JP3955038B2 - Curable resin composition for liquid crystal display element - Google Patents
Curable resin composition for liquid crystal display element Download PDFInfo
- Publication number
- JP3955038B2 JP3955038B2 JP2004122032A JP2004122032A JP3955038B2 JP 3955038 B2 JP3955038 B2 JP 3955038B2 JP 2004122032 A JP2004122032 A JP 2004122032A JP 2004122032 A JP2004122032 A JP 2004122032A JP 3955038 B2 JP3955038 B2 JP 3955038B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal display
- display element
- curable resin
- resin composition
- 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 - Lifetime
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 113
- 239000011342 resin composition Substances 0.000 title claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- -1 acryl groups Chemical group 0.000 claims description 25
- 238000007789 sealing Methods 0.000 claims description 22
- 125000000524 functional group Chemical group 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 229920001187 thermosetting polymer Polymers 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000010419 fine particle Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000007870 radical polymerization initiator Substances 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 239000000565 sealant Substances 0.000 description 22
- 150000002009 diols Chemical class 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 229920000647 polyepoxide Polymers 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 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
- 229920003986 novolac Polymers 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229920006295 polythiol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-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
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 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 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- LOZWAPSEEHRYPG-UHFFFAOYSA-N 1,4-dithiane Chemical group C1CSCCS1 LOZWAPSEEHRYPG-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QISZCVLALJOROC-UHFFFAOYSA-N 3-(2-hydroxyethyl)-4-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OCCC1=C(CCOC(=O)C=C)C=CC(C(O)=O)=C1C(O)=O QISZCVLALJOROC-UHFFFAOYSA-N 0.000 description 1
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-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
- 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 1
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ADYVCZCQSVYNPQ-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 ADYVCZCQSVYNPQ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052604 silicate mineral 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
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明は、滴下工法による液晶表示素子の製造における液晶滴下工法用シール剤に用いた場合にも、液晶を汚染しにくく、色むら等の少ない画像表示が可能な液晶表示素子が得られる液晶表示素子用硬化性組成物、該液晶表示素子用硬化性組成物からなる液晶滴下工法用シール剤、上下導通用材料及び液晶表示素子に関する。 The present invention provides a liquid crystal display that can provide a liquid crystal display element that is less likely to contaminate the liquid crystal and that can display an image with little color unevenness, even when used as a sealant for a liquid crystal dropping method in the production of a liquid crystal display element by the dropping method. The present invention relates to a curable composition for an element, a sealing agent for a liquid crystal dropping method comprising the curable composition for a liquid crystal display element, a material for vertical conduction, and a liquid crystal display element.
従来、液晶表示セル等の液晶表示素子は、２枚の電極付き透明基板を、所定の間隔をおいて対向させ、その周囲をシール剤で封着してセルを形成し、その一部に設けられた液晶注入口からセル内に液晶を注入し、その液晶注入口をシール剤又は封口剤を用いて封止することにより作製されていた。 Conventionally, a liquid crystal display element such as a liquid crystal display cell is formed by forming a cell by facing two transparent substrates with electrodes facing each other at a predetermined interval and sealing the periphery with a sealing agent. The liquid crystal was injected into the cell from the liquid crystal injection port, and the liquid crystal injection port was sealed using a sealing agent or a sealing agent.
この方法では、まず、２枚の電極付き透明基板のいずれか一方に、スクリーン印刷により熱硬化性シール剤を用いた液晶注入口を設けたシールパターンを形成し、６０〜１００℃でプリベイクを行いシール剤中の溶剤を乾燥させる。次いで、スペーサーを挟んで２枚の基板を対向させてアライメントを行い貼り合わせ、１１０〜２２０℃で１０〜９０分間熱プレスを行いシール近傍のギャップを調整した後、オーブン中で１１０〜２２０℃で１０〜１２０分間加熱しシール剤を本硬化させる。次いで、液晶注入口から液晶を注入し、最後に封口剤を用いて液晶注入口を封止して、液晶表示素子を作製していた。 In this method, first, a seal pattern provided with a liquid crystal injection port using a thermosetting sealant is formed on one of two transparent substrates with electrodes by screen printing, and prebaked at 60 to 100 ° C. Dry the solvent in the sealant. Next, alignment is performed with the two substrates facing each other with a spacer interposed therebetween, and the gap in the vicinity of the seal is adjusted by performing hot pressing at 110 to 220 ° C. for 10 to 90 minutes, and then at 110 to 220 ° C. in an oven. Heat for 10 to 120 minutes to fully cure the sealant. Next, liquid crystal was injected from the liquid crystal injection port, and finally, the liquid crystal injection port was sealed using a sealing agent to produce a liquid crystal display element.
しかし、この作製方法によると、熱歪により位置ズレ、ギャップのバラツキ、シール剤と基板との密着性の低下等が発生する；残留溶剤が熱膨張して気泡が発生しキャップのバラツキやシールパスが発生する；シール硬化時間が長い；プリベイクプロセスが煩雑；溶剤の揮発によりシール剤の使用可能時間が短い；液晶の注入に時間がかかる等の問題があった。とりわけ、近年の大型の液晶表示装置にあっては、液晶の注入に非常に時間がかかることが大きな問題となっていた。 However, according to this manufacturing method, the positional displacement, gap variation, decrease in adhesion between the sealing agent and the substrate, etc. occur due to thermal strain; residual solvent thermally expands to generate bubbles, resulting in cap variation and seal path. The seal curing time is long; the prebaking process is complicated; the usable time of the sealant is short due to the volatilization of the solvent; and it takes time to inject liquid crystal. In particular, in a large liquid crystal display device in recent years, it takes a very long time to inject liquid crystal.
これに対して、滴下工法と呼ばれる液晶表示素子の製造方法が検討されている。滴下工法では、まず、２枚の電極付き透明基板の一方に、スクリーン印刷により長方形状のシールパターンを形成する。次いで、シール剤未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下塗布し、すぐに他方の透明基板を重ねあわせた後、液晶アニール時に加熱して熱硬化を行い、液晶表示素子を作製する。基板の貼り合わせを減圧下で行うようにすれば、極めて高い効率で液晶表示素子を製造することができる。今後はこの滴下工法が液晶表示装置の製造方法の主流となると期待されている。 On the other hand, a method for manufacturing a liquid crystal display element called a dripping method has been studied. In the dropping method, first, a rectangular seal pattern is formed on one of the two transparent substrates with electrodes by screen printing. Next, liquid crystal micro-drops are applied to the entire surface of the transparent substrate in an uncured state with the sealant uncured. The other transparent substrate is immediately overlaid, and then heat-cured by annealing during liquid crystal annealing. An element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency. In the future, this dripping method is expected to become the mainstream of liquid crystal display manufacturing methods.
従来工法に用いられるシール剤としては、例えば、特許文献１に、ビスフェノールＡ型エポキシ樹脂の部分（メタ）アクリル化物を主成分とする接着剤が開示されている。また、特許文献２、特許文献３、特許文献４、特許文献５、特許文献６等には、（メタ）アクリレートを主成分とする液晶シール剤が開示されている。
しかしながら、これらのシール剤は液晶材料と親和しやすい性質を有することから、これらのシール剤を用いて組み立てられた液晶表示素子では、液晶中にシール剤の成分が溶出し、シール剤の周辺部に液晶の配向乱れが生じ、色むら等の表示不良を引き起こすことがあった。とりわけ、滴下工法では未硬化のシール剤が直接液晶と接する工程があることから、シール剤成分による液晶汚染が大きな問題となっていた。
また、光によって硬化するシール剤を用いた場合、液晶表示素子の素子構造によっては、ブラックマトリックスや配線のためにシール剤に光が充分に照射されず、未硬化のシール剤成分が残留することにより、液晶汚染が発生するという問題もあった。
As a sealing agent used in a conventional construction method, for example, Patent Document 1 discloses an adhesive mainly composed of a partial (meth) acrylate of a bisphenol A type epoxy resin. Further, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6, and the like disclose liquid crystal sealants containing (meth) acrylate as a main component.
However, since these sealants have properties that are easily compatible with liquid crystal materials, in liquid crystal display elements assembled using these sealants, the components of the sealant are eluted in the liquid crystal, and the periphery of the sealant In this case, the alignment of the liquid crystal is disturbed, which may cause display defects such as color unevenness. In particular, in the dropping method, there is a process in which an uncured sealant is in direct contact with liquid crystal, so liquid crystal contamination due to the sealant component has been a major problem.
In addition, when a sealant that is cured by light is used, depending on the element structure of the liquid crystal display element, the sealant is not sufficiently irradiated with light due to the black matrix and wiring, and an uncured sealant component remains. As a result, there is a problem that liquid crystal contamination occurs.
本発明は、上記の現状に鑑み、滴下工法による液晶表示素子の製造における液晶滴下工法用シール剤に用いた場合にも、液晶を汚染しにくく、色むら等の少ない画像表示が可能な液晶表示素子が得られる液晶表示素子用硬化性組成物、該液晶表示素子用硬化性組成物からなる液晶滴下工法用シール剤、上下導通用材料及び液晶表示素子を提供することを目的とする。 In view of the above-mentioned present situation, the present invention is a liquid crystal display that is less likely to contaminate liquid crystals and can display images with little color unevenness even when used as a sealant for liquid crystal dropping methods in the production of liquid crystal display elements by the dropping method. It aims at providing the curable composition for liquid crystal display elements from which an element is obtained, the sealing compound for liquid crystal dropping methods which consists of this curable composition for liquid crystal display elements, the material for vertical conduction, and a liquid crystal display element.
本発明は、熱のみによって硬化する液晶表示素子用硬化性樹脂組成物であって、１分子中に水素結合性官能基と２以上の（メタ）アクリル基とを有し、１分子中の水素結合性官能基量が３．５×１０-3以上である硬化性樹脂１００重量部に対して、熱硬化剤３〜４０重量部を含有する液晶表示素子用硬化性樹脂組成物である。
以下に本発明を詳述する。
The present invention is a curable resin composition for a liquid crystal display element that is cured only by heat, and has a hydrogen-bonding functional group and two or more (meth) acryl groups in one molecule, and hydrogen in one molecule. It is a curable resin composition for a liquid crystal display element containing 3 to 40 parts by weight of a thermosetting agent with respect to 100 parts by weight of a curable resin having a binding functional group amount of 3.5 × 10 −3 or more.
The present invention is described in detail below.
本発明の液晶表示素子用硬化性樹脂組成物（以下、本発明の樹脂組成物ともいう）は、分子中に水素結合性官能基と２以上の（メタ）アクリル基とを有し、１分子中の水素結合性官能基量が３．５×１０-3以上である硬化性樹脂を樹脂成分として含有する。
本発明者らは、鋭意検討の結果、１分子中の水素結合性官能基量が一定以上である樹脂は液晶に溶出しにくく、液晶を汚染しないことを見出した。従来の液晶表示素子用シール剤等に使用される樹脂組成物では、極性が低く液晶に溶出しやすい樹脂を用いていたり、たとえ極性の高い樹脂を用いる場合であっても、製造の工程において生成した副生成物や未反応樹脂等の極性の低い樹脂の混入したりすることについては何らの考慮もしていなかったことから、このような樹脂組成物を用いた液晶表示素子用シール剤は液晶を汚染しやすいものであった。
本発明では、樹脂成分を上述の要件を満たす樹脂のみとすることにより、液晶を汚染することがない。
The curable resin composition for liquid crystal display elements of the present invention (hereinafter also referred to as the resin composition of the present invention) has a hydrogen-bonding functional group and two or more (meth) acryl groups in the molecule. A curable resin having a hydrogen bondable functional group amount of 3.5 × 10 −3 or more is contained as a resin component.
As a result of intensive studies, the present inventors have found that a resin having a certain amount of hydrogen bonding functional groups in one molecule is not easily eluted into the liquid crystal and does not contaminate the liquid crystal. In resin compositions used for conventional sealants for liquid crystal display elements, etc., even if a resin with low polarity and easily eluted into liquid crystals is used, or even when a highly polar resin is used, it is generated in the manufacturing process. Since no consideration was given to the incorporation of low polarity resins such as by-products and unreacted resins, liquid crystal display element sealants using such a resin composition have no liquid crystals. It was easily contaminated.
In the present invention, the liquid crystal is not contaminated by using only the resin that satisfies the above-mentioned requirements as the resin component.
上記硬化性樹脂の水素結合性官能基量の下限は、３．５×１０-3である。３．５×１０-3未満であると、本発明の樹脂組成物を液晶表示素子用のシール剤として用いた場合に、硬化性樹脂が液晶に溶出して液晶を汚染してしまう。好ましい下限は４．０×１０-3である。
なお、本明細書において水素結合性官能基量とは、下記式（１）により算出される値を意味する。
The lower limit of the hydrogen bondable functional group amount of the curable resin is 3.5 × 10 −3 . When it is less than 3.5 × 10 −3 , when the resin composition of the present invention is used as a sealant for a liquid crystal display element, the curable resin is eluted into the liquid crystal and contaminates the liquid crystal. A preferred lower limit is 4.0 × 10 −3 .
In addition, in this specification, the hydrogen bondable functional group amount means a value calculated by the following formula (1).
水素結合性官能基量
＝（硬化性樹脂１分子中の水素合性官能基数）／（硬化性樹脂の分子量） （１）
Amount of hydrogen bonding functional group = (number of hydrogen bonding functional groups in one molecule of curable resin) / (molecular weight of curable resin) (1)
上記水素結合性官能基としては、水素結合性を有する官能基又は残基等であれば特に限定されず、例えば、−ＯＨ基、−ＮＨ2基、−ＮＨＲ基（Ｒは、芳香族、脂肪族炭化水素又はこれらの誘導体を表す）、−ＣＯＯＨ基、−ＣＯＮＨ2基、−ＮＨＯＨ基等や、分子中に存在する−ＮＨＣＯ−結合、−ＮＨ−結合、−ＣＯＮＨＣＯ−結合、−ＮＨ−ＮＨ−結合等の残基を有する基等が挙げられる。なかでも、水酸基及び／又はウレタン基が好適である。 The hydrogen bonding functional group is not particularly limited as long as it is a functional group or a residue having hydrogen bonding properties. For example, —OH group, —NH 2 group, —NHR group (R is aromatic, aliphatic, -COOH group, -CONH 2 group, -NHOH group, etc., -NHCO- bond, -NH- bond, -CONHCO- bond, -NH-NH present in the molecule -Groups having a residue such as a bond. Of these, a hydroxyl group and / or a urethane group are preferred.
また、上記硬化性樹脂は、１分子中に上記水素結合性官能基と２以上の（メタ）アクリル基とを有する。これにより、本発明の樹脂組成物は熱硬化型となる。
なお、本明細書において（メタ）アクリル基とは、アクリル基又はメタクリル基のことをいう。
Moreover, the said curable resin has the said hydrogen bondable functional group and two or more (meth) acryl groups in 1 molecule. Thereby, the resin composition of this invention becomes a thermosetting type.
In addition, in this specification, a (meth) acryl group means an acryl group or a methacryl group.
上記１分子中に水素結合性官能基と２以上の（メタ）アクリル基とを有する硬化性樹脂としては特に限定されないが、例えば、ウレタン結合を有するウレタン（メタ）アクリレート樹脂、エポキシ基を（メタ）アクリル酸で変性することにより得られる（メタ）アクリル酸変性エポキシ樹脂、ＯＨ基を含むポリオールと(メタ)アクリル酸とからＯＨ基を１つ以上残した状態で誘導された（メタ）アクリレート等が挙げられる。 Although it does not specifically limit as curable resin which has a hydrogen bondable functional group and two or more (meth) acryl groups in said 1 molecule, For example, urethane (meth) acrylate resin which has a urethane bond, an epoxy group (meta ) (Meth) acrylic acid-modified epoxy resin obtained by modification with acrylic acid, (meth) acrylate derived from OH group-containing polyol and (meth) acrylic acid leaving one or more OH groups, etc. Is mentioned.
上記ウレタン（メタ）アクリレート樹脂を得る方法としては特に限定されないが、例えば、ジイソシアネート化合物に活性水素基を有する（メタ）アクリル酸エステルモノマーを反応させる方法；ジオール化合物とジイソシアネート化合物とをモル比で１：１〜１：２の割合で反応させて得られる末端にイソシアネート基を有するプレポリマーに、残りのイソシアネート基と完全に反応するだけの活性水素基を有するアクリル酸エステルモノマーを反応させる方法；ポリオールとイソシアネート基を有する（メタ）アクリレートとを反応させる方法等により得ることができる。 Although it does not specifically limit as a method of obtaining the said urethane (meth) acrylate resin, For example, the method of making the (meth) acrylic acid ester monomer which has an active hydrogen group react with a diisocyanate compound; A diol compound and a diisocyanate compound are 1 by molar ratio. : A method of reacting a prepolymer having an isocyanate group at the terminal obtained by reacting at a ratio of 1 to 1: 2 with an acrylate monomer having an active hydrogen group that only reacts completely with the remaining isocyanate group; polyol And a method of reacting (meth) acrylate having an isocyanate group.
上記ジイソシアネート化合物としては、例えば、ジフェニルエタンジイソシアネート（ＭＤＩ）、トリレンジイソシアネート（ＴＤＩ）、キシレンジイソシアネート（ＸＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、ナフチレンジイソシアネート（ＮＤＩ）、トリジンジイソシアネート（ＴＰＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、ジシクロヘキシルメタンジイソシアネート（ＨＭＤＩ）、トリメチルヘキサメチレンジイソシアネート（ＴＭＨＤＩ）等が挙げられる。また、イソシアネート基を有する（メタ）アクリレートのうち市販されているものとしては、例えば、昭和電工社製のＭＯＩ等が挙げられる。 Examples of the diisocyanate compound include diphenylethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), naphthylene diisocyanate (NDI), tolidine diisocyanate (TPDI), hexamethylene diisocyanate. (HDI), dicyclohexylmethane diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMHDI) and the like. Examples of commercially available (meth) acrylates having an isocyanate group include MOI manufactured by Showa Denko KK.
上記活性水素を持った（メタ）アクリレートとしては特に限定されないが、例えば、ＯＨ基を有するものでは、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、グリセリンジ（メタ）アクリレート、２−ヒドロキシ−３−アクリロイルオキシプロピル（メタ）アクリレート、２−（メタ）アクリロイルオキシエチル−２−ヒドロキシエチルフタル酸エポキシエステル、ペンタエリスリトールトリアクリレート等が挙げられ、ＣＯＯ基を有するものでは、（メタ）アクリル酸、２−（メタ）アクリロイルオキシエチルコハク酸、２−（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、２−アクリロイルオキシエチルフタル酸等が挙げられる。 Although it does not specifically limit as said (meth) acrylate with active hydrogen, For example, in what has OH group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerin di (meth) acrylate , 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid epoxy ester, pentaerythritol triacrylate, etc., and those having a COO group, Examples include meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and 2-acryloyloxyethyl phthalic acid.
上記ジオール化合物としては特に限定されず、例えば、アルキルジオール、ポリエーテルジオール、ポリエステルジオール等が挙げられる。
上記アルキルジオールとしては特に限定されず、例えば、エチレングリコール、プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、１，９−ノナンジオール、ネオペンチルグリコール、１，４−シクロヘキサンジオール等が挙げられる。
上記ポリエーテルジオールとしては特に限定されず、例えば、ポリ（エチレンオキサイド）ジオール、ポリ（プロピレンオキサイド）ジオール、ポリ（テトラメチレンオキサイド）ジオール、ビスフェノールＡのエチレンオキサイド付加物、ビスフェノールＡのプロピレンオキサイド付加物等が挙げられる。
上記ポリエステルジオールとしては特に限定されず、例えば、ポリ（カプロラクトン）ジオール、ポリ（カーボネート）ジオール等や、アジピン酸、コハク酸、テレフタル酸、イソフタル酸等の酸性分とエチレングリコール、ジエチレングリコール、１，４−ブタンジオール等のジオール成分とを脱水反応して得られるポリエステルジオール等が挙げられる。
これらアルキルジオール、ポリエーテルジオール、ポリエステルジオールは単独で用いてもよく、複数種を用いてもよい。なかでも、接着性、硬化収縮の観点からビスフェノールＡのエチレンオキサイド付加物やポリ（カプロラクトン）ジオールが特に好ましい。
The diol compound is not particularly limited, and examples thereof include alkyl diol, polyether diol, and polyester diol.
The alkyl diol is not particularly limited. For example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, Examples include 1,4-cyclohexanediol.
The polyether diol is not particularly limited. For example, poly (ethylene oxide) diol, poly (propylene oxide) diol, poly (tetramethylene oxide) diol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct Etc.
The polyester diol is not particularly limited. For example, poly (caprolactone) diol, poly (carbonate) diol, etc., acidic components such as adipic acid, succinic acid, terephthalic acid, isophthalic acid, ethylene glycol, diethylene glycol, 1, 4 -Polyester diol obtained by dehydration reaction with diol components such as butanediol.
These alkyl diols, polyether diols, and polyester diols may be used alone or in combination. Of these, bisphenol A ethylene oxide adduct and poly (caprolactone) diol are particularly preferred from the viewpoints of adhesiveness and cure shrinkage.
上記（メタ）アクリル酸変性エポキシ樹脂の原料となるエポキシ樹脂としては、例えば、ノボラック型としてはフェノールノボラック型、クレゾールノボラック型、ビフェニルノボラック型、トリスフェノールノボラック型、ジシクロペンタジエンノボラック型等が挙げられ、また、ビスフェノール型としてはビスフェノールＡ型、ビスフェノールＦ型、２，２’−ジアリルビスフェノール型、ビスフェノールＳ型、水添ビスフェノール型、ポリオキシプロピレンビスフェノールＡ型等が挙げられる。 Examples of the epoxy resin used as a raw material for the (meth) acrylic acid-modified epoxy resin include, for example, a novolak type such as a phenol novolak type, a cresol novolak type, a biphenyl novolak type, a trisphenol novolak type, and a dicyclopentadiene novolak type. Examples of the bisphenol type include bisphenol A type, bisphenol F type, 2,2′-diallyl bisphenol type, bisphenol S type, hydrogenated bisphenol type, and polyoxypropylene bisphenol A type.
上記（メタ）アクリル酸変性エポキシ樹脂の原料となるエポキシ樹脂のうち市販されているものとしては、例えば、フェノールノボラック型としては、エピクロンＮ−７４０、エピクロンＮ−７７０、エピクロンＮ−７７５（以上、大日本インキ化学社製）、エピコート１５２、エピコート１５４（以上、ジャパンエポキシレジン社製）等が挙げれれ、クレゾールノボラック型としては、エピクロンＮ−６６０、エピクロンＮ−６６５、エピクロンＮ−６７０、エピクロンＮ−６７３、エピクロンＮ−６８０、エピクロンＮ−６９５、エピクロンＮ−６６５−ＥＸＰ、エピクロンＮ−６７２−ＥＸＰ（以上、大日本インキ化学社製）等が挙げられる。 Among the epoxy resins that are commercially available as raw materials for the (meth) acrylic acid-modified epoxy resin, for example, as a phenol novolak type, Epicron N-740, Epicron N-770, Epicron N-775 (or more, Dainippon Ink Chemical Co., Ltd.), Epicoat 152, Epicoat 154 (above, Japan Epoxy Resin Co., Ltd.), and the like. Examples of the cresol novolak type include Epicron N-660, Epicron N-665, Epicron N-670, and Epicron N. -673, Epicron N-680, Epicron N-695, Epicron N-665-EXP, Epicron N-672-EXP (above, manufactured by Dainippon Ink and Chemicals, Inc.) and the like.
上記エポキシ樹脂の（メタ）アクリル化物は、例えば、エポキシ樹脂と（メタ）アクリル酸とを、常法に従って塩基性触媒の存在下で反応することにより得ることができる。エポキシ樹脂と（メタ）アクリル酸との配合量を適宜変更することにより、所望のアクリル化率のエポキシ樹脂を得ることが可能である。 The (meth) acrylated product of the epoxy resin can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. By appropriately changing the blending amount of the epoxy resin and (meth) acrylic acid, it is possible to obtain an epoxy resin having a desired acrylation rate.
上記ＯＨ基を含むポリオールと(メタ)アクリル酸とからＯＨ基を１つ以上残した状態で誘導された（メタ）アクリレートとしては、例えば、グリセリンジ（メタ）アクリレート等が挙げられる。 Examples of (meth) acrylate derived from the polyol containing OH group and (meth) acrylic acid in a state where one or more OH groups are left include glycerin di (meth) acrylate and the like.
上記熱硬化剤は、加熱により硬化性樹脂中の（メタ）アクリル基を反応性させ、架橋させるためのものであり、硬化後の硬化性樹脂組成物の接着性、耐熱性、耐湿性を向上させる役割を有する。上記熱硬化剤としては、融点が１００℃以上の潜在性硬化剤が好適に用いられる。融点が１００℃以下の硬化剤を使用すると保存安定性が著しく悪くなることがある。なかでも、（メタ）アクリル基との反応性の点から、アミン基及び／又はチオール基を有する熱硬化剤が好適である。 The thermosetting agent reacts and crosslinks the (meth) acrylic group in the curable resin by heating, and improves the adhesiveness, heat resistance, and moisture resistance of the curable resin composition after curing. Have a role to play. As the thermosetting agent, a latent curing agent having a melting point of 100 ° C. or higher is preferably used. When a curing agent having a melting point of 100 ° C. or lower is used, the storage stability may be remarkably deteriorated. Especially, the thermosetting agent which has an amine group and / or a thiol group from a reactive point with a (meth) acryl group is suitable.
上記アミン基を有する熱硬化剤としては、例えば、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］等のヒドラジド化合物、各種アミンとエポキシ樹脂との付加生成物等が挙げられる。
上記チオール基を有する熱硬化剤としては、例えば、エタンジチオール、プロパンジチオール、ヘキサメチレンジチオール、デカメチレンジチオール、トリレン−２，４−ジチオール等の脂肪族ポリチオール；キシレンジチオール等の芳香族ポリチオール；ジグリコールジメルカプタン、トリグリコールジメルカプタン、テトラグリコールジメルカプタン、チオジグリコールジメルカプタン、チオトリグリコールジメルカプタン、チオテトラグリコールジメルカプタン、トリメチロールプロパントリス−β−メルカプトプロピオネート、１，４−ジチアン環含有ポリチオール化合物等の環状スルフィド化合物等が挙げられる。これらの熱硬化剤は単独で用いてもよく、２種類以上が併用されてもよい。
Examples of the thermosetting agent having an amine group include hydrazide compounds such as 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin], addition products of various amines and epoxy resins, and the like.
Examples of the thermosetting agent having a thiol group include aliphatic polythiols such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-2,4-dithiol; aromatic polythiols such as xylenedithiol; Contains dimercaptan, triglycol dimercaptan, tetraglycol dimercaptan, thiodiglycol dimercaptan, thiotriglycol dimercaptan, thiotetraglycol dimercaptan, trimethylolpropane tris-β-mercaptopropionate, 1,4-dithiane ring Examples thereof include cyclic sulfide compounds such as polythiol compounds. These thermosetting agents may be used alone or in combination of two or more.
上記熱硬化剤としては、固体硬化剤粒子の表面が微粒子により被覆されている被覆硬化剤も好適である。このような被覆硬化剤を用いれば、予め熱硬化剤を配合していても高い保存安定性を有する樹脂組成物が得られる。 As the thermosetting agent, a coating curing agent in which the surface of solid curing agent particles is coated with fine particles is also suitable. If such a coating curing agent is used, a resin composition having high storage stability can be obtained even if a thermosetting agent is blended in advance.
本発明の液晶表示素子用硬化性組成物における上記熱硬化剤の配合量の下限は、上記硬化性樹脂１００重量部に対して３重量部、上限は４０重量部である。３重量部未満又は４０重量部を超えると、硬化物の接着性、耐薬品性が低下し、高温高湿動作試験での液晶の特性劣化が早まる。好ましい下限は５重量部、好ましい上限は２５重量部である。 The minimum of the compounding quantity of the said thermosetting agent in the curable composition for liquid crystal display elements of this invention is 3 weight part with respect to 100 weight part of said curable resins, and an upper limit is 40 weight part. If it is less than 3 parts by weight or more than 40 parts by weight, the adhesiveness and chemical resistance of the cured product are lowered, and the characteristic deterioration of the liquid crystal in the high temperature and high humidity operation test is accelerated. A preferred lower limit is 5 parts by weight and a preferred upper limit is 25 parts by weight.
本発明の液晶表示素子用硬化性組成物は、更に、熱ラジカル重合開始剤を含有してもよい。上記熱ラジカル重合開始剤としては特に限定されず、例えば、アゾブチロニトリル（ＡＩＢＮ）等のアゾ化合物、過酸化ベンゾイル（ＢＰＯ）等の過酸化物等が挙げられる。 The curable composition for liquid crystal display elements of the present invention may further contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is not particularly limited, and examples thereof include azo compounds such as azobutyronitrile (AIBN), peroxides such as benzoyl peroxide (BPO), and the like.
本発明の樹脂組成物は、シランカップリング剤を含有していてもよい。シランカップリング剤は、主に本発明の樹脂組成物をシール剤又は上下導通用材料として用いた場合に、透明基板との接着性を向上させる接着助剤としての役割を有する。
上記シランカップリング剤としては特に限定されないが、基板等との接着性向上効果に優れ、硬化性樹脂と化学結合することにより液晶材料中への流出を防止するとができることから、例えば、γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−イソシアネートプロピルトリメトキシシラン等が好適に用いられる。これらのシランカップリング剤は単独で用いてもよく、２種以上を併用してもよい。
The resin composition of the present invention may contain a silane coupling agent. The silane coupling agent has a role as an adhesion aid for improving the adhesion to the transparent substrate mainly when the resin composition of the present invention is used as a sealing agent or a material for vertical conduction.
The silane coupling agent is not particularly limited, but is excellent in the effect of improving adhesion to a substrate and the like, and can be prevented from flowing into the liquid crystal material by chemically bonding with a curable resin. Propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane and the like are preferably used. These silane coupling agents may be used alone or in combination of two or more.
本発明の樹脂組成物は、応力分散効果による接着性の改善、線膨張率の改善等のためにフィラーを含有してもよい。上記フィラーとしては特に限定されず、例えば、シリカ、珪藻土、アルミナ、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、水酸化マグネシウム、水酸化アルミニウム、炭酸マグネシウム、硫酸バリウム、石膏、珪酸カルシウム、タルク、ガラスビーズ、セリサイト活性白土、ベントナイト、窒化アルミニウム、窒化珪素等の無機フィラー等が挙げられる。 The resin composition of the present invention may contain a filler for the purpose of improving adhesiveness due to the stress dispersion effect, improving the linear expansion coefficient, and the like. The filler is not particularly limited. For example, silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, gypsum, calcium silicate , Talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride, and other inorganic fillers.
本発明の樹脂組成物を製造する方法としては特に限定されず、上記硬化性樹脂及び熱硬化剤等を、従来公知の方法により混合する方法等が挙げられる。このとき、イオン性の不純物を除去するために層状珪酸塩鉱物等のイオン吸着性固体と接触させてもよい。 It does not specifically limit as a method to manufacture the resin composition of this invention, The method etc. which mix the said curable resin, a thermosetting agent, etc. by a conventionally well-known method are mentioned. At this time, in order to remove ionic impurities, it may be brought into contact with an ion-adsorbing solid such as a layered silicate mineral.
本発明の樹脂組成物は、１分子中に水素結合性官能基と２以上の（メタ）アクリル基とを有し、１分子中の水素結合性官能基量が３．５×１０-3以上である硬化性樹脂、熱硬化剤を含有することから、樹脂成分の溶出による液晶の汚染がほとんどなく、液晶表示素子用のシール剤又は上下導通用材料として滴下工法による液晶表示素子の製造に用いた場合にも、液晶を汚染しにくく、色むら等の少ない画像表示が可能な液晶表示素子が得られる。
本発明の液晶表示素子用硬化性樹脂組成物からなる液晶滴下工法用シール剤もまた、本発明の１つである。
The resin composition of the present invention has a hydrogen bonding functional group and two or more (meth) acryl groups in one molecule, and the amount of the hydrogen bonding functional group in one molecule is 3.5 × 10 −3 or more. Because it contains a curable resin and a thermosetting agent, there is almost no contamination of the liquid crystal due to elution of the resin component, and it is used for manufacturing a liquid crystal display element by a dripping method as a sealing agent for liquid crystal display elements or a material for vertical conduction In this case, it is possible to obtain a liquid crystal display element which can hardly contaminate the liquid crystal and can display an image with little color unevenness.
The sealing agent for a liquid crystal dropping method comprising the curable resin composition for a liquid crystal display element of the present invention is also one aspect of the present invention.
本発明の液晶表示素子用硬化性樹脂組成物及び／又は本発明の液晶滴下工法用シール剤に、導電性微粒子を配合することにより、上下導通材料を製造することができる。このような上下導通材料を用いれば、液晶を汚染することなく透明基板の電極を導電接続することができる。
本発明の液晶表示素子用硬化性樹脂組成物及び／又は本発明の液晶滴下工法用シール剤と、導電性微粒子とを含有する上下導通材料もまた、本発明の１つである。
A vertical conduction material can be produced by blending conductive fine particles with the curable resin composition for a liquid crystal display element of the present invention and / or the sealing agent for a liquid crystal dropping method of the present invention. By using such a vertical conduction material, the electrodes of the transparent substrate can be conductively connected without contaminating the liquid crystal.
The vertical conduction material containing the curable resin composition for liquid crystal display elements of the present invention and / or the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
上記導電性微粒子としては特に限定されず、金属ボール、樹脂微粒子の表面に導電金属層を形成したもの等を用いることができる。なかでも、樹脂微粒子の表面に導電金属層を形成したものは、樹脂微粒子の優れた弾性により、透明基板等を損傷することなく導電接続が可能であることから好適である。 The conductive fine particles are not particularly limited, and metal balls, those obtained by forming a conductive metal layer on the surface of resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
本発明の液晶滴下工法用シール剤及び／又は本発明の上下導通材料を用いてなる液晶表示素子もまた、本発明の１つである。 The liquid crystal display element using the sealing compound for liquid crystal dropping method of the present invention and / or the vertical conduction material of the present invention is also one aspect of the present invention.
本発明によれば、滴下工法による液晶表示素子の製造における液晶滴下工法用シール剤に用いた場合にも、液晶を汚染しにくく、色むら等の少ない画像表示が可能な液晶表示素子が得られる液晶表示素子用硬化性組成物、該液晶表示素子用硬化性組成物からなる液晶滴下工法用シール剤、上下導通用材料及び液晶表示素子を提供できる。 According to the present invention, a liquid crystal display element capable of displaying an image with little color unevenness is obtained even when used as a sealant for a liquid crystal dropping method in the production of a liquid crystal display element by a dropping method. A curable composition for liquid crystal display elements, a sealing agent for liquid crystal dropping method comprising the curable composition for liquid crystal display elements, a material for vertical conduction, and a liquid crystal display element can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
固体のビスフェノールＡジグリシジルエーテル（大日本インキ化学社製「８５０ＣＲＰ」）１３６０重量部、重合禁止剤としてｐ−メトキシフェノール２重量部、反応触媒としてトリエチルアミン２重量部、アクリル酸５７６重量部を、空気を送り込みながら１１０℃で還流攪拌して、５時間反応させた。得られた樹脂１００重量部を、反応物中のイオン性不純物を吸着させるために、クオルツとカオリンとの天然結合物（ホフマンミネラル社製「シリチンＶ８５」）１０重量部が充填されたカラムで濾過し、アクリル酸変性ビスフェノールＡエポキシ樹脂を得た。
得られたアクリル酸変性ビスフェノールＡエポキシ樹脂の水素結合性官能基量を算出したところ、４．１×１０-3であった。
Example 1
1360 parts by weight of solid bisphenol A diglycidyl ether (Dainippon Ink & Chemicals "850CRP"), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 576 parts by weight of acrylic acid, The mixture was refluxed and stirred at 110 ° C. for 5 hours. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (“Siritin V85” manufactured by Hoffman Mineral Co.). As a result, an acrylic acid-modified bisphenol A epoxy resin was obtained.
The amount of the hydrogen bonding functional group of the obtained acrylic acid-modified bisphenol A epoxy resin was calculated to be 4.1 × 10 −3 .
次に、得られたアクリル酸変性ビスフェノールＡエポキシ樹脂６０重量部、潜在性熱硬化剤としてヒドラジド系硬化剤（味の素ファインテクノ社製、アミキュアＶＤＨ）１５重量部、シリカ粒子（平均粒径１．５μｍ）２２重量部、γ−グリシドキシプロピルトリメトキシシラン１重量部を均一な液となるように三本ロールを用いて充分に混合し、液晶表示素子用硬化性樹脂組成物を得た。 Next, 60 parts by weight of the resulting acrylic acid-modified bisphenol A epoxy resin, 15 parts by weight of a hydrazide-based curing agent (Ajinomoto Fine Techno Co., Amicure VDH) as a latent thermosetting agent, silica particles (average particle size 1.5 μm) ) 22 parts by weight and 1 part by weight of γ-glycidoxypropyltrimethoxysilane were sufficiently mixed using a three roll so as to form a uniform liquid, thereby obtaining a curable resin composition for a liquid crystal display device.
得られた液晶表示素子用硬化性樹脂組成物を液晶滴下工法用シール剤とし、透明電極付きの２枚の透明基板の一方に、液晶滴下工法用シール剤を長方形の枠を描くようにディスペンサーで塗布した。続いて、液晶（チッソ社製、ＪＣ−５００４ＬＡ）の微小滴を透明基板の枠内全面に滴下塗布し、その後、液晶アニールを１２０℃にて１時間行い熱硬化させ、液晶表示セルを作製した。
得られた液晶表示セルについて、６０℃、９５％ＲＨ、５００時間放置前後に、シール部周辺の液晶に生じる色むらを目視で観察したところ、色むらは全く認められなかった。
The obtained curable resin composition for a liquid crystal display element is used as a sealing agent for a liquid crystal dropping method, and the dispenser is used to draw a rectangular frame on one of two transparent substrates with a transparent electrode. Applied. Subsequently, fine droplets of liquid crystal (manufactured by Chisso Co., Ltd., JC-5004LA) were dropped onto the entire surface of the transparent substrate frame, and then liquid crystal annealing was performed at 120 ° C. for 1 hour to thermally cure, thereby producing a liquid crystal display cell. .
When the obtained liquid crystal display cell was visually observed for color unevenness generated in the liquid crystal around the seal portion before and after being left at 60 ° C. and 95% RH for 500 hours, no color unevenness was observed.
（比較例１）
硬化性樹脂として、実施例１で調製したアクリル酸変性ビスフェノールＡエポキシ樹脂３０重量部とビスフェノールＡ型エポキシ樹脂（大日本インキ化学工業社製「８５０ＣＲＰ」）３０重量部との混合樹脂を用いた以外は、実施例１と同様の方法により液晶表示素子用硬化性樹脂組成物を得、これを液晶滴下工法用シール剤として液晶表示セルを製造した。
この混合樹脂の水素結合性官能基量を算出したところ、２．１×１０-3であった。
得られた液晶表示セルについて、６０℃、９５％ＲＨ、５００時間放置前後に、シール部周辺の液晶に生じる色むらを目視で観察したところ、一部に色むらが認められた。
(Comparative Example 1)
As the curable resin, a mixed resin of 30 parts by weight of acrylic acid-modified bisphenol A epoxy resin prepared in Example 1 and 30 parts by weight of bisphenol A type epoxy resin (“850CRP” manufactured by Dainippon Ink and Chemicals, Inc.) was used. Obtained the curable resin composition for liquid crystal display elements by the method similar to Example 1, and manufactured the liquid crystal display cell by using this as the sealing compound for liquid crystal dropping methods.
It was 2.1 * 10 < -3 > when the amount of hydrogen bondable functional groups of this mixed resin was computed.
When the obtained liquid crystal display cell was visually observed for color unevenness generated in the liquid crystal around the seal portion before and after being left at 60 ° C. and 95% RH for 500 hours, color unevenness was partially recognized.
本発明によれば、滴下工法による液晶表示素子の製造における液晶滴下工法用シール剤に用いた場合にも、液晶を汚染しにくく、色むら等の少ない画像表示が可能な液晶表示素子が得られる液晶表示素子用硬化性組成物、該液晶表示素子用硬化性組成物からなる液晶滴下工法用シール剤、上下導通用材料及び液晶表示素子を提供できる。
According to the present invention, a liquid crystal display element capable of displaying an image with little color unevenness is obtained even when used as a sealant for a liquid crystal dropping method in the production of a liquid crystal display element by a dropping method. A curable composition for liquid crystal display elements, a sealing agent for liquid crystal dropping method comprising the curable composition for liquid crystal display elements, a material for vertical conduction, and a liquid crystal display element can be provided.
Claims (7)
１分子中に水素結合性官能基と２以上の（メタ）アクリル基とを有し、１分子内の水素結合性官能基量が３．５×１０-3以上である硬化性樹脂１００重量部に対して、熱硬化剤３〜４０重量部を含有する
ことを特徴とする液晶表示素子用硬化性樹脂組成物。 A curable resin composition for a liquid crystal display element that is cured only by heat,
100 parts by weight of a curable resin having a hydrogen bonding functional group and two or more (meth) acryl groups in one molecule, and the amount of the hydrogen bonding functional group in one molecule is 3.5 × 10 −3 or more A curable resin composition for a liquid crystal display element, comprising 3 to 40 parts by weight of a thermosetting agent.
A liquid crystal display element comprising the sealing agent for liquid crystal dropping method according to claim 5 and / or the material for vertical conduction according to claim 6.
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| JP2004122032A JP3955038B2 (en) | 2004-04-16 | 2004-04-16 | Curable resin composition for liquid crystal display element |
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| JP2004122032A JP3955038B2 (en) | 2004-04-16 | 2004-04-16 | Curable resin composition for liquid crystal display element |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170002632A (en) | 2014-07-24 | 2017-01-06 | 미쓰이 가가쿠 가부시키가이샤 | Liquid crystal sealing agent and production method for liquid crystal display panel |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE554126T1 (en) | 2006-01-26 | 2012-05-15 | Showa Denko Kk | CURABLE COMPOSITION CONTAINING A THIOLEN COMPOUND |
| JP5149487B2 (en) * | 2006-02-22 | 2013-02-20 | 三井化学株式会社 | Liquid crystal sealant and liquid crystal display panel using the same |
| WO2008102550A1 (en) * | 2007-02-20 | 2008-08-28 | Mitsui Chemicals, Inc. | Curable resin composition for sealing liquid crystal, and method for production of liquid crystal display panel using the same |
| JP6676833B1 (en) * | 2018-06-01 | 2020-04-08 | 積水化学工業株式会社 | Method for producing sealant for liquid crystal display element |
-
2004
- 2004-04-16 JP JP2004122032A patent/JP3955038B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170002632A (en) | 2014-07-24 | 2017-01-06 | 미쓰이 가가쿠 가부시키가이샤 | Liquid crystal sealing agent and production method for liquid crystal display panel |
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