル基、Ｃ１〜Ｃ６アルコキシカルボニル置換フェニル基等を挙げることが出来る。The liquid crystal sealant of the present invention may contain a component (c) a tertiary amine compound, and by containing the tertiary amine compound, the curability of the light shielding part can be further improved.
Here, the tertiary amine compound is a compound in which all three hydrogen atoms of ammonia are substituted with hydrocarbon groups, and examples thereof include compounds exemplified in the following formula (4).
In formula (4), Z 1 to Z 3 are each independently a C1-C4 alkyl group, a hydroxy C1-C4 alkyl group, a hydroxy C1-C4 alkoxy C1-C4 alkyl group, a glycidyl group, an acryloxy C1-C4 alkyl group. Or an aromatic ring group (preferably a C6-C10 aromatic ring group, more preferably a phenyl group) which may have a C1-C6 alkoxycarbonyl group or a C1-C3 alkyl group as a substituent.
Examples of the C1-C4 alkyl group include methyl, ethyl and the like. Similarly, examples of the hydroxy C1-C4 alkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. Similarly, examples of the hydroxy C1-C4 alkoxy C1-C4 alkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, 3- (hydroxyethoxy) butyl, 2- (hydroxyethoxy ) Butyl and the like. Examples of the aromatic ring group include a naphthyl group, a phenyl group, a C1-C3 alkyl-substituted phenyl group, a C1-C6 alkoxycarbonyl-substituted phenyl group, and the like.
Ｚ1〜Ｚ3のいずれか1つが、芳香環である化合物は好ましい化合物の1つである。例えばＺ1〜Ｚ3のいずれか1つが上記したＣ１〜Ｃ６アルコキシカルボニル基またはＣ１〜Ｃ３アルキル基等の置換基を有してもよい芳香環基（好ましくはＣ６〜Ｃ１０芳香環基、更に好ましくはフェニル基）である化合物は好ましい。特に光重合促進剤として作用する化合物は好適である。具体的には、ＫＡＹＡＣＵＲＥＴＲＭ ＤＭＢＩ、ＫＡＹＡＣＵＲＥＴＲＭ ＥＰＡ（いずれも日本化薬株式会社製）等は市販品として市場より入手可能である。
更に、当該３級アミン化合物による液晶汚染を防止する観点から、分子内にアクリル基、エポキシ基といった反応性基を有することも好ましい態様である。この化合物としては、例えばＮ，Ｎ−ジグリシジル−ｏ−トルイジン（ＧＯＴ：日本化薬株式会社製）等が挙げられる。
以上から、より好ましい化合物としては、上記式（４）におけるＺ1〜Ｚ3の２つがＣ１−Ｃ３アルキル基、またはグリシジル基、残りの1つがＣ１〜Ｃ６アルコキシカルボニル基またはＣ１〜Ｃ３アルキル基等の置換基を有してもよいフェニル基である。A compound in which any one of Z 1 to Z 3 is an aromatic ring is one of preferred compounds. For example, any one of Z 1 to Z 3 may have an aromatic ring group (preferably a
Furthermore, from the viewpoint of preventing liquid crystal contamination by the tertiary amine compound, it is also a preferred embodiment to have a reactive group such as an acrylic group or an epoxy group in the molecule. Examples of this compound include N, N-diglycidyl-o-toluidine (GOT: manufactured by Nippon Kayaku Co., Ltd.).
From the above, as a more preferable compound, two of Z 1 to Z 3 in the above formula (4) are a C1-C3 alkyl group or a glycidyl group, and the remaining one is a C1-C6 alkoxycarbonyl group or a C1-C3 alkyl group. This is a phenyl group which may have a substituent.
本発明の液晶シール剤では更にエポキシ樹脂（ｅ）を用いることにより、接着強度向上を図ることができる。用いられるエポキシ樹脂（ｅ）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（少なくとも２つのエポキシ基を有するエポキシ樹脂）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、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。これらのうち液晶汚染性の観点より好ましいのはビスフェノール型エポキシ樹脂またはノボラック型エポキシ樹脂である。場合により、ビスフェノール型エポキシ樹脂はより好ましく、ビスフェノールＡエポキシ樹脂はより好ましい。
該エポキシ樹脂（ｅ）の液晶シール剤中に占める含有量（液晶シール剤全体に対する含有割合：以下同じ）は、１〜３０質量％程度、好ましくは７〜３０質量％である。In the liquid crystal sealing agent of the present invention, the adhesive strength can be improved by further using the epoxy resin (e). The epoxy resin (e) used is not particularly limited, but is preferably a bifunctional or higher epoxy resin (an epoxy resin having at least two epoxy groups), for example, a bisphenol A type epoxy resin or a bisphenol F type epoxy. Resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type Epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having triphenolmethane skeleton, other bifunctional Diglycidyl ethers of Nord acids, difunctional alcohols diglycidyl ethers of, and their halides, and the like hydrogenated product. Among these, bisphenol type epoxy resin or novolac type epoxy resin is preferable from the viewpoint of liquid crystal contamination. In some cases, bisphenol-type epoxy resins are more preferred, and bisphenol A epoxy resins are more preferred.
The content of the epoxy resin (e) in the liquid crystal sealant (content ratio relative to the entire liquid crystal sealant: the same applies hereinafter) is about 1 to 30% by mass, preferably 7 to 30% by mass.
本発明の液晶シール剤で用いられる熱硬化剤（ｆ）は特に限定されるものではないが、固形の有機酸ヒドラジドが好適に用いられる。例えば、芳香族ヒドラジドであるサリチル酸ヒドラジド、安息香酸ヒドラジド、１−ナフトエ酸ヒドラジド、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バリンヒダントイン骨格を有するジヒドラジド類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２官能であるジヒドラジドであり、より好ましくは、Ｃ３−Ｃ６炭化水素上に２つのカルボキシ基を有するジカルボン酸のジヒドラジドが好ましい。更に好ましくはアジピン酸ジヒドラジドまたはイソフタル酸ジヒドラジドである。また、場合により、アジピン酸ジヒドラジドが更に好ましい。かかる熱硬化剤（ｆ）を使用する場合、エポキシ樹脂(ｅ)のエポキシ基のエポキシ当量を１とした場合、通常０．５〜２．０当量程度であり、好ましくは０．８〜１．２当量程度である。The thermosetting agent (f) used in the liquid crystal sealant of the present invention is not particularly limited, but solid organic acid hydrazide is preferably used. For example, the aromatic hydrazide salicylic acid hydrazide, benzoic acid hydrazide, 1-naphthoic acid hydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzene Examples include trihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide and the like. 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) And dihydrazides having a valine hydantoin skeleton such as ethyl) -5-isopropylhydantoin.
The dihydrazide is preferably a bifunctional dihydrazide from the balance of curing reactivity and latency, and more preferably a dihydrazide of a dicarboxylic acid having two carboxy groups on a C3-C6 hydrocarbon. More preferred is adipic acid dihydrazide or isophthalic acid dihydrazide. In some cases, adipic acid dihydrazide is more preferable. When using this thermosetting agent (f), when the epoxy equivalent of the epoxy group of an epoxy resin (e) is set to 1, it is about 0.5-2.0 equivalent normally, Preferably it is 0.8-1. About 2 equivalents.
本発明の液晶シール剤ではシランカップリング剤（ｇ）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。グリシドキシプロピルトリＣ１〜Ｃ３アルコキシシランまたはグリシドキシプロピルＣ１〜Ｃ３アルキルジＣ１〜Ｃ３アルコキシシラン等が好ましい。シランカップリング剤（ｇ）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全体を１００質量％とした場合、０．０５〜３質量％が好適である。 In the liquid crystal sealing agent of the present invention, the silane coupling agent (g) can be used to improve the adhesive strength and 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. Glycidoxypropyl tri-C1 to C3 alkoxysilane or glycidoxypropyl C1 to C3 alkyldiC1 to C3 alkoxysilane is preferable. The content of the silane coupling agent (g) in the liquid crystal sealant is preferably 0.05 to 3% by mass when the entire liquid crystal sealant of the present invention is 100% by mass.
本発明の液晶シール剤では無機フィラー（ｈ）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。この無機フィラー（ｈ）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、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）により測定することができる。 In the liquid crystal sealing agent of the present invention, the inorganic filler (h) can be used to improve the adhesive strength and improve the moisture resistance reliability. Examples of the inorganic filler (h) include 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 inability to form a gap when the upper and lower glass substrates are bonded together when manufacturing a narrow gap liquid crystal cell. Therefore, 3 μm or less is appropriate, and preferably 2 μm or less. . The particle size can be measured by 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（ｈ）の液晶シール剤中の含有量は、本発明の液晶シール剤の全体を１００質量％とした場合、通常１０〜６０質量％、好ましくは２０〜５０質量％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場合、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 (h) that can be used in the liquid crystal sealant of the present invention in the liquid crystal sealant is usually 10 to 60% by mass, preferably 100% by mass, preferably 100% by mass. It is 20-50 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には、さらに必要に応じて、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。
本発明の好ましい液晶シール剤をまとめると次の通りである。
１．前記光増感剤（ａ）を０．０１〜５質量％および前記硬化性樹脂（ｂ）を３０〜８０質量％含み、残部として、（ｄ）光重合開始剤、（ｅ）エポキシ樹脂と（ｆ）熱硬化剤、および（ｇ）シランカップリング剤からなる群から選ばれる少なくとも１種を含む液晶シール剤。
２．（ｄ）光重合開始剤を０．０１〜５質量％含む上記１に記載の液晶シール剤。
３．（ｅ）エポキシ樹脂を１〜３０質量％および（ｆ）熱硬化剤をエポキシ樹脂のエポキシ基1当量に対して、０．５〜２当量の割合で含有する上記１または２に記載の液晶シール剤。
４．（ｇ）シランカップリング剤を０．０５〜３質量％含有する上記１〜３の何れか一項に記載の液晶シール剤。
５．（ｈ）無機フィラーを１０〜６０質量％含有する上記１〜４の何れか一項に記載の液晶シール剤。
６．更に（ｃ）３級アミン化合物を０〜６質量％、好ましくは０．１〜５質量％含有する上記１〜５の何れか一項に記載の液晶シール剤。
７．前記光増感剤（ａ）が、チオキサントンカルボン酸とグリシジル（メタ）アクリレート化合物との反応生成物または４−Ｃ１ーＣ４アルコキシ−１−（２−（メタ）アクリルオキシ−２−Ｒ１−エトキシ）ナフタレン（Ｒ１は水素原子またはＣ１ーＣ２アルキル基を表す）である上記１〜６の何れか一項に記載の液晶シール剤。
８．前記光増感剤（ａ）が、前記式（１）〜（３）で表される化合物からなる群から選ばれる少なくとも１つである上記１〜７の何れか一項に記載の液晶シール剤。
９．前記硬化性樹脂（ｂ）がエポキシ（メタ）アクリレートである上記１〜８の何れか一項に記載の液晶シール剤。If necessary, the liquid crystal sealant of the present invention may further contain additives such as organic fillers, pigments, leveling agents, antifoaming agents and solvents.
The preferred liquid crystal sealant of the present invention is summarized as follows.
1. The photosensitizer (a) is 0.01 to 5% by mass and the curable resin (b) is 30 to 80% by mass, with the remainder being (d) a photopolymerization initiator, (e) an epoxy resin and ( f) A liquid crystal sealing agent comprising at least one selected from the group consisting of a thermosetting agent and (g) a silane coupling agent.
2. (D) The liquid crystal sealing agent according to 1 above, containing 0.01 to 5% by mass of a photopolymerization initiator.
3. (E) 1 to 30% by mass of an epoxy resin and (f) a liquid crystal seal according to 1 or 2 containing a thermosetting agent in a proportion of 0.5 to 2 equivalents with respect to 1 equivalent of epoxy groups of the epoxy resin. Agent.
4). (G) Liquid crystal sealing agent as described in any one of said 1-3 which contains 0.05-3 mass% of silane coupling agents.
5. (H) The liquid crystal sealing agent according to any one of 1 to 4 above, containing 10 to 60% by mass of an inorganic filler.
6). Furthermore, (c) Liquid crystal sealing agent as described in any one of said 1-5 containing 0-6 mass%, preferably 0.1-5 mass% of tertiary amine compounds.
7). The photosensitizer (a) is a reaction product of thioxanthonecarboxylic acid and a glycidyl (meth) acrylate compound or 4-C1-C4 alkoxy-1- (2- (meth) acryloxy-2-R 1 -ethoxy ) naphthalene (R 1 is a liquid crystal sealing material according to any one of the above 1 to 6, a represents a hydrogen atom or a C1 over C2 alkyl group).
8). The liquid crystal sealant according to any one of the above 1 to 7, wherein the photosensitizer (a) is at least one selected from the group consisting of compounds represented by the formulas (1) to (3). .
9. The liquid crystal sealing agent according to any one of 1 to 8, wherein the curable resin (b) is an epoxy (meth) acrylate.
１０．エポキシ（メタ）アクリレートがレゾルシンジグリシジルエーテルと（メタ）アクリル酸との反応生成物である上記９に記載の液晶シール剤。
１１．（ｄ）光重合開始剤が前記式（Ａ’）で表される（メタ）アクリル基を有する重合開始剤である上記１〜１０の何れか一項に記載の液晶シール剤。
１２．（ｅ）エポキシ樹脂がビスフェノール型エポキシ樹脂またはノボラック型エポキシ樹脂である上記１〜１１の何れか一項に記載の液晶シール剤。
１３．（ｆ）熱硬化剤がジヒドラジドである上記１〜１２の何れか一項に記載の液晶シール剤。
１４．（ｃ）３級アミン化合物が前記式（４）におけるＺ1〜Ｚ3の２つがＣ１−Ｃ３アルキル基、またはグリシジル基、残りの1つが置換基としてＣ１〜Ｃ６アルコキシカルボニル基またはＣ１〜Ｃ３アルキル基を有してもよいフェニル基である３級アミンである上記６〜１３の何れか一項に記載の液晶シール剤。10. 10. The liquid crystal sealant according to 9 above, wherein the epoxy (meth) acrylate is a reaction product of resorcin diglycidyl ether and (meth) acrylic acid.
11. (D) The liquid-crystal sealing compound as described in any one of 1 to 10 above, wherein the photopolymerization initiator is a polymerization initiator having a (meth) acryl group represented by the formula (A ′).
12 (E) The liquid crystal sealing agent according to any one of 1 to 11 above, wherein the epoxy resin is a bisphenol type epoxy resin or a novolac type epoxy resin.
13. (F) Liquid crystal sealing agent as described in any one of said 1-12 whose thermosetting agent is dihydrazide.
14 (C) The tertiary amine compound is a C1-C3 alkyl group or glycidyl group in which Z 1 to Z 3 in the formula (4) are two, and the remaining one is a C1-C6 alkoxycarbonyl group or C1-C3 alkyl as a substituent. The liquid crystal sealing agent according to any one of the above 6 to 13, which is a tertiary amine which is a phenyl group which may have a group.
本発明の液晶シール剤は次の様にして得ることができる。
まず（ｂ）成分に、必要に応じ、エポキシ樹脂（ｅ）および／またはシランカップリング剤（ｇ）を溶解混合する。次いで、そこに光増感剤（ａ）及び、必要に応じ、光重合開始剤（ｄ）を溶解し、更に、そこに、必要に応じ、熱硬化剤（ｆ）、および／または無機充填剤（ｈ）、並びに、必要に応じ有機フィラー、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、金属メッシュ等で、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。The liquid crystal sealant of the present invention can be obtained as follows.
First, the epoxy resin (e) and / or the silane coupling agent (g) are dissolved and mixed in the component (b) as necessary. Next, the photosensitizer (a) and, if necessary, the photopolymerization initiator (d) are dissolved therein, and further, if necessary, a thermosetting agent (f) and / or an inorganic filler. (H) and, if necessary, an organic filler, an antifoaming agent, a leveling agent, a solvent and the like are added, and uniformly mixed by a known mixing device such as a three roll, sand mill, ball mill, etc. The liquid crystal sealant of the present invention can be produced by filtration.
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ー（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、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、紫外線照射機により液晶シール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。スペーサーとしては、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％に対し通常０．１〜４質量％、好ましくは０．５〜２質量％、更に、好ましくは０．９〜１．５質量％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. After that, the liquid crystal is dropped inside the weir of the liquid crystal sealing agent, and the other glass substrate is overlaid in a vacuum to create a gap. After forming the gap, the liquid crystal seal portion is irradiated with ultraviolet rays by an ultraviolet irradiator to be 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 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, polymer beads and the like. 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% by mass, preferably 0.5 to 2% by mass, and more preferably about 0.9 to 1.5% by mass with respect to 100% by mass of the liquid crystal sealant of the present invention. is there.
以下実施例により本発明を更に詳細に説明する。実施例において部は質量部を、％は質量％をそれぞれ意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. In Examples, “part” means “part by mass”, and “%” means “% by mass”.
実施例１〜６、比較例１〜２
（液晶滴下工法用のシール剤の調製）
下記表１に示す割合で各樹脂成分を混合攪拌した後、光増感剤（ａ）、光重合開始剤（ｄ）、必要に応じて、第３級アミンを加熱溶解させた。その後、必要に応じて、シランカップリング剤（ｇ）、無機フィラー（ｈ）、熱硬化剤（ｆ）等を適宜添加し、攪拌した後、３本ロールミルにて分散させた後、金属メッシュで濾過し、液晶滴下工法用シール剤実施例１〜６、比較例１〜２を調製した。Examples 1-6, Comparative Examples 1-2
(Preparation of sealant for liquid crystal dropping method)
After mixing and stirring each resin component in the ratio shown in Table 1 below, the photosensitizer (a), the photopolymerization initiator (d), and, if necessary, a tertiary amine were dissolved by heating. Thereafter, if necessary, a silane coupling agent (g), an inorganic filler (h), a thermosetting agent (f), etc. are added as appropriate, and after stirring, the mixture is dispersed with a three-roll mill, and then a metal mesh is used. Filtration was performed to prepare sealants Examples 1 to 6 and Comparative Examples 1 and 2 for a liquid crystal dropping method.
以下に、調製した各液晶滴下工法用シール剤の評価項目の内容とその結果の一部を示し、表１に全ての結果を示す。 Below, the contents of the evaluation items of each prepared liquid crystal dropping method sealing agent and some of the results are shown, and Table 1 shows all the results.
液晶汚染性試験
それぞれの１０ｍｌバイアル瓶の底に、３０００ｍＪ／ｃｍ2の紫外線を照射した後の各液晶滴下工法用シール剤を１００ｍｇ程度塗布した。次いで、そこに、液晶（ＭＬＣ−６８６６−１００：メルク株式会社製）を、塗布した各シール剤の１０倍量加えた。得られたバイアル瓶を加熱して、１２０℃で１時間保持した後、室温になるまで、３０分冷却した。それぞれの上澄み（液晶）をデカンテーションにて分け取り、デジタル超高抵抗計（Ｒ８３４０：株式会社アドバンテスト製）にて電気抵抗値を測定し、シール剤なしのものの値に対する比抵抗値で、以下の基準により判定を行った。
○ １．０Ｅ＋１２以上
△ １．０Ｅ＋１１以上１．０Ｅ＋１２未満
× １．０Ｅ＋１１未満
なお、比抵抗値の「１．０Ｅ＋１２」は「１．０×１０12」を表し、他の記載も同様である。
各実施例における比抵抗値は、それぞれ、下記の通りであった。
実施例１：２．１Ｅ＋１２、実施例２：１．６Ｅ＋１２、実施例３：１．８Ｅ＋１２、実施例４：７．３Ｅ＋１１、実施例５：２．３Ｅ＋１２、実施例６：６．２Ｅ＋１１Liquid Crystal Contamination Test About 100 mg of each sealing agent for liquid crystal dropping method after irradiating 3000 mJ / cm 2 ultraviolet rays was applied to the bottom of each 10 ml vial. Next, 10 times the amount of each applied sealing agent was added to the liquid crystal (MLC-6866-100: manufactured by Merck Ltd.). The obtained vial was heated and held at 120 ° C. for 1 hour, and then cooled for 30 minutes until it reached room temperature. Each supernatant (liquid crystal) is separated by decantation, and the electrical resistance value is measured with a digital ultrahigh resistance meter (R8340: manufactured by Advantest Co., Ltd.). Judgment was made based on the criteria.
○ 1.0E + 12 or more Δ 1.0E + 11 or more and less than 1.0E + 12 × less than 1.0E + 11 The specific resistance value “1.0E + 12” represents “1.0 × 10 12 ”, and the other descriptions are also the same.
The specific resistance values in the respective examples were as follows.
Example 1: 2.1E + 12, Example 2: 1.6E + 12, Example 3: 1.8E + 12, Example 4: 7.3E + 11, Example 5: 2.3E + 12, Example 6: 6.2E + 11
遮光部硬化性試験
クロムメッキをしたガラス基板のクロムメッキを、中央に１本線（幅０．８ｃｍ）を残してエッチングしたガラス基板を用いて、それぞれの基板の中央に、各液晶シール剤（表１に示す組成のものに５μｍのグラスファイバーを１ｗ％添加したもの）を円形に塗付し、対向基板としてブラックマトリックス基板を用いて貼りあわせ、クリップで固定し、図１の１−１に示す遮光部硬化性試験用サンプルを作成した。この試験用サンプルのそれぞれに、クロムをエッチングしたガラス基板側から、３０００ｍＪ／ｃｍ2の紫外線を照射し、シール剤を硬化した（図１の１−２）。その後、貼り合わせたブラックマトリックスを剥がし、クロムの下で遮光されていた部分を顕微鏡で観察し、遮光部の硬化幅を測定した。Light-shielding part curability test Using a glass substrate etched with chrome plating on a chrome-plated glass substrate leaving a single line (width 0.8 cm) in the center, each liquid crystal sealant (
接着強度試験
液晶シール剤１００ｇにスペーサーとして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の紫外線を照射した後、１２０℃オーブンに１時間投入して硬化させた。その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。Adhesive strength test 1 g of 5 μm glass fiber is added as a spacer to 100 g of liquid crystal sealant, and mixed and stirred. After applying this liquid crystal sealing agent on a 50 mm × 50 mm glass substrate, bonding a 1.5 mm × 1.5 mm glass piece on the liquid crystal sealing agent, and irradiating 3000 mJ / cm 2 of ultraviolet rays with a UV irradiator, It was cured by putting it in a 120 ° C. oven 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.).
以上のように本発明の液晶シール剤は、直接紫外線が届かない遮光部において、漏れ光の様な弱いエネルギーの光でも良好な硬化性を有し、これにより液晶パネル設計の幅を広げられる上、高い信頼性を保証する事ができる。 As described above, the liquid crystal sealant of the present invention has good curability even in light of weak energy such as leaked light in a light shielding portion where direct ultraviolet rays do not reach, thereby widening the range of liquid crystal panel design. High reliability can be guaranteed.
本発明の液晶シール剤は液晶汚染が少なく、かつ、直接紫外線が届かない遮光部をもかなりの幅で硬化できることから、配線の陰で紫外線等が直接当たらなくなる部分ができても、充分にシール剤を一様に硬化でき、かつ、硬化後のシール剤の接着強度も優れることから、液晶のシール剤として非常に有用である。 Since the liquid crystal sealant of the present invention is less contaminated with liquid crystal and can cure the light-shielding part where ultraviolet rays do not reach with a considerable width, even if there is a part where ultraviolet rays etc. are not directly exposed behind the wiring, it can seal well Since the agent can be uniformly cured and the adhesive strength of the cured sealant is also excellent, it is very useful as a liquid crystal sealant.
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| PCT/JP2011/003366 WO2012011220A1 (en) | 2010-07-20 | 2011-06-14 | Liquid crystal sealing agent and liquid crystal display cell using same |
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| WO2014010446A1 (en) * | 2012-07-11 | 2014-01-16 | 協立化学産業株式会社 | Curing agent and resin composition using same |
| TW201420735A (en) * | 2012-07-12 | 2014-06-01 | Nippon Kayaku Kk | Liquid crystal sealing agent and liquid crystal display cell using same |
| KR102256146B1 (en) * | 2013-12-05 | 2021-05-25 | 세키스이가가쿠 고교가부시키가이샤 | Polymerizable monomer, polymer compound, photocurable resin composition, sealing element for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| JP6259657B2 (en) * | 2013-12-24 | 2018-01-10 | 協立化学産業株式会社 | Sealant for liquid crystal display elements |
| JP6216260B2 (en) * | 2014-02-12 | 2017-10-18 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| 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 |
| CN104478265A (en) * | 2014-12-12 | 2015-04-01 | 宜兴天力化工纳米科技有限公司 | Calcium carbonate and silicon carbide complexing agent and preparation method thereof |
| WO2017002362A1 (en) * | 2015-06-30 | 2017-01-05 | 三井化学株式会社 | Photocurable resin composition, display element sealing agent, liquid crystal sealing agent, liquid crystal display panel and method for producing liquid crystal display panel |
| KR20190021467A (en) * | 2016-07-08 | 2019-03-05 | 헨켈 아게 운트 코. 카게아아 | A method of manufacturing a liquid crystal display and a curable resin composition used in the method |
| CN109661449B (en) * | 2016-08-26 | 2022-01-18 | 夏普株式会社 | Sealing material composition, liquid crystal cell, and method for producing liquid crystal cell |
| CN106405946A (en) * | 2016-11-29 | 2017-02-15 | 深圳市华星光电技术有限公司 | Sealant curing method and liquid crystal panel manufacturing method |
| JP6486571B1 (en) * | 2017-06-06 | 2019-03-20 | 日本化薬株式会社 | Adhesive for electronic parts |
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| CN103003742A (en) | 2013-03-27 |
| WO2012011220A1 (en) | 2012-01-26 |
| JPWO2012011220A1 (en) | 2013-09-09 |
| TW201204749A (en) | 2012-02-01 |
| KR20130140544A (en) | 2013-12-24 |
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