JP2013015646A - 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
- JP2013015646A JP2013015646A JP2011147814A JP2011147814A JP2013015646A JP 2013015646 A JP2013015646 A JP 2013015646A JP 2011147814 A JP2011147814 A JP 2011147814A JP 2011147814 A JP2011147814 A JP 2011147814A JP 2013015646 A JP2013015646 A JP 2013015646A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- component
- epoxy resin
- 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.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 174
- 239000000565 sealant Substances 0.000 title claims abstract description 57
- 239000003822 epoxy resin Substances 0.000 claims abstract description 63
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims description 35
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000011109 contamination Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 5
- -1 1-hydrazinocarbonylmethyl Chemical group 0.000 description 19
- 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 19
- 239000000758 substrate Substances 0.000 description 18
- 210000004027 cell Anatomy 0.000 description 17
- 238000001723 curing Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 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 description 10
- 229920003986 novolac Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 150000008064 anhydrides Chemical class 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
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical group O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 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-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 2
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-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
- 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
- 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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 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
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 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
- 235000010354 butylated hydroxytoluene Nutrition 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
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 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
- 238000004090 dissolution Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229940091173 hydantoin Drugs 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin 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
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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
- 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
- ROFVGYAMRSGUSQ-UHFFFAOYSA-N 1-(2-bromoethyl)piperazine;hydrobromide Chemical compound Br.BrCCN1CCNCC1 ROFVGYAMRSGUSQ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 0 CC(C)(C)*(NN)=O Chemical compound CC(C)(C)*(NN)=O 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-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
- 229910000831 Steel Inorganic materials 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000007513 acids Chemical class 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
- 150000001298 alcohols Chemical class 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
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 230000008901 benefit Effects 0.000 description 1
- GPBKPJXNAVXOJU-UHFFFAOYSA-N benzene-1,2,4-tricarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C(C(=O)NN)=C1 GPBKPJXNAVXOJU-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
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 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
- 230000001588 bifunctional effect Effects 0.000 description 1
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- 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
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- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 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
- 238000010908 decantation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-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
- 238000005886 esterification reaction 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
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- OXAGUPFRAIIDLT-UHFFFAOYSA-N heptanedihydrazide Chemical compound NNC(=O)CCCCCC(=O)NN OXAGUPFRAIIDLT-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 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
- 229950000688 phenothiazine Drugs 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
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 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
- 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
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 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
- 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 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
- 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
-
- 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
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0647—Polyepoxides
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (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滴下工法用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滴下工法用液晶シール剤、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 sealant for a liquid crystal dropping method that has good curability by heat. More specifically, a liquid crystal sealant for liquid crystal dropping method having good curability by heat, excellent storage stability, and excellent moisture resistance of the cured product, and liquid crystal sealed with the cured product Regarding display cells.
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、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、これらの方法では、熱反応性は向上するものの、使用した熱ラジカル開始剤や硬化促進剤自体が液晶に溶出し、表示不良を引き起こすといった問題がある。また、カルボン酸のような高極性の官能基の存在は、シール剤硬化物の吸水性を上げ、その結果耐湿信頼性の低下といった問題を引き起こすことが知られている。更に、硬化促進剤の添加は、熱反応性を向上する反面、常温においても反応進行させる為、保存安定性を極度に低下させる。 However, in these methods, although the thermal reactivity is improved, there is a problem that the used thermal radical initiator or the curing accelerator itself elutes in the liquid crystal and causes display defects. In addition, it is known that the presence of a highly polar functional group such as carboxylic acid increases the water absorption of the cured sealant and as a result causes problems such as a decrease in moisture resistance reliability. Furthermore, the addition of a curing accelerator improves the thermal reactivity, but on the other hand, the reaction proceeds at room temperature, so that the storage stability is extremely lowered.
以上述べたように、液晶滴下工法用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もち、更には硬化物特性にも優れるといった液晶シール剤は未だ実現していない。 As mentioned above, despite the fact that the development of the liquid crystal sealant for the liquid crystal dropping method has been carried out very vigorously, it also has good storage stability while having excellent thermal reactivity, Furthermore, a liquid crystal sealant having excellent cured product properties has not yet been realized.
本発明は、加熱のみ、又は光熱併用によって硬化する液晶滴下工法用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 sealing agent for a liquid crystal dropping method which is cured only by heating or combined with light heat, and since the reaction by heat is fast, it is extremely low in contamination with liquid crystal throughout the process, and also in storage stability. The present invention proposes a liquid crystal sealing agent for a liquid crystal dropping method which is excellent in cured product characteristics such as moisture resistance reliability.
本発明者らは、鋭意検討の結果、カルボキシ基を有する特定の化合物を含有する液晶滴下工法用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、更には保存安定性や耐湿信頼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）〜１０）に関するものである。なお、本明細書中、全ての成分（ａ）について、「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種以上を含有する硬化性樹脂」と記載する煩雑さを避ける為、「成分（ａ）硬化性樹脂」又は単に「成分（ａ）」と記載する場合がある。
As a result of intensive studies, the present inventors have found that the liquid crystal sealing agent for a liquid crystal dropping method containing a specific compound having a carboxy group has excellent thermal reactivity, and as a result, it is possible to suppress liquid crystal contamination. Has been found to be excellent in storage stability and moisture resistance reliability, and has completed the present invention.
That is, the present invention relates to the following 1) to 10). In addition, in this specification, about all component (a), "curability containing 1 type (s) or 2 or more types selected from an epoxy resin, a (meth) acrylated epoxy resin, and a partial (meth) acrylated epoxy resin" In order to avoid complications described as “resin”, it may be described as “component (a) curable resin” or simply “component (a)”.
１）
（ａ）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種以上を含有する硬化性樹脂、（ｂ）熱硬化剤、（ｃ）分子内にカルボキシ基を有し、且つ酸価が５０〜２５０ｍｇＫＯＨ／ｇである化合物を含有することを特徴とする液晶滴下工法用液晶シール剤。
２）
上記成分（ｃ）の重量平均分子量が３０００〜１００００ｇ／ｍｏｌである上記１）に記載の液晶滴下工法用液晶シール剤。
３）
上記成分（ｃ）の含有量が成分（ａ）を１００質量部とした場合に、０．１〜２０質量部である上記１）又は２）に記載の液晶滴下工法用液晶シール剤。
４）
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３）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
５）
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４）に記載の液晶滴下工法用液晶シール剤。
で表される分子骨格を示す］
６）
前記成分（ａ）硬化性樹脂が、（メタ）アクリル化エポキシ樹脂及びエポキシ樹脂の混合物である上記１）乃至５）のいずれか一項に記載の液晶滴下工法用液晶シール剤。
７）
更に、成分（ｄ）シランカップリング剤を含有する、上記１）乃至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）
更に、成分（ｅ）無機フィラーを含有する上記１）乃至７）の何れか一項に記載の液晶滴下工法用液晶シール剤。
９）
更に、（ｆ）光重合開始剤を含有する上記１）乃至８）の何れか一項に記載の液晶滴下工法用液晶シール剤。
１０）
上記１）乃至９）の何れか一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。
1)
(A) a curable resin containing one or more selected from an epoxy resin, a (meth) acrylated epoxy resin and a partial (meth) acrylated epoxy resin, (b) a thermosetting agent, and (c) a molecule A liquid crystal sealing agent for a liquid crystal dropping method, comprising a compound having a carboxy group therein and an acid value of 50 to 250 mg KOH / g.
2)
The liquid-crystal sealing compound for liquid crystal dropping methods as described in said 1) whose weight average molecular weights of the said component (c) are 3000-10000 g / mol.
3)
The liquid crystal sealing agent for a liquid crystal dropping method according to 1) or 2), wherein the content of the component (c) is 0.1 to 20 parts by mass when the component (a) is 100 parts by mass.
4)
The liquid crystal sealing agent for a liquid crystal dropping method according to any one of 1) to 3), wherein the component (b) thermosetting agent is a polyhydric hydrazide compound.
5)
The liquid crystal sealing agent for liquid crystal dropping method according to 4), wherein the component (b) thermosetting agent is one or more hydrazide compounds represented by the following formula (1).
The molecular skeleton represented by
6)
The liquid crystal sealing agent for a liquid crystal dropping method according to any one of 1) to 5), wherein the component (a) curable resin is a mixture of a (meth) acrylated epoxy resin and an epoxy resin.
7)
Furthermore, the liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 1) thru | or 6) which contains a component (d) silane coupling agent.
8)
Furthermore, the liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 1) thru | or 7) containing a component (e) inorganic filler.
9)
Furthermore, (f) The liquid-crystal sealing compound for liquid crystal dropping methods as described in any one of said 1) thru | or 8) containing a photoinitiator.
10)
The liquid crystal display cell sealed with the hardened | cured material obtained by hardening | curing the liquid crystal sealing agent for liquid crystal dropping methods as described in any one of said 1) thru | or 9).
本発明の液晶滴下工法用液晶シール剤は、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 for the liquid crystal dropping method of the present invention has a fast reaction rate at the time of thermosetting, it has sufficient curability even under wiring where light is difficult to reach in the photothermal combined liquid crystal dropping method. The degree of freedom in wiring design can be secured, and a highly reliable liquid crystal display panel can be easily manufactured. Further, application to a liquid crystal dropping method in which a liquid crystal sealant is cured only by heat is possible.
本発明の液晶シール剤は、成分（ｃ）分子内にカルボキシ基を有し、且つ酸価が５０〜２５０ｍｇＫＯＨ／ｇである化合物を含有し、それによって熱反応性と保存安定性を両立することが可能となっている。この化合物が有するカルボキシ基は熱硬化促進剤として機能する。従って、酸化が５０ｍｇ未満の場合には十分な熱反応性が得られない。また、酸化が２５０ｍｇより大きい場合、分子の極性が大きくなり、硬化物の耐湿信頼性を劣化させる。この酸価としてより好ましくは５０〜１８０ｍｇＫＯＨ／ｇであり、更に好ましくは５０〜１００ｍｇＫＯＨ／ｇ、特に好ましくは６０〜１００ｍｇＫＯＨ／ｇである。なお、酸価は成分（ｃ）１ｇ中に存在するカルボン酸を中和するのに必要な水酸化カリウムのｍｇ数で定義する。 The liquid crystal sealant of the present invention contains component (c) a compound having a carboxy group in the molecule and an acid value of 50 to 250 mgKOH / g, thereby achieving both thermal reactivity and storage stability. Is possible. The carboxy group of this compound functions as a thermosetting accelerator. Therefore, when the oxidation is less than 50 mg, sufficient thermal reactivity cannot be obtained. Moreover, when oxidation is larger than 250 mg, the polarity of a molecule | numerator will become large and the moisture resistance reliability of hardened | cured material will deteriorate. The acid value is more preferably 50 to 180 mgKOH / g, still more preferably 50 to 100 mgKOH / g, and particularly preferably 60 to 100 mgKOH / g. The acid value is defined as the number of mg of potassium hydroxide required to neutralize the carboxylic acid present in 1 g of component (c).
また、成分（ｃ）は、重量平均分子量が３０００〜１００００ｇ／ｍｏｌであることが好ましい。重量平均分子量が小さすぎると、それ自体が液晶に溶解し、表示不良を引き起こす。また重量平均分子量が大きすぎると、他の成分との相溶性が悪くなり、熱反応促進効果が著しく減少する。この重量平均分子量として、更に好ましくは、４０００〜８０００ｇ／ｍｏｌである。 The component (c) preferably has a weight average molecular weight of 3000 to 10000 g / mol. If the weight average molecular weight is too small, it itself dissolves in the liquid crystal and causes display defects. On the other hand, if the weight average molecular weight is too large, the compatibility with other components is deteriorated, and the thermal reaction promoting effect is remarkably reduced. The weight average molecular weight is more preferably 4000 to 8000 g / mol.
成分（ｃ）は、成分（ａ）硬化性樹脂の総量を１００質量部とした場合に、０．１〜２０質量部含有することが好ましく、１〜１０質量部であることが特に好ましい。含有量が少な過ぎると十分な熱硬化性が得られず、また多過ぎると液晶シール剤が高粘度化する為、その他の成分の配合に制約を生じることになり、不適である。 The component (c) is preferably contained in an amount of 0.1 to 20 parts by mass, particularly preferably 1 to 10 parts by mass, when the total amount of the component (a) curable resin is 100 parts by mass. If the content is too small, sufficient thermosetting property cannot be obtained. If the content is too large, the liquid crystal sealant has a high viscosity, which is unsuitable because it imposes restrictions on the blending of other components.
成分（ｃ）の具体例としては、水酸基を有するエポキシ（メタ）アクリレートに酸無水物及び／又は多価カルボン酸（無水物を含む）を反応さて得られる化合物や、一種類以上の多価カルボン酸と一種類以上の多価アルコールを脱水縮合反応させて得られるポリエステル樹脂の末端アルコール性水酸基に、多価カルボン酸（無水物を含む）を反応させて得られる化合物等が挙げられる。水酸基を有するエポキシ（メタ）アクリレートに酸無水物や多価カルボン酸（無水物を含む）を反応さて得られる化合物は、例えば、特開平５−３２７４６号公報等に記載の方法で得る事が可能である。このうちビスフェノールＡ型エポキシ（メタ）アクリレートに酸無水物を反応させて得られる化合物が好ましい。また、一種類以上の多価カルボン酸と一種類以上の多価アルコールを脱水縮合反応させて得られるポリエステル樹脂の末端アルコール性水酸基に、多価カルボン酸（無水物を含む）を反応させて得られる化合物は、例えば、ユピカコートＧＶ２３０、ユピカコートＧＶ２５０という商品名（日本ユピカ株式会社）で市場より容易に入手することができる。このうち、ユピカコートＧＶ２３０（酸価５３ｍｇＫＯＨ／ｇ、重量平均分子量７９００ｇ／ｍｏｌ）、ユピカコートＧＶ２５０（酸価７４ｍｇＫＯＨ／ｇ、重量平均分子量５２００ｇ／ｍｏｌ）が好ましく用いられ、ユピカコートＧＶ２５０が特に好ましく用いられる。 Specific examples of the component (c) include a compound obtained by reacting an acid anhydride and / or a polyvalent carboxylic acid (including an anhydride) with an epoxy (meth) acrylate having a hydroxyl group, or one or more polyvalent carboxylic acids. Examples thereof include compounds obtained by reacting a terminal alcoholic hydroxyl group of a polyester resin obtained by subjecting an acid and one or more types of polyhydric alcohols to a dehydration condensation reaction with a polyvalent carboxylic acid (including anhydride). A compound obtained by reacting an acid anhydride or a polyvalent carboxylic acid (including an anhydride) with an epoxy (meth) acrylate having a hydroxyl group can be obtained, for example, by the method described in JP-A-5-32746. It is. Among these, a compound obtained by reacting bisphenol A type epoxy (meth) acrylate with an acid anhydride is preferable. Also obtained by reacting polyhydric carboxylic acid (including anhydride) with terminal alcoholic hydroxyl group of polyester resin obtained by dehydration condensation reaction of one or more polycarboxylic acids and one or more polyhydric alcohols. The compound to be obtained can be easily obtained from the market under, for example, trade names (Iupika Coat GV250, Iupika Coat GV250). Among these, Iupika Coat GV230 (acid value 53 mgKOH / g, weight average molecular weight 7900 g / mol) and Iupika Coat GV250 (acid value 74 mgKOH / g, weight average molecular weight 5200 g / mol) are preferably used, and Iupika Coat GV250 is particularly preferably used.
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、成分(ａ)硬化性樹脂の総量を１００質量部とした場合に、０．１〜２０質量部含有する場合が好ましく、更に好ましくは １〜１０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 0.1 to 20 parts by mass, more preferably 100 parts by mass when the total amount of the component (a) curable resin is 100 parts by mass. Is 1 to 10 parts by mass, and two or more kinds may be mixed and used.
本発明の液晶シール剤は、（ａ）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。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。（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。）本発明で用いる成分（ａ）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、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、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。 The liquid-crystal sealing compound of this invention contains the curable resin which consists of 1 type (s) or 2 or more types selected from (a) epoxy resin, (meth) acrylated epoxy resin, and partial (meth) acrylated epoxy resin. 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. (Here, “(meth) acryl” means “acryl” and / or “methacryl”. The same applies hereinafter.) The component (a) used in the present invention has low contamination and solubility in liquid crystals. Examples of suitable epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolak type epoxy resins, and bisphenols. F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, pheno having triphenolmethane skeleton Examples include, but are not limited to, luminolac-type epoxy resins, diglycidyl etherified products of difunctional phenols, diglycidyl etherified products of difunctional alcohols, halides thereof, and hydrogenated products thereof. . 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 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 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, diglycidyl ethers of difunctional phenols, difunctional alcohols Diglycidyl ether compound, 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.
成分（ａ）としての使用量は、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、通常、液晶シール剤中に２５〜８０質量％程度であり、好ましくは２５〜７５質量％である。 The amount used as the component (a) is appropriately determined in consideration of workability and physical properties of the obtained liquid crystal sealant, and is usually about 25 to 80% by mass in the liquid crystal sealant, preferably 25 to 75% by mass. %.
本発明の液晶シール剤では（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 sealant of the present invention, (d) a silane coupling agent can be used to improve adhesive strength and 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 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（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）により測定した。 In the liquid crystal sealant of the present invention, (e) an 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 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 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過ぎる場合、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過ぎる場合、フィラー含有量が多すぎるため、つぶれにくく液晶セルのギャップ形成ができなくなってしまう場合がある。 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 generally 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, since there is too much filler content, it is hard to be crushed and it may 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）光重合開始剤を含有しても良い。光重合開始剤は、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) photopolymerization initiator in order to obtain a photothermal combined curing liquid crystal sealant. The photopolymerization 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. 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Etc. 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全体を１００質量％とした場合、通常０．１〜５質量％、好ましくは０．２〜３質量％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 0.1 to 5 when the total amount of the liquid crystal sealant of the present invention is 100% by mass. % By mass, preferably 0.2 to 3% 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 sealant of the present invention may further contain additives such as 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）成分を有機溶剤に溶解した後、（ｃ）成分を添加し、加熱混合を行い（ｃ）成分を溶解する。その後有機溶剤を加熱等によって除去し、更に必要に応じ、（ｆ）成分を加熱下で溶解混合する。室温まで冷却後、（ｂ）成分を添加し、必要に応じ（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, after the component (a) is dissolved in an organic solvent, the component (c) is added and mixed by heating to dissolve the component (c). Thereafter, the organic solvent is removed by heating or the like, and if necessary, the component (f) is dissolved and mixed under heating. 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 known mixing devices such as The liquid-crystal sealing compound of this invention can be manufactured by mixing uniformly with a 3 roll, a sand mill, a ball mill etc., 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、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１〜２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. 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 to 130 ° C. for 1 to 2 hours. When used as a photothermal combination type, the liquid crystal sealant is irradiated with ultraviolet rays by an ultraviolet irradiator and photocured. 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.
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。
[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.
［合成例１−１］
合成例１で得られた反応液を水洗し、トルエンを留去することにより、目的とするビスフェノールＡ型のエポキシアクリレート３９５ｇを得た（ＫＡＹＡＲＡＤＲＴＭＲ−９３１００）。
［合成例１−２］
合成例１で得られた反応液にさらにテトラヒドロ無水フタル酸を１５１．６ｇ加え９８℃で約３０時間攪拌した。得られた反応液を６回水洗した後、エバポレーターでトルエンを留去することにより、目的とする化合物を６４０ｇ得た。（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）ＧＰＣ（ゲルパーミエーションクロマトグラフィー）測定による、この化合物の重量平均分子量は８２８ｇ／ｍｏｌであった。
[Synthesis Example 1-1]
The reaction solution obtained in Synthesis Example 1 was washed with water, and toluene was distilled off to obtain 395 g of the desired bisphenol A type epoxy acrylate (KAYARAD RTM R-93100).
[Synthesis Example 1-2]
To the reaction solution obtained in Synthesis Example 1, 151.6 g of tetrahydrophthalic anhydride was further added and stirred at 98 ° C. for about 30 hours. The obtained reaction solution was washed 6 times with water, and then toluene was distilled off with an evaporator to obtain 640 g of the intended compound. (Acid anhydride adduct of bisphenol A type epoxy acrylate) The weight average molecular weight of this compound as measured by GPC (gel permeation chromatography) was 828 g / mol.
（液晶滴下工法用のシール剤の調製）
［実施例１、２］
下記表１に示す割合で各樹脂成分（成分（ａ））を混合攪拌した後アセトンを添加し、樹脂成分を溶解した。そこへ、成分（ｃ）を添加し、７０℃で加熱溶解した後、エバポレーターで、アセトンを留去した。そこへ、ラジカル重合開始剤（成分（ｆ））を添加し、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、２を調製した。
(Preparation of sealant for liquid crystal dropping method)
[Examples 1 and 2]
Each resin component (component (a)) was mixed and stirred at the ratio shown in Table 1 below, and then acetone was added to dissolve the resin component. Thereto, component (c) was added and dissolved by heating at 70 ° C., and then acetone was distilled off with an evaporator. A radical polymerization initiator (component (f)) was added thereto, dissolved by heating, then cooled to room temperature, a silane coupling agent (component (d)), an inorganic filler (component (e)), and thermosetting. The agent (component (b)) was added and stirred, and then dispersed with a three-roll mill and filtered through a metal mesh (635 mesh) to prepare liquid crystal dropping method sealing agents Examples 1 and 2.
［実施例３］
下記表１に示す割合で各樹脂成分（成分（ａ））を混合攪拌した後、成分（ｃ）を添加し、９０℃で加熱溶解した。そこへ、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３を調製した。
[Example 3]
Each resin component (component (a)) was mixed and stirred at the ratio shown in Table 1 below, and then component (c) was added and dissolved by heating at 90 ° C. The 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 with a three-roll mill and filtered through a metal mesh (635 mesh) to prepare a sealing agent example 3 for a liquid crystal dropping method.
［比較例１〜３］
下記表１に示す割合で各樹脂成分（成分（ａ））を混合攪拌した後、ラジカル重合開始剤（成分（ｆ））を９０℃で加熱溶解させた。室温まで冷却し、成分（ｃ）、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比較例１〜３を調製した。
[Comparative Examples 1-3]
Each resin component (component (a)) was mixed and stirred at the ratio shown in Table 1 below, and then the radical polymerization initiator (component (f)) was heated and dissolved at 90 ° C. Cool to room temperature, add component (c), silane coupling agent (component (d)), inorganic filler (component (e)), thermosetting agent (component (b)), and stir, then 3 roll mill And filtered through a metal mesh (635 mesh) to prepare sealant comparative examples 1 to 3 for 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内容とその結果を示す。 The evaluation item contents and the results of the sealing agents for liquid crystal dropping methods prepared below are shown.
（熱硬化性試験）
各液晶滴下工法用シール剤をポリエチレンテレフタレートフィルム間に塗布した後、ラミネーターを用いて１００μｍの厚みに伸ばし、３０００ｍＪ／ｃｍ2の紫外線を照射した（サンプル１）。できたフィルムを１２０℃×１時間熱硬化した（サンプル２）。サンプル１、サンプル２のエンタルピーを示差走査型熱量計（セイコーインスツル社製、測定条件：３０℃から２５０℃、昇温速度１０℃）を用いて測定し、下記計算式により熱反応率を計算した。
熱反応率＝[１−（サンプル１のエンタルピー − サンプル２のエンタルピー）／サンプル１のエンタルピー]×１００
結果を以下のように判定した。
○ 熱反応率９０％以上
× 熱反応率９０％未満
実施例１は、９２％、実施例２は９１％ 実施例３は９４％であった。
(Thermosetting test)
After applying each liquid crystal dropping method sealing agent between polyethylene terephthalate films, it was stretched to a thickness of 100 μm using a laminator and irradiated with 3000 mJ / cm 2 of ultraviolet rays (sample 1). The resulting film was heat cured at 120 ° C. for 1 hour (Sample 2). The enthalpies of Sample 1 and Sample 2 were measured using a differential scanning calorimeter (Seiko Instruments Inc., measurement conditions: 30 ° C. to 250 ° C., heating rate 10 ° C.), and the thermal reaction rate was calculated using the following formula. did.
Thermal reaction rate = [1- (Enthalpy of sample 1−Enthalpy of sample 2) / Enthalpy of sample 1] × 100
The result was determined as follows.
O Thermal reaction rate of 90% or more x Thermal reaction rate of less than 90% Example 1 was 92%, Example 2 was 91%, and Example 3 was 94%.
（液晶汚染性試験）
１０ｍｌバイアル瓶に３０００ｍＪ／ｃｍ2の紫外線を照射した液晶滴下工法用シール剤のフィルム（上記サンプル１）を５ｍｍ2程度の大きさに切ったものを１００ｍｇ程度入れた後、液晶（ＭＬＣ−６８６６−１００：メルク株式会社製）をその質量基準で１０倍量加えた。１時間１２０℃で加熱した後、３０分冷却した。それぞれの上澄み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）にて測定し、シール剤なしのものの値と比較した。以下により判定を行った。
○ ９．５Ｅ＋１１以上
△ １．０Ｅ＋１１以上９．５Ｅ＋１１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。
実施例１は３．８Ｅ＋１２、実施例２は９．７Ｅ＋１１、実施例３は２．７Ｅ＋１２であった。
(LCD contamination test)
After putting about 100 mg of a film of a sealing agent for liquid crystal dropping method (sample 1 above) irradiated with 3000 mJ / cm 2 ultraviolet rays into a 10 ml vial, about 5 mm 2 , liquid crystal (MLC-6866- 100: manufactured by Merck & Co., Inc.) was added in an amount of 10 times based on its mass. After heating at 120 ° C. for 1 hour, it was cooled for 30 minutes. Each supernatant was separated by decantation, measured with a digital ultrahigh resistance meter (R8340: manufactured by Advantest Co., Ltd.), and compared with the value without the sealant. The determination was made as follows.
○ 9.5E + 11 or more Δ1.0E + 11 or more, but less than 9.5E + 11 × less than 1.0E + 11 Note that the specific resistance value “1.0E + 12” represents “1.0 × 10 12 ”, and other descriptions are also the same.
Example 1 was 3.8E + 12, Example 2 was 9.7E + 11, and Example 3 was 2.7E + 12.
（保存安定性試験）
各液晶滴下工法用シール剤を２３℃高温槽で保温し、２４時間後の粘度を測定した。
初期の粘度と比較をし、下記のように判定した。なお粘度はＥ型粘度計（東機産業社製）を用いて測定した。
○ 粘度増加率５％未満
△ 粘度増加率５％以上１０％未満
× 粘度増加率１０％以上もしくはゲル化
実施例１は３％、実施例２は３％、実施例３は４％であった。
(Storage stability test)
Each liquid crystal dropping method sealing agent was kept warm in a 23 ° C. high temperature bath, and the viscosity after 24 hours was measured.
The viscosity was compared with the initial viscosity and judged as follows. The viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
○ Viscosity increase rate of less than 5% Δ Viscosity increase rate of 5% or more and less than 10% x Viscosity increase rate of 10% or more or gelation Example 1 was 3%, Example 2 was 3%, and Example 3 was 4% .
（耐湿接着性試験）
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測定した。また、硬化後のガラス基板を用いてＰＣＴ試験（条件：温度１２０℃、湿度１００％、気圧２ａｔｍ、試験時間１２時間）を行い、その後のガラス片のせん断接着強度を測定し、ＰＣＴ試験前後での接着保持率計算し、以下のように判定した。
○ ５０％以上
△ ２５％以上５０％未満
× ２５％未満
実施例１は６９％、実施例２は６５％、実施例３は５５％であった。
(Moisture resistance test)
1 g of 5 μm glass fiber is added as a spacer to 100 g of the 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 piece was measured. Also, a PCT test (conditions: temperature 120 ° C., humidity 100%, atmospheric pressure 2 atm, test time 12 hours) was performed using the cured glass substrate, and the shear adhesive strength of the subsequent glass pieces was measured before and after the PCT test. The adhesion retention rate was calculated and judged as follows.
○ 50% or more Δ 25% or more and less than 50% x less than 25% Example 1 was 69%, Example 2 was 65%, and Example 3 was 55%.
（パネル表示特性試験）
調整した各液晶滴下工法用シール剤をシリンジに充填・脱泡した後、ディスペンサー（武蔵エンジニアリング社製 ショットマスター３００）にてガラス基板上にシール剤を塗布し、適量の液晶をシール枠内に滴下した。その基板を真空張り合わせ装置に設置し、真空下でもう一方の基板を重ね合わせた後、１２０℃で１時間硬化した。できた模擬パネルに通電し、偏光フィルム上で観察した。観察結果は以下のように判定した。
○ 配向不良が確認されなかった
× 配向不良が確認された
※ シール剤から気泡が発生し、液晶漏れを引き起こした
(Panel display characteristics test)
After filling and defoaming the prepared sealing agent for each liquid crystal dropping method in the syringe, the sealing agent is applied onto the glass substrate with a dispenser (Musashi Engineering Shot Master 300), and an appropriate amount of liquid crystal is dropped into the sealing frame. did. The substrate was placed in a vacuum laminating apparatus, and the other substrate was superposed under vacuum, and then cured at 120 ° C. for 1 hour. The resulting simulated panel was energized and observed on a polarizing film. The observation result was determined as follows.
○ Alignment failure was not confirmed × Alignment failure was confirmed * Bubbles were generated from the sealant, causing liquid crystal leakage
表１の結果より、硬化促進剤成分を含有しない比較例３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、硬化促進剤として熱ラジカル開始剤や、ＣＩＣ酸を用いたものは、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 3 containing no curing accelerator component is inferior in curability, and as a result, orientation failure occurs in the panel display characteristics. Moreover, although the thing using the thermal radical initiator and CIC acid as a hardening accelerator has improved sclerosis | hardenability, it has produced the malfunction in liquid-crystal stain | contamination property and moisture-proof adhesiveness. 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 (10)
で表される分子骨格を示す］ The liquid crystal sealing agent for a liquid crystal dropping method according to claim 4, 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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| JP2011147814A JP5645765B2 (en) | 2011-07-03 | 2011-07-03 | Liquid crystal sealant and liquid crystal display cell using the same |
| TW101123493A TW201319156A (en) | 2011-07-03 | 2012-06-29 | Liquid crystal sealant and liquid crystal display cell using same |
| KR1020147000426A KR20140036301A (en) | 2011-07-03 | 2012-06-29 | Liquid crystal sealant and liquid crystal display cell using same |
| CN201280032943.1A CN103635854B (en) | 2011-07-03 | 2012-06-29 | Liquid crystal sealing agent and use its liquid crystal display |
| PCT/JP2012/066793 WO2013005693A1 (en) | 2011-07-03 | 2012-06-29 | Liquid crystal sealant and liquid crystal display cell using same |
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| JP2017026736A (en) * | 2015-07-21 | 2017-02-02 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
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| JP6535002B2 (en) * | 2014-07-17 | 2019-06-26 | 日本化薬株式会社 | Liquid crystal sealing agent and liquid crystal display cell using the same |
| WO2018201428A1 (en) * | 2017-05-05 | 2018-11-08 | Henkel Ag & Co. Kgaa | Thermally curable sealant composition and use thereof |
| CN110136581B (en) * | 2019-04-01 | 2022-01-04 | 陈波 | Thermoplastic optical adhesive attaching method and application and display |
| FR3121790A1 (en) | 2021-04-09 | 2022-10-14 | Valeo Systemes Thermiques | Compartment for equipment likely to generate heat |
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| WO2013005693A1 (en) | 2013-01-10 |
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| CN103635854B (en) | 2016-04-13 |
| TW201319156A (en) | 2013-05-16 |
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