TWI815888B - Sealants for liquid crystal display elements, upper and lower conductive materials, and liquid crystal display elements - Google Patents
Sealants for liquid crystal display elements, upper and lower conductive materials, and liquid crystal display elements Download PDFInfo
- Publication number
- TWI815888B TWI815888B TW108116528A TW108116528A TWI815888B TW I815888 B TWI815888 B TW I815888B TW 108116528 A TW108116528 A TW 108116528A TW 108116528 A TW108116528 A TW 108116528A TW I815888 B TWI815888 B TW I815888B
- Authority
- TW
- Taiwan
- Prior art keywords
- liquid crystal
- crystal display
- meth
- acrylate
- display elements
- Prior art date
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 163
- 239000000565 sealant Substances 0.000 title claims abstract description 62
- 239000004020 conductor Substances 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 13
- -1 hydrazine compound Chemical class 0.000 claims description 68
- 239000004593 Epoxy Substances 0.000 claims description 43
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 15
- 239000010419 fine particle Substances 0.000 claims description 9
- 238000007789 sealing Methods 0.000 abstract description 48
- 238000003860 storage Methods 0.000 abstract description 15
- 230000007547 defect Effects 0.000 abstract description 12
- 150000002429 hydrazines Chemical class 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 91
- 239000003822 epoxy resin Substances 0.000 description 41
- 229920000647 polyepoxide Polymers 0.000 description 41
- 239000000126 substance Substances 0.000 description 22
- 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 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 19
- 239000010936 titanium Substances 0.000 description 19
- 229910052719 titanium Inorganic materials 0.000 description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 17
- 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 15
- 239000000758 substrate Substances 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 239000007870 radical polymerization initiator Substances 0.000 description 11
- 229930185605 Bisphenol Natural products 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000011109 contamination Methods 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 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 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- XDUZWPPSSHEDFK-VVXQKDJTSA-N C(C(C)(C)C)C([C@H](O)[C@H](O)CO)O Chemical compound C(C(C)(C)C)C([C@H](O)[C@H](O)CO)O XDUZWPPSSHEDFK-VVXQKDJTSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 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
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 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
- 238000004364 calculation method Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229940050410 gluconate Drugs 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- CYXLGABBVLIUJZ-UHFFFAOYSA-N 2-(2-hydroxypropoxycarbonyl)benzoic acid Chemical compound CC(O)COC(=O)C1=CC=CC=C1C(O)=O CYXLGABBVLIUJZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- RUVNKAUVVBCURD-UHFFFAOYSA-N 2-[[4-[2-[4-(oxiran-2-ylmethoxy)-3-prop-2-enylphenyl]propan-2-yl]-2-prop-2-enylphenoxy]methyl]oxirane Chemical compound C=1C=C(OCC2OC2)C(CC=C)=CC=1C(C)(C)C(C=C1CC=C)=CC=C1OCC1CO1 RUVNKAUVVBCURD-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- PDKDLYHHQBVFJL-UHFFFAOYSA-N 2-hydroxypropyl dihydrogen phosphate Chemical compound CC(O)COP(O)(O)=O PDKDLYHHQBVFJL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-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
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 1
- LOCXTTRLSIDGPS-FVDSYPCUSA-N [(z)-[1-oxo-1-(4-phenylsulfanylphenyl)octan-2-ylidene]amino] benzoate Chemical compound C=1C=C(SC=2C=CC=CC=2)C=CC=1C(=O)C(/CCCCCC)=N\OC(=O)C1=CC=CC=C1 LOCXTTRLSIDGPS-FVDSYPCUSA-N 0.000 description 1
- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 239000004927 clay Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical class [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 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
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-L malate(2-) Chemical compound [O-]C(=O)C(O)CC([O-])=O BJEPYKJPYRNKOW-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004904 shortening Methods 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 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
- 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 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
本發明之目的在於提供一種保存穩定性及硬化性優異，且即便於用於薄型之液晶顯示元件之情形時亦可抑制顯示不良之產生之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 本發明係一種液晶顯示元件用密封劑，其含有硬化性樹脂及熱硬化劑，且上述熱硬化劑含有溶解度參數為37.0（J/cm3 ）1/2 以上且60.0（J/cm3 ）1/2 以下之醯肼化合物。An object of the present invention is to provide a sealing compound for a liquid crystal display element that is excellent in storage stability and curability and that can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Furthermore, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element using the sealant for liquid crystal display elements. The present invention is a sealant for liquid crystal display elements, which contains a curable resin and a thermosetting agent, and the thermosetting agent contains a solubility parameter of 37.0 (J/cm 3 ) 1/2 or more and 60.0 (J/cm 3 ) 1 /2 or less hydrazine compounds.
Description
本發明係關於一種保存穩定性及硬化性優異，且即便於用於薄型之液晶顯示元件之情形時亦可抑制顯示不良之產生之液晶顯示元件密封劑。又，本發明係關於一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。The present invention relates to a liquid crystal display element sealing compound that is excellent in storage stability and curability and can suppress the occurrence of display defects even when used for thin liquid crystal display elements. Furthermore, the present invention relates to an upper and lower conductive material and a liquid crystal display element using the sealant for liquid crystal display elements.
近年來，作為液晶顯示單元等液晶顯示元件之製造方法，就產距時間縮短、使用液晶量之最佳化等觀點而言，使用如專利文獻1、專利文獻2中所揭示之使用密封劑之被稱作滴下工法之液晶滴下方式。 於滴下工法中，首先，於2片之附電極之基板之一者，藉由滴塗形成框狀之密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微小滴滴加至密封圖案之框內，於真空下重疊另一基板後使密封劑硬化，製作液晶顯示元件。目前該滴下工法成為液晶顯示元件之製造方法之主流。In recent years, as a manufacturing method of liquid crystal display elements such as liquid crystal display units, from the viewpoint of shortening the lead time and optimizing the amount of liquid crystal used, sealants using sealants as disclosed in Patent Document 1 and Patent Document 2 have been used. The liquid crystal dripping method is called the dripping method. In the dropping method, first, a frame-shaped sealing pattern is formed on one of the two substrates with electrodes by dropping coating. Then, while the sealant is not hardened, tiny droplets of liquid crystal are added dropwise into the frame of the sealing pattern, another substrate is overlapped under vacuum, and the sealant is hardened to produce a liquid crystal display element. At present, the dripping method has become the mainstream method of manufacturing liquid crystal display elements.
但是，於行動電話、攜帶型遊戲機等各種附液晶面板之行動機器普及之現代，裝置之小型化為最為要求之課題。作為裝置之小型化之方法，可列舉液晶顯示部之窄邊緣化，例如進行將密封部之位置配置於黑矩陣下（以下亦稱作窄邊緣設計）。However, in today's era when various mobile devices equipped with LCD panels such as mobile phones and portable game consoles are widespread, miniaturization of devices has become the most demanding issue. An example of a method for miniaturizing the device is to narrow the edge of the liquid crystal display portion, for example, arranging the position of the sealing portion under the black matrix (hereinafter also referred to as narrow edge design).
然而，於窄邊緣設計中，由於密封劑配置於黑矩陣之正下方，故而若進行滴下工法，則於使密封劑光硬化時照射之光被遮擋，光難以到達密封劑之內部，習知之密封劑中硬化不足。若如此密封劑之硬化不足，則存在未硬化之密封劑成分溶出至液晶中而易於產生液晶污染之問題。However, in the narrow edge design, since the sealant is placed directly under the black matrix, if the dripping method is used, the light irradiated when the sealant is photohardened will be blocked, making it difficult for the light to reach the inside of the sealant. Conventional sealing Insufficient hardening in the agent. If the sealant is not hardened enough in this way, there is a problem that unhardened sealant components are eluted into the liquid crystal and liquid crystal contamination is likely to occur.
於如此難以使密封劑光硬化之情形時，考慮藉由加熱使其硬化，作為用以使密封劑藉由加熱而硬化之方法，進行於密封劑中摻合熱硬化劑。然而，於為了提高密封劑之硬化性而使用對熱之反應性較高之熱硬化劑之情形時，有所獲得之密封劑之保存穩定性較差之情況。 又，近年來，液晶顯示元件之薄型化不斷發展，但存在於薄型之液晶顯示元件中使用習知之密封劑之情形時，有產生顯示不良之情況之問題。 [先前技術文獻] [專利文獻]In such a case where it is difficult to light-cure the sealant, it is considered to harden the sealant by heating. As a method for curing the sealant by heating, a thermosetting agent is blended into the sealant. However, when a thermosetting agent with high reactivity to heat is used in order to improve the curability of the sealant, the storage stability of the obtained sealant may be poor. In addition, in recent years, liquid crystal display elements have been increasingly thinned. However, when conventional sealants are used in thin liquid crystal display elements, there is a problem that display defects occur. [Prior technical literature] [Patent Document]
專利文獻1：日本特開2001-133794號公報 專利文獻2：國際公開第02/092718號Patent Document 1: Japanese Patent Application Publication No. 2001-133794 Patent Document 2: International Publication No. 02/092718
[發明所欲解決之課題][Problem to be solved by the invention]
本發明之目的在於提供一種保存穩定性及硬化性優異，且即便於用於薄型之液晶顯示元件之情形時亦可抑制顯示不良之產生之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 [解決課題之技術手段]An object of the present invention is to provide a sealing compound for a liquid crystal display element that is excellent in storage stability and curability and that can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Furthermore, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element using the sealant for liquid crystal display elements. [Technical means to solve the problem]
本發明係一種液晶顯示元件用密封劑，其含有硬化性樹脂及熱硬化劑，且上述熱硬化劑含有溶解度參數為37.0（J/cm3 ）1/2 以上且60.0（J/cm3 ）1/2 以下之醯肼化合物。 以下對本發明進行詳細說明。The present invention is a sealant for liquid crystal display elements, which contains a curable resin and a thermosetting agent, and the thermosetting agent contains a solubility parameter of 37.0 (J/cm 3 ) 1/2 or more and 60.0 (J/cm 3 ) 1 /2 or less hydrazine compounds. The present invention will be described in detail below.
與液晶顯示元件之薄型化相對應，大多使用極性高者作為液晶，該極性高者包含具有氟基、氯基、氰基等極性基之液晶分子。本發明者認為，於薄型之液晶顯示元件中使用習知之密封劑之情形時產生顯示不良之原因在於，藉由包含具有此種極性基之液晶分子之極性高之液晶與密封劑之相容性（尤其與密封劑中所包含之熱硬化劑之相容性）較高，而易於產生液晶污染。對此，本發明者發現，藉由使用具有特定範圍之溶解度參數之醯肼化合物作為熱硬化劑，可獲得保存穩定性及硬化性優異，且即便於用於薄型之液晶顯示元件之情形時亦可抑制顯示不良之產生之液晶顯示元件用密封劑，從而完成本發明。 再者，本發明之液晶顯示元件用密封劑由於相對於極性較低之習知液晶而言為相容性更低者，故而即便於使用此種習知液晶之液晶顯示元件中亦可抑制顯示不良之產生。In response to the thinning of liquid crystal display elements, liquid crystals with high polarity are mostly used as liquid crystals. The high polarity liquid crystals include liquid crystal molecules having polar groups such as fluorine group, chlorine group, and cyano group. The inventors of the present invention believe that the reason why display defects occur when conventional sealants are used in thin liquid crystal display elements is due to the compatibility between highly polar liquid crystals containing liquid crystal molecules having such polar groups and the sealant. (Especially the compatibility with the thermal hardener contained in the sealant) is high and prone to liquid crystal contamination. In this regard, the present inventors have discovered that by using a chelylhydrazine compound having a solubility parameter in a specific range as a thermal hardener, it is possible to achieve excellent storage stability and curability even when used in a thin liquid crystal display element. The present invention was completed by providing a sealant for liquid crystal display elements that can suppress the occurrence of display defects. Furthermore, since the sealant for liquid crystal display elements of the present invention has lower compatibility than conventional liquid crystals with lower polarity, it can suppress display even in liquid crystal display elements using such conventional liquid crystals. The occurrence of bad things.
本發明之液晶顯示元件用密封劑含有熱硬化劑。 上述熱硬化劑具有藉由加熱與液晶顯示元件用密封劑中之環氧基或(甲基)丙烯醯基形成共價鍵而交聯，提高硬化後之液晶顯示元件用密封劑之接著性及耐濕性之作用。 再者，於本說明書中，上述「(甲基)丙烯醯基」意指丙烯醯基或甲基丙烯醯基。The sealing compound for liquid crystal display elements of the present invention contains a thermosetting agent. The above-mentioned thermosetting agent has the ability to cross-link by forming covalent bonds with the epoxy group or (meth)acryl group in the sealing agent for liquid crystal display elements through heating, thereby improving the adhesion of the hardened sealing agent for liquid crystal display elements and The role of moisture resistance. In addition, in this specification, the above-mentioned "(meth)acrylyl group" means an acrylyl group or a methacrylyl group.
上述熱硬化劑含有溶解度參數（以下亦稱作「SP值」）為37.0（J/cm3 ）1/ 2 以上且60.0（J/cm3 ）1/ 2 以下之醯肼化合物。以下，亦將SP值為37.0（J/cm3 ）1/ 2 以上且60.0（J/cm3 ）1/2 以下之醯肼化合物稱作「本發明之醯肼化合物」。 藉由含有SP值為該範圍之醯肼化合物，本發明之液晶顯示元件用密封劑成為保存穩定性及硬化性優異，且即便於用於薄型之液晶顯示元件之情形時亦可抑制顯示不良之產生者。本發明之醯肼化合物之SP值之較佳之下限為40（J/cm3 ）1/2 ，更佳之下限為45（J/cm3 ）1/2 。 又，本發明之醯肼化合物之SP值之較佳之上限為50.0（J/cm3 ）1/2 。 再者，於本說明書中，上述「SP值」係基於Fedors發明之計算方法而算出之值（參照日本接著學會誌，vol.22，no.10（1986）（53）（566）（Journal of Adhesion Society of Japan）等）。於該計算方法中，由於不需要密度之值，故而可容易地算出溶解度參數。上述Fedors之理論SP值利用以下之式算出。 SP值＝（∑Δei/∑Δvi）1/2 其中，∑Δei係原子及原子團之蒸發能之和，∑Δvi＝莫耳體積之和。The above-mentioned thermal hardener contains a hydrazine compound with a solubility parameter (hereinafter also referred to as "SP value") of 37.0 (J/cm 3 ) 1/2 or more and 60.0 (J/cm 3 ) 1/2 or less. Hereinafter, a hydrazine compound with an SP value of 37.0 (J/cm 3 ) 1/2 or more and 60.0 (J/cm 3 ) 1/2 or less is also referred to as "the hydrazine compound of the present invention". By containing a hydrazine compound with an SP value within this range, the sealing compound for liquid crystal display elements of the present invention has excellent storage stability and curability, and can suppress display defects even when used for thin liquid crystal display elements. Producer. The preferred lower limit of the SP value of the hydrazine compound of the present invention is 40 (J/cm 3 ) 1/2 , and the more preferred lower limit is 45 (J/cm 3 ) 1/2 . Furthermore, a preferable upper limit of the SP value of the hydrazine compound of the present invention is 50.0 (J/cm 3 ) 1/2 . In addition, in this specification, the above-mentioned "SP value" is a value calculated based on the calculation method invented by Fedors (see Journal of the Japan Society of Bonding, vol. 22, no. 10 (1986) (53) (566) (Journal of Adhesion Society of Japan), etc.). In this calculation method, since the value of density is not required, the solubility parameter can be easily calculated. The theoretical SP value of the above Fedors is calculated using the following formula. SP value = (ΣΔei/ΣΔvi) 1/2 where, ΣΔei is the sum of the evaporation energies of atoms and atomic groups, and ΣΔvi = the sum of molar volumes.
本發明之醯肼化合物較佳為於1分子中具有1個以上之羥基。藉由本發明之醯肼化合物於1分子中具有1個以上之羥基，所獲得之液晶顯示元件用密封劑成為兼具保存穩定性及硬化性之效果更優異者。The hydrazine compound of the present invention preferably has one or more hydroxyl groups in one molecule. Since the hydrazine compound of the present invention has one or more hydroxyl groups in one molecule, the sealing compound for a liquid crystal display element obtained has a better effect of having both storage stability and curability.
作為本發明之醯肼化合物，具體而言，例如可列舉：蘋果酸二醯肼（SP值39.7（J/cm3 ）1/2 ）、2-羥基丙烷-1,2,3-三卡肼（SP值40.5（J/cm3 ）1/2 ）、酒石酸二醯肼（SP值45.9（J/cm3 ）1/2 ）、葡萄糖酸醯肼（SP值48.5（J/cm3 ）1/2 ）等。其中，較佳為選自由2-羥基丙烷-1,2,3-三卡肼、酒石酸二醯肼、及葡萄糖酸醯肼所組成之群中之至少1種。Specific examples of the hydrazine compound of the present invention include dihydrazide malate (SP value: 39.7 (J/cm 3 ) 1/2 ), 2-hydroxypropane-1,2,3-tricarbazide (SP value 40.5 (J/cm 3 ) 1/2 ), dihydrazide tartrate (SP value 45.9 (J/cm 3 ) 1/2 ), gluconate hydrazine (SP value 48.5 (J/cm 3 ) 1/ 2 ) etc. Among them, at least one selected from the group consisting of 2-hydroxypropane-1,2,3-tricarbohydrazine, dihydrazide tartrate, and gluconate hydrazine is preferred.
上述熱硬化劑中之本發明之醯肼化合物之含有比率較佳為80莫耳%以上，更佳為90莫耳%以上，進而較佳為95莫耳%以上，最佳為100莫耳%。The content ratio of the chelazine compound of the present invention in the above-mentioned thermal hardener is preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and most preferably 100 mol% .
上述熱硬化劑之含量相對於硬化性樹脂100重量份，較佳之下限為1重量份，較佳之上限為10重量份。藉由上述熱硬化劑之含量為該範圍，所獲得之液晶顯示元件用密封劑成為兼具保存穩定性及硬化性之效果更優異者。上述熱硬化劑之含量之更佳之下限為3重量份，更佳之上限為8重量份。The content of the above-mentioned thermal hardener is preferably lower limit is 1 part by weight and upper limit is preferably 10 parts by weight relative to 100 parts by weight of the curable resin. When the content of the thermosetting agent is within this range, the sealing compound for a liquid crystal display element obtained has a more excellent effect of both storage stability and curing properties. A more preferable lower limit of the content of the thermal hardener is 3 parts by weight, and a more preferable upper limit is 8 parts by weight.
本發明之液晶顯示元件用密封劑含有硬化性樹脂。 上述硬化性樹脂較佳為含有環氧化合物。 作為上述環氧化合物，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚E型環氧樹脂、雙酚S型環氧樹脂、2,2'-二芳基雙酚A型環氧樹脂、氫化雙酚型環氧樹脂、環氧丙烷加成雙酚A型環氧樹脂、間苯二酚型環氧樹脂、聯苯型環氧樹脂、硫醚型環氧樹脂、二苯醚型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、酚系酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、二環戊二烯酚醛清漆型環氧樹脂、聯苯酚醛清漆型環氧樹脂、萘酚系酚醛清漆型環氧樹脂、縮水甘油胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧樹脂、縮水甘油酯化合物等。The sealing compound for liquid crystal display elements of the present invention contains curable resin. The curable resin preferably contains an epoxy compound. Examples of the epoxy compound include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol E-type epoxy resin, bisphenol S-type epoxy resin, and 2,2'-diaryl Bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, thioether epoxy Resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenolic novolak type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene Novolak-type epoxy resin, biphenyl novolak-type epoxy resin, naphthol-based novolak-type epoxy resin, glycidylamine-type epoxy resin, alkyl polyol-type epoxy resin, rubber-modified epoxy resin , glycidyl ester compounds, etc.
作為上述雙酚A型環氧樹脂中之市售者，例如可列舉jER828EL、jER1004（均為三菱化學公司製造）、Epiclon850（DIC公司製造）等。 作為上述雙酚F型環氧樹脂中之市售者，例如可列舉jER806、jER4004（均為三菱化學公司製造）等。 作為上述雙酚E型環氧樹脂中之市售者，例如可列舉Epomic R710（三井化學公司製造）等。 作為上述雙酚S型環氧樹脂中之市售者，例如可列舉Epiclon EXA1514（DIC公司製造）等。 作為上述2,2'-二芳基雙酚A型環氧樹脂中之市售者，例如可列舉RE-810NM（日本化藥公司製造）等。 作為上述氫化雙酚型環氧樹脂中之市售者，例如可列舉Epiclon EXA7015（DIC公司製造）等。 作為上述環氧丙烷加成雙酚A型環氧樹脂中之市售者，例如可列舉EP-4000S（ADEKA公司製造）等。 作為上述間苯二酚型環氧樹脂中之市售者，例如可列舉EX-201（Nagase chemteX公司製造）等。 作為上述聯苯型環氧樹脂中之市售者，例如可列舉jER YX-4000H（三菱化學公司製造）等。 作為上述硫醚型環氧樹脂中之市售者，例如可列舉YSLV-50TE（NIPPON STEEL Chemical & Material公司製造）等。 作為上述二苯醚型環氧樹脂中之市售者，例如可列舉YSLV-80DE（NIPPON STEEL Chemical & Material公司製造）等。 作為上述二環戊二烯型環氧樹脂中之市售者，例如可列舉EP-4088S（ADEKA公司製造）等。 作為上述萘型環氧樹脂中之市售者，例如可列舉Epiclon HP4032、Epiclon EXA-4700（均為DIC公司製造）等。 作為上述酚系酚醛清漆型環氧樹脂中之市售者，例如可列舉Epiclon N-770（DIC公司製造）等。 作為上述鄰甲酚酚醛清漆型環氧樹脂中之市售者，例如可列舉Epiclon N-670-EXP-S（DIC公司製造）等。 作為上述二環戊二烯酚醛清漆型環氧樹脂中之市售者，例如可列舉Epiclon HP7200（DIC公司製造）等。 作為上述聯苯酚醛清漆型環氧樹脂中之市售者，例如可列舉NC-3000P（日本化藥公司製造）等。 作為上述萘酚系酚醛清漆型環氧樹脂中之市售者，例如可列舉ESN-165S（NIPPON STEEL Chemical & Material公司製造）等。 作為上述縮水甘油胺型環氧樹脂中之市售者，例如可列舉jER630（三菱化學公司製造）、Epiclon430（DIC公司製造）、TETRAD-X（三菱瓦斯化學公司製造）等。 作為上述烷基多元醇型環氧樹脂中之市售者，例如可列舉ZX-1542（NIPPON STEEL Chemical & Material公司製造）、Epiclon726（DIC公司製造）、Epolight 80MFA（共榮社化學公司製造）、Denacol EX-611（Nagase chemteX公司製造）等。 作為上述橡膠改質型環氧樹脂中之市售者，例如可列舉YR-450、YR-207（均為NIPPON STEEL Chemical & Material公司製造）、Epolead PB（Daicel公司製造）等。 作為上述縮水甘油酯化合物中之市售者，例如可列舉Denacol EX-147（Nagase chemteX公司製造）等。 作為上述環氧化合物中之其他市售者，例如可列舉YDC-1312、YSLV-80XY、YSLV-90CR（均為NIPPON STEEL Chemical & Material公司製造）、XAC4151（旭化成公司製造）、jER1031、jER1032（均為三菱化學公司製造）、EXA-7120（DIC公司製造）、TEPIC（日產化學公司製造）等。Examples of commercially available bisphenol A-type epoxy resins include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), Epiclon850 (manufactured by DIC Corporation), and the like. Examples of commercially available bisphenol F-type epoxy resins include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation). Examples of commercially available bisphenol E-type epoxy resins include Epomic R710 (manufactured by Mitsui Chemicals Co., Ltd.). Examples of commercially available bisphenol S-type epoxy resins include Epiclon EXA1514 (manufactured by DIC Corporation). Examples of commercially available 2,2'-diarylbisphenol A-type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available hydrogenated bisphenol-type epoxy resins include Epiclon EXA7015 (manufactured by DIC Corporation). Examples of commercially available propylene oxide-added bisphenol A-type epoxy resins include EP-4000S (manufactured by ADEKA). Examples of commercially available resorcinol-type epoxy resins include EX-201 (manufactured by Nagase ChemteX Co., Ltd.). Examples of commercially available biphenyl-type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation). Examples of commercially available sulfide-type epoxy resins include YSLV-50TE (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.). Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.). Examples of commercially available dicyclopentadiene-type epoxy resins include EP-4088S (manufactured by ADEKA). Examples of commercially available naphthalene-type epoxy resins include Epiclon HP4032 and Epiclon EXA-4700 (both manufactured by DIC Corporation). Examples of commercially available phenolic novolac-type epoxy resins include Epiclon N-770 (manufactured by DIC Corporation). Examples of commercially available o-cresol novolak type epoxy resins include Epiclon N-670-EXP-S (manufactured by DIC Corporation). Examples of commercially available dicyclopentadiene novolak-type epoxy resins include Epiclon HP7200 (manufactured by DIC Corporation). Examples of commercially available biphenyl novolak-type epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available naphthol-based novolak-type epoxy resins include ESN-165S (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.). Examples of commercially available glycidyl amine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), Epiclon430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like. Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), Epiclon726 (manufactured by DIC Co., Ltd.), Epolight 80MFA (manufactured by Kyeisha Chemical Co., Ltd.), Denacol EX-611 (manufactured by Nagase chemteX Corporation), etc. Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (all manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), Epolead PB (manufactured by Daicel Corp.), and the like. Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Co., Ltd.). Examples of other commercially available epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), XAC4151 (all manufactured by Asahi Kasei Co., Ltd.), jER1031, and jER1032 (all manufactured by (manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), etc.
作為上述環氧化合物，亦可較佳地使用部分(甲基)丙烯酸改質環氧樹脂。 再者，於本說明書中，上述所謂部分(甲基)丙烯酸改質環氧樹脂，意指可藉由使具有2個以上之環氧基之環氧化合物之一部分之環氧基與(甲基)丙烯酸反應而獲得的於1分子中具有分別1個以上之環氧基及(甲基)丙烯醯基之化合物。As the above-mentioned epoxy compound, a partially (meth)acrylic acid-modified epoxy resin can also be preferably used. Furthermore, in this specification, the above-mentioned partially (meth)acrylic modified epoxy resin means that it can be modified by combining an epoxy group of a part of an epoxy compound having two or more epoxy groups with a (methyl) ) A compound obtained by reacting acrylic acid and having at least one epoxy group and one (meth)acrylyl group in one molecule.
作為上述部分(甲基)丙烯酸改質環氧樹脂中之市售者，例如可列舉UVACURE1561、KRM8287（均為Daicel-Allnex公司製造）等。Examples of commercially available partially (meth)acrylic modified epoxy resins include UVACURE1561 and KRM8287 (both manufactured by Daicel-Allnex).
上述硬化性樹脂100重量份中之上述環氧化合物之含量之較佳之下限為5重量份，較佳之上限為60重量份。藉由上述環氧化合物之含量為該範圍，所獲得之液晶顯示元件用密封劑成為硬化性及低液晶污染性更優異者。上述環氧化合物之含量之更佳之上限為45重量份。The preferred lower limit of the content of the above-mentioned epoxy compound in 100 parts by weight of the above-mentioned curable resin is 5 parts by weight, and the preferred upper limit is 60 parts by weight. When the content of the above-mentioned epoxy compound is within this range, the sealing compound for liquid crystal display elements obtained becomes one that is more excellent in curability and low liquid crystal contamination properties. A more preferable upper limit of the content of the above-mentioned epoxy compound is 45 parts by weight.
又，上述硬化性樹脂亦可包含(甲基)丙烯酸化合物。作為上述(甲基)丙烯酸化合物，例如可列舉：(甲基)丙烯酸酯化合物、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺酯等。其中，較佳為環氧(甲基)丙烯酸酯。又，就反應性較高而言，上述(甲基)丙烯酸化合物較佳為於1分子中具有2個以上之(甲基)丙烯醯基者。 再者，於本說明書中，上述所謂「(甲基)丙烯酸」意指丙烯酸或甲基丙烯酸，上述所謂「(甲基)丙烯酸化合物」意指具有(甲基)丙烯醯基之化合物。又，上述所謂「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯，上述所謂「環氧(甲基)丙烯酸酯」表示使環氧化合物中之全部環氧基與(甲基)丙烯酸反應而得之化合物。Moreover, the said curable resin may contain a (meth)acrylic acid compound. Examples of the (meth)acrylic compound include (meth)acrylic acid ester compounds, epoxy (meth)acrylic acid esters, (meth)acrylic acid amine esters, and the like. Among them, epoxy (meth)acrylate is preferred. Moreover, in terms of high reactivity, the (meth)acrylic acid compound preferably has two or more (meth)acrylyl groups in one molecule. In addition, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylic acid compound" means a compound having a (meth)acrylyl group. In addition, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" means that all the epoxy groups in the epoxy compound are combined with (methyl) A compound obtained by the reaction of acrylic acid.
作為上述(甲基)丙烯酸酯化合物中之單官能者，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、甲基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、醯亞胺(甲基)丙烯酸酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、琥珀酸2-(甲基)丙烯醯氧基乙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙基2-羥基丙基酯、磷酸2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸縮水甘油酯等。Examples of the monofunctional ones among the above-mentioned (meth)acrylate compounds include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid n-butyl ester Ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isocamphenyl methacrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, methyl carbitol ( Meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth)acrylic acid 1H,1H,5H -Octafluoropentyl, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acrylamide succinate Oxyethyl ester, 2-(meth)acryloxyethyl hexahydrophthalate, 2-(meth)acryloxyethyl 2-hydroxypropyl phthalate, 2-hydroxypropyl phosphate (Meth)acryloyloxyethyl ester, (meth)acrylic acid glycidyl ester, etc.
又，作為上述(甲基)丙烯酸酯化合物中之2官能者，例如可列舉：1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、二羥甲基二環戊二烯基二(甲基)丙烯酸酯、環氧乙烷改質異三聚氰酸二(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、碳酸酯二醇二(甲基)丙烯酸酯、聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己內酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。Moreover, examples of the bifunctional ones among the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylate. , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol diacrylate (Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol Alcohol di(meth)acrylate, ethylene oxide added to bisphenol A di(meth)acrylate, propylene oxide added to bisphenol A di(meth)acrylate, ethylene oxide added to bisphenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanurate di(meth)acrylate, (meth) 2-hydroxy-3-(meth)acryloyloxypropyl acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate ) acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.
又，作為上述(甲基)丙烯酸酯化合物中之3官能以上者，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成異三聚氰酸三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、環氧丙烷加成甘油三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、磷酸三(甲基)丙烯醯氧乙酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等。Furthermore, examples of the above-mentioned (meth)acrylate compounds having trifunctional or higher functions include: trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, ) Acrylate, propylene oxide added to trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide added to isocyanuride Acid tri(meth)acrylate, glyceryl tri(meth)acrylate, propylene oxide addition glyceryl tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, phosphate tri(meth)acrylate Acryloxyethyl ester, di-trimethylolpropane tetra(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, dineopenterythritol Alcohol hexa(meth)acrylate, etc.
作為上述環氧(甲基)丙烯酸酯，例如可列舉使環氧化合物與(甲基)丙烯酸依據常法於鹼性觸媒之存在下進行反應而得者等。Examples of the epoxy (meth)acrylate include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of an alkaline catalyst according to a common method.
作為成為用以合成上述環氧(甲基)丙烯酸酯之原料之環氧化合物，可使用與上文作為本發明之液晶顯示元件用密封劑所含有之硬化性樹脂所述之環氧化合物相同者。As the epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth)acrylate, the same epoxy compound as described above as the curable resin contained in the sealing compound for liquid crystal display elements of the present invention can be used. .
作為上述環氧(甲基)丙烯酸酯中之市售者，例如可列舉Daicel-Allnex公司製造之環氧(甲基)丙烯酸酯、新中村化學工業公司製造之環氧(甲基)丙烯酸酯、共榮社化學公司製造之環氧(甲基)丙烯酸酯、Nagase chemteX公司製造之環氧(甲基)丙烯酸酯等。 作為上述Daicel-Allnex公司製造之環氧(甲基)丙烯酸酯，例如可列舉EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3708、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182等。 作為上述新中村化學工業公司製造之環氧(甲基)丙烯酸酯，例如可列舉EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020等。 作為上述共榮社化學公司製造之環氧(甲基)丙烯酸酯，例如可列舉Epoxy Ester M-600A、Epoxy Ester 40EM、Epoxy Ester 70PA、Epoxy Ester 200PA、Epoxy Ester 80MFA、Epoxy Ester 3002M、Epoxy Ester 3002A、Epoxy Ester 1600A、Epoxy Ester 3000M、Epoxy Ester 3000A、Epoxy Ester 200EA、Epoxy Ester 400EA等。 作為上述Nagase chemteX公司製造之環氧(甲基)丙烯酸酯，例如可列舉Denacol Acrylate DA-141、Denacol Acrylate DA-314、Denacol Acrylate DA-911等。Examples of commercially available epoxy (meth)acrylates include epoxy (meth)acrylates manufactured by Daicel-Allnex Co., Ltd., epoxy (meth)acrylates manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Epoxy (meth)acrylate manufactured by Kyeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase chemteX Co., Ltd., etc. Examples of the epoxy (meth)acrylates manufactured by Daicel-Allnex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, and EBECRYL3800. , EBECRYL6040, EBECRYL RDX63182, etc. Examples of the epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020, and the like. Examples of the epoxy (meth)acrylates manufactured by Kyeisha Chemical Co., Ltd. include Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, and Epoxy Ester 3002A. , Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA, etc. Examples of the epoxy (meth)acrylate manufactured by Nagase ChemteX include Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911, and the like.
上述(甲基)丙烯酸胺酯例如可藉由使具有羥基之(甲基)丙烯酸衍生物與異氰酸酯化合物於觸媒量之錫系化合物存在下進行反應而獲得。The above-mentioned (meth)acrylic acid amine ester can be obtained, for example, by reacting a (meth)acrylic acid derivative having a hydroxyl group and an isocyanate compound in the presence of a catalyst amount of a tin-based compound.
作為上述異氰酸酯化合物，例如可列舉：異佛爾酮二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯（MDI）、氫化MDI、聚合MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯（XDI）、氫化XDI、離胺酸二異氰酸酯、三苯基甲烷三異氰酸酯、硫代磷酸三(異氰酸基苯基)酯、四甲基苯二甲基二異氰酸酯、1,6,11-十一烷三異氰酸酯等。Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diisocyanate. Phenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, toluidine diisocyanate, xylylene diisocyanate (XDI) , Hydrogenated Triisocyanate, etc.
又，作為上述異氰酸酯化合物，亦可使用藉由多元醇與過量之異氰酸酯化合物之反應而獲得之經擴鏈之異氰酸酯化合物。 作為上述多元醇，例如可列舉：乙二醇、丙二醇、甘油、山梨醇、三羥甲基丙烷、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等。Furthermore, as the isocyanate compound, a chain-extended isocyanate compound obtained by reaction of a polyol and an excess isocyanate compound can also be used. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.
作為上述具有羥基之(甲基)丙烯酸衍生物，例如可列舉：單(甲基)丙烯酸羥基烷基酯、二元醇之單(甲基)丙烯酸酯、三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等。 作為上述單(甲基)丙烯酸羥基烷基酯，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。 作為上述二元醇，例如可列舉：乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、聚乙二醇等。 作為上述三元醇，例如可列舉：三羥甲基乙烷、三羥甲基丙烷、甘油等。 作為上述環氧(甲基)丙烯酸酯，例如可列舉雙酚A型環氧丙烯酸酯等。Examples of the (meth)acrylic acid derivatives having a hydroxyl group include: hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of dihydric alcohol, and mono(meth)acrylic acid of trihydric alcohol. Ester or di(meth)acrylate, epoxy (meth)acrylate, etc. Examples of the above-mentioned hydroxyalkyl mono(meth)acrylate include: (2-hydroxyethylmeth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, and the like. Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, glycerin, and the like. Examples of the epoxy (meth)acrylate include bisphenol A-type epoxy acrylate.
作為上述(甲基)丙烯酸胺酯中之市售者，例如可列舉：東亞合成公司製造之(甲基)丙烯酸胺酯、Daicel-Allnex公司製造之(甲基)丙烯酸胺酯、根上工業公司製造之(甲基)丙烯酸胺酯、新中村化學工業公司製造之(甲基)丙烯酸胺酯、共榮社化學公司製造之(甲基)丙烯酸胺酯等。 作為上述東亞合成公司製造之(甲基)丙烯酸胺酯，例如可列舉M-1100、M-1200、M-1210、M-1600等。 作為上述Daicel-Allnex公司製造之(甲基)丙烯酸胺酯，例如可列舉EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、EBECRYL8803、EBECRYL8804、EBECRYL8807、EBECRYL9260。 作為上述根上工業公司製造之(甲基)丙烯酸胺酯，例如可列舉Art Resin UN-330、Art Resin SH-500B、Art Resin UN-1200TPK、Art Resin UN-1255、Art Resin UN-3320HB、Art Resin UN-7100、Art Resin UN-9000A、Art Resin UN-9000H等。 作為上述新中村化學工業公司製造之(甲基)丙烯酸胺酯，例如可列舉U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6HA、U-6LPA、U-10H、U-15HA、U-108、U-108A、U-122A、U-122P、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4000、UA-4100、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A等。 作為上述共榮社化學公司製造之(甲基)丙烯酸胺酯，例如可列舉AH-600、AI-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T等。Examples of commercially available (meth)acrylic acid urethanes include Toagosei Co., Ltd.'s (meth)acrylic acid urethane, Daicel-Allnex's (meth)acrylic acid urethane, and Negami Kogyo Co., Ltd.'s (meth)acrylic urethane, (meth)acrylic urethane manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth)acrylic amine ester manufactured by Kyeisha Chemical Co., Ltd., etc. Examples of the (meth)acrylic acid amine ester manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210, M-1600, and the like. Examples of the above-mentioned (meth)acrylic amine esters manufactured by Daicel-Allnex include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL6700, and EBECRYL4842. L8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 . Examples of the above-mentioned (meth)acrylic acid urethane manufactured by Negami Kogyo Co., Ltd. include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H, etc. Examples of the (meth)acrylic acid amine ester manufactured by Shin Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U- 10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc. Examples of the above-mentioned (meth)acrylic acid amine esters manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA- 306T etc.
於除上述環氧化合物以外含有上述(甲基)丙烯酸化合物作為上述硬化性樹脂之情形時，或者於含有上述部分(甲基)丙烯酸改質環氧化合物之情形時，較佳為使上述硬化性樹脂中之環氧基與(甲基)丙烯醯基之合計中之(甲基)丙烯醯基之比率成為30莫耳%以上且95莫耳%以下。藉由上述(甲基)丙烯醯基之比率為該範圍，抑制液晶污染之產生，且所獲得之液晶顯示元件用密封劑成為接著性更優異者。When the (meth)acrylic compound is contained as the curable resin in addition to the epoxy compound, or when a part of the (meth)acrylic modified epoxy compound is contained, it is preferred that the curable resin be The ratio of (meth)acrylyl groups in the total of epoxy groups and (meth)acrylyl groups in the resin is 30 mol% or more and 95 mol% or less. When the ratio of the above-mentioned (meth)acrylyl groups is within this range, the occurrence of liquid crystal contamination is suppressed, and the obtained sealing compound for liquid crystal display elements becomes one with more excellent adhesiveness.
就進一步抑制液晶污染之觀點而言，上述硬化性樹脂較佳為具有-OH基、-NH-基、-NH2 基等氫鍵結性之單元者。From the viewpoint of further suppressing liquid crystal contamination, the curable resin preferably has hydrogen-bonding units such as -OH groups, -NH- groups, and -NH 2 groups.
上述硬化性樹脂整體之SP值之較佳之下限為25.0（J/cm3 ）1/2 ，較佳之上限為50.0（J/cm3 ）1/2 。藉由上述硬化性樹脂整體之SP值為該範圍，所獲得之液晶顯示元件用密封劑成為低液晶污染性更優異，抑制液晶顯示元件之顯示不良之效果更優異者。 再者，上述硬化性樹脂整體之SP值於上述硬化性樹脂由多種構成成分構成之情形時，意指利用各硬化性樹脂構成成分之重量分率所得之SP值之平均值。The preferred lower limit of the SP value of the entire curable resin is 25.0 (J/cm 3 ) 1/2 , and the preferred upper limit is 50.0 (J/cm 3 ) 1/2 . When the SP value of the whole curable resin is within this range, the sealing compound for a liquid crystal display element obtained is more excellent in low liquid crystal contamination and has an excellent effect of suppressing display defects of the liquid crystal display element. In addition, when the above-mentioned curable resin is composed of a plurality of constituent components, the SP value of the entire curable resin means the average SP value obtained by using the weight fraction of each curable resin constituent component.
本發明之液晶顯示元件用密封劑較佳為含有自由基聚合起始劑。 作為上述自由基聚合起始劑，可列舉藉由光照射產生自由基之光自由基聚合起始劑或藉由加熱產生自由基之熱自由基聚合起始劑。The sealing compound for liquid crystal display elements of the present invention preferably contains a radical polymerization initiator. Examples of the radical polymerization initiator include a photo radical polymerization initiator that generates radicals by light irradiation or a thermal radical polymerization initiator that generates radicals by heating.
作為上述光自由基聚合起始劑，例如可列舉：二苯甲酮系化合物、苯乙酮系化合物、醯基氧化膦系化合物、二茂鈦系化合物、肟酯系化合物、安息香醚系化合物、9-氧硫𠮿等。Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, phosphine oxide compounds, titanocene compounds, oxime ester compounds, and benzoin ether compounds. 9-oxysulfur𠮿 wait.
作為上述光自由基聚合起始劑，具體而言，例如可列舉：1-羥基環己基苯基酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-1-丁酮、2-(二甲胺基)-2-((4-甲基苯基)甲基)-1-(4-(4-嗎啉基)苯基)-1-丁酮、2,2-二甲氧基-2-苯基苯乙酮、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2-甲基-1-(4-甲基噻吩基)-2-嗎啉基丙烷-1-酮、1-(4-(2-羥基乙氧基)-苯基)-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-(苯硫基)苯基)-1,2-辛二酮2-(O-苯甲醯肟)、2,4,6-三甲基苯甲醯基二苯基氧化膦、安息香甲醚、安息香乙醚、安息香異丙醚等。 上述光自由基聚合起始劑可單獨使用，亦可組合2種以上使用。Specific examples of the photoradical polymerization initiator include: 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) -1-Butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone , 2,2-dimethoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methyl methylthienyl)-2-morpholinylpropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one , 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime), 2,4,6-trimethylbenzyl diphenyl oxidation Phosphine, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. The above-mentioned photo radical polymerization initiator can be used alone or in combination of two or more kinds.
作為上述熱自由基聚合起始劑，例如可列舉由偶氮化合物或有機過氧化物等構成者。其中，就抑制液晶污染之觀點而言，較佳為由偶氮化合物構成之起始劑（以下亦稱作「偶氮起始劑」），更佳為由高分子偶氮化合物構成之起始劑（以下亦稱作「高分子偶氮起始劑」）。 上述熱自由基聚合起始劑可單獨使用，亦可組合2種以上使用。 再者，於本說明書中，上述所謂「高分子偶氮化合物」，意指具有偶氮基，且藉由熱而生成可使(甲基)丙烯醯基硬化之自由基的數量平均分子量為300以上之化合物。Examples of the thermal radical polymerization initiator include those composed of azo compounds, organic peroxides, and the like. Among them, from the viewpoint of suppressing liquid crystal contamination, a initiator composed of an azo compound (hereinafter also referred to as an "azo initiator") is preferred, and a initiator composed of a polymeric azo compound is more preferred. agent (hereinafter also referred to as "polymer azo starter"). The above-mentioned thermal radical polymerization initiator can be used alone or in combination of two or more kinds. In addition, in this specification, the above-mentioned "polymer azo compound" means a compound having an azo group and having a number average molecular weight of 300 to generate free radicals that can harden (meth)acrylyl groups by heat. The above compounds.
上述高分子偶氮化合物之數量平均分子量之較佳之下限為1000，較佳之上限為30萬。藉由上述高分子偶氮化合物之數量平均分子量為該範圍，可防止對液晶之不良影響，且容易混合至硬化性樹脂。上述高分子偶氮化合物之數量平均分子量之更佳之下限為5000，更佳之上限為10萬，進而較佳之下限為1萬，進而較佳之上限為9萬。 再者，於本說明書中，上述數量平均分子量係利用凝膠滲透層析法（GPC）使用四氫呋喃作為溶劑進行測定，並藉由聚苯乙烯換算而求出之值。作為利用GPC測定利用聚苯乙烯換算所得之數量平均分子量時之管柱，例如可列舉Shodex LF-804（昭和電工公司製造）等。The preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 1,000, and the preferable upper limit is 300,000. By having the number average molecular weight of the above-mentioned polymeric azo compound within this range, adverse effects on the liquid crystal can be prevented and the mixture can be easily mixed into the curable resin. A more preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 5,000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a further preferable upper limit is 90,000. In addition, in this specification, the said number average molecular weight is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and it is the value calculated|required by polystyrene conversion. Examples of a column for measuring the number average molecular weight in terms of polystyrene using GPC include Shodex LF-804 (manufactured by Showa Denko Co., Ltd.).
作為上述高分子偶氮化合物，例如可列舉具有聚環氧烷或聚二甲基矽氧烷等單元經由偶氮基鍵結多個之結構者。 作為上述具有聚環氧烷等單元經由偶氮基鍵結多個之結構之高分子偶氮化合物，較佳為具有聚環氧乙烷結構者。 作為上述高分子偶氮化合物，具體而言，例如可列舉4,4'-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之縮聚物、或4,4'-偶氮雙(4-氰基戊酸)與具有末端胺基之聚二甲基矽氧烷之縮聚物等。 作為上述高分子偶氮起始劑中之市售者，例如可列舉VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001（均為富士膠片和光純藥公司製造）等。 又，作為非高分子之偶氮起始劑，例如可列舉V-65、V-501（均為富士膠片和光純藥公司製造）等。Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via azo groups. As the above-mentioned polymeric azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via azo groups, those having a polyethylene oxide structure are preferred. Specific examples of the polymeric azo compound include a condensation polymer of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'-azo Condensation polymers of bis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amine groups, etc. Examples of commercially available polymeric azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.). Examples of non-polymer azo initiators include V-65 and V-501 (both manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.).
作為上述有機過氧化物，例如可列舉：過氧化酮、過氧縮酮、過氧化氫、二烷基過氧化物、過氧酯、二醯基過氧化物、過氧化二碳酸酯等。Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diyl peroxide, peroxydicarbonate, and the like.
上述自由基聚合起始劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為0.1重量份，較佳之上限為30重量份。藉由上述自由基聚合起始劑之含量為該範圍，所獲得之液晶顯示元件用密封劑成為抑制液晶污染，且保存穩定性或硬化性更優異者。上述自由基聚合起始劑之含量之更佳之下限為1重量份，更佳之上限為10重量份，進而較佳之上限為5重量份。The content of the radical polymerization initiator is preferably 0.1 parts by weight and 30 parts by weight relative to 100 parts by weight of the curable resin. When the content of the radical polymerization initiator is within this range, the sealing compound for a liquid crystal display element obtained suppresses liquid crystal contamination and is more excellent in storage stability or curability. A more preferable lower limit of the content of the above-mentioned radical polymerization initiator is 1 part by weight, a more preferable upper limit is 10 parts by weight, and a further preferable upper limit is 5 parts by weight.
本發明之液晶顯示元件用密封劑亦可以黏度之提高、利用應力分散效果之接著性之改善、線膨脹率之改善、硬化物之耐濕性之提高等為目的而含有填充劑。The sealant for a liquid crystal display element of the present invention may contain a filler for the purpose of increasing the viscosity, improving the adhesion utilizing the stress dispersion effect, improving the linear expansion rate, and improving the moisture resistance of the cured product.
作為上述填充劑，可使用無機填充劑或有機填充劑。 作為上述無機填充劑，例如可列舉：二氧化矽（silica）、滑石、玻璃珠、石棉、石膏、矽藻土、膨潤石、膨潤土、蒙脫石、絹雲母、活性白土、氧化鋁、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、氮化鋁、氮化矽、硫酸鋇、矽酸鈣等。 作為上述有機填充劑，例如可列舉：聚酯微粒子、聚胺酯（polyurethane）微粒子、乙烯系聚合物微粒子、丙烯酸聚合物微粒子等。 上述填充劑可單獨使用，亦可組合2種以上使用。As the above-mentioned filler, an inorganic filler or an organic filler can be used. Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, aluminum oxide, and zinc oxide. , iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc. Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like. The above-mentioned fillers can be used alone or in combination of two or more kinds.
本發明之液晶顯示元件用密封劑100重量份中之上述填充劑之含量之較佳之下限為10重量份，較佳之上限為70重量份。藉由上述填充劑之含量為該範圍，成為不會使塗佈性等惡化，而改善接著性等效果更優異者。上述填充劑之含量之更佳之下限為20重量份，更佳之上限為60重量份。The preferred lower limit of the content of the above-mentioned filler in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferred upper limit is 70 parts by weight. When the content of the above-mentioned filler is within this range, the effect of improving adhesion and the like will be more excellent without deteriorating the coating properties. A more preferable lower limit of the content of the above filler is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.
本發明之液晶顯示元件用密封劑亦可含有矽烷偶合劑。上述矽烷偶合劑主要具有作為用以將密封劑與基板等良好地接著之接著助劑之作用。The sealing compound for liquid crystal display elements of the present invention may also contain a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhesion aid for satisfactorily adhering the sealant to the substrate and the like.
作為上述矽烷偶合劑，例如可較佳地使用3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷等。該等之提高與基板等之接著性之效果優異，可藉由與硬化性樹脂化學鍵結而抑制硬化性樹脂流出至液晶中。 上述矽烷偶合劑可單獨使用，亦可組合2種以上使用。As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanate can be preferably used. Acidyl propyltrimethoxysilane, etc. These have an excellent effect of improving adhesion with substrates and the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin. The above-mentioned silane coupling agents can be used alone or in combination of two or more kinds.
本發明之液晶顯示元件用密封劑100重量份中之上述矽烷偶合劑之含量之較佳之下限為0.1重量份，較佳之上限為10重量份。藉由上述矽烷偶合劑之含量為該範圍，成為抑制液晶污染之產生，且提高接著性之效果更優異者。上述矽烷偶合劑之含量之更佳之下限為0.3重量份，更佳之上限為5重量份。The preferred lower limit of the content of the above-mentioned silane coupling agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the effect of suppressing the occurrence of liquid crystal contamination and improving the adhesion becomes more excellent. A more preferable lower limit of the content of the above-mentioned silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.
本發明之液晶顯示元件用密封劑亦可含有遮光劑。藉由含有上述遮光劑，本發明之液晶顯示元件用密封劑可較佳地用作遮光密封劑。The sealing compound for liquid crystal display elements of the present invention may also contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the sealing compound for liquid crystal display elements of the present invention can be preferably used as a light-shielding sealing agent.
作為上述遮光劑，例如可列舉：氧化鐵、鈦黑、苯胺黑、花青黑、富勒烯、碳黑、樹脂被覆型碳黑等。其中，較佳為鈦黑。Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, and the like. Among them, titanium black is preferred.
上述鈦黑係與對波長300 nm以上且800 nm以下之光之平均穿透率相比，對紫外線區域附近，尤其對波長370 nm以上且450 nm以下之光之穿透率增高之物質。即，上述鈦黑係具有藉由充分遮蔽可見光區域之波長之光而對本發明之液晶顯示元件用密封劑賦予遮光性，但另一方面使紫外線區域附近之波長之光穿透之性質之遮光劑。因此，藉由使用可藉由上述鈦黑之穿透率增高之波長（370 nm以上且450 nm以下）之光而開始反應者作為上述光自由基聚合起始劑，可進一步增大本發明之液晶顯示元件用密封劑之光硬化性。又，另一方面，作為本發明之液晶顯示元件用密封劑中所含有之遮光劑，較佳為絕緣性較高之物質，作為絕緣性較高之遮光劑，亦較佳為鈦黑。上述鈦黑之每1 μm之光學濃度（OD值）較佳為3以上，更佳為4以上。上述鈦黑之遮光性越高越好，上述鈦黑之OD值之較佳之上限並無特別限定，通常為5以下。The above-mentioned titanium black is a substance that has an increased transmittance to light near the ultraviolet region, especially to light with a wavelength of 370 nm or more and below 450 nm, compared to the average transmittance to light with a wavelength of 300 nm or more and 800 nm or less. That is, the above-mentioned titanium black is a light-shielding agent that has the property of imparting light-shielding properties to the sealing compound for liquid crystal display elements of the present invention by fully blocking light of wavelengths in the visible light range, but on the other hand, transmitting light of wavelengths near the ultraviolet range. . Therefore, by using as the above-mentioned photoradical polymerization initiator a light of a wavelength (370 nm or more and 450 nm or less) that can increase the transmittance of the titanium black, the reaction can be started, thereby further increasing the efficiency of the present invention. Photocurable properties of sealants for liquid crystal display elements. On the other hand, the light-shielding agent contained in the sealing compound for liquid crystal display elements of the present invention is preferably a substance with high insulation properties, and the light-shielding agent with high insulation properties is also preferably titanium black. The optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The upper limit of the OD value of the titanium black is not particularly limited, but is usually 5 or less.
上述鈦黑即便為未經表面處理者亦發揮充分之效果，但亦可使用表面由偶合劑等有機成分處理者，或由氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等經表面處理之鈦黑。其中，由有機成分處理者就可進一步提高絕緣性之觀點而言較佳。 又，使用摻合上述鈦黑作為遮光劑之本發明之液晶顯示元件用密封劑而製造之液晶顯示元件由於具有充分之遮光性，故而可實現無光之漏出而具有較高之對比度，具有優異之圖像顯示品質之液晶顯示元件。The above-mentioned titanium black can exert sufficient effects even if it is not surface-treated, but it can also be used with the surface treated with organic components such as coupling agents, or with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Surface-treated titanium black coated with inorganic components. Among them, those treated with organic components are preferable from the viewpoint of further improving insulation properties. In addition, the liquid crystal display element manufactured using the sealing compound for liquid crystal display elements of the present invention mixed with the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, so it can achieve no light leakage and has a high contrast ratio and excellent performance. LCD display components with excellent image display quality.
作為上述鈦黑中之市售者，例如可列舉三菱綜合材料公司製造之鈦黑、赤穗化成公司製造之鈦黑等。 作為上述三菱綜合材料公司製造之鈦黑，例如可列舉12S、13M、13M-C、13R-N、14M-C等。 作為上述赤穗化成公司製造之鈦黑，例如可列舉Tilack D等。Examples of commercially available titanium blacks include titanium black manufactured by Mitsubishi Materials Corporation, titanium black manufactured by Ako Chemicals Co., Ltd., and the like. Examples of the titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, 14M-C, and the like. Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilack D and the like.
上述鈦黑之比表面積之較佳之下限為13 m2 /g，較佳之上限為30 m2 /g，更佳之下限為15 m2 /g，更佳之上限為25 m2 /g。 又，上述鈦黑之體積電阻之較佳之下限為0.5 Ω·cm，較佳之上限為3 Ω·cm，更佳之下限為1 Ω·cm，更佳之上限為2.5 Ω·cm。The preferred lower limit of the specific surface area of the titanium black is 13 m 2 /g, the preferred upper limit is 30 m 2 /g, the preferred lower limit is 15 m 2 /g, and the preferred upper limit is 25 m 2 /g. In addition, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 2.5 Ω·cm.
上述遮光劑之一次粒徑只要為液晶顯示元件之基板間之距離以下，則無特別限定，較佳之下限為1 nm，較佳之上限為5000 nm。藉由上述遮光劑之一次粒徑為該範圍，可成為不會使所獲得之液晶顯示元件用密封劑之塗佈性等惡化而遮光性更優異者。上述遮光劑之一次粒徑之更佳之下限為5 nm，更佳之上限為200 nm，進而較佳之下限為10 nm，進而較佳之上限為100 nm。 再者，上述遮光劑之一次粒徑可使用NICOMP 380ZLS（PARTICLE SIZING SYSTEMS公司製造），使上述遮光劑分散於溶劑（水、有機溶劑等）中進行測定。The primary particle size of the above-mentioned light-shielding agent is not particularly limited as long as it is less than the distance between the substrates of the liquid crystal display element. The preferred lower limit is 1 nm and the preferred upper limit is 5000 nm. By having the primary particle diameter of the light-shielding agent within this range, it is possible to achieve better light-shielding properties without deteriorating the applicability and the like of the sealing compound for liquid crystal display elements obtained. A more preferable lower limit of the primary particle size of the above-mentioned sunscreen agent is 5 nm, a more preferable upper limit is 200 nm, a further preferable lower limit is 10 nm, and a further preferable upper limit is 100 nm. In addition, the primary particle size of the above-mentioned light-shielding agent can be measured by dispersing the above-mentioned light-shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
本發明之液晶顯示元件用密封劑100重量份中之上述遮光劑之含量之較佳之下限為5重量份，較佳之上限為80重量份。藉由上述遮光劑之含量為該範圍，可不會使所獲得之液晶顯示元件用密封劑之接著性、硬化後之強度、及描繪性大幅度降低，而發揮更優異之遮光性。上述遮光劑之含量之更佳之下限為10重量份，更佳之上限為70重量份，進而較佳之下限為30重量份，進而較佳之上限為60重量份。The preferred lower limit of the content of the above-mentioned light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferred upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, the obtained sealing compound for liquid crystal display elements can exhibit more excellent light-shielding properties without significantly reducing the adhesiveness, strength after curing, and drawing properties. A more preferable lower limit of the content of the above-mentioned sunscreen agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a further preferable lower limit is 30 parts by weight, and a further preferable upper limit is 60 parts by weight.
本發明之液晶顯示元件用密封劑亦可進而視需要含有應力緩和劑、反應性稀釋劑、觸變劑、間隙劑、硬化促進劑、消泡劑、調平劑、聚合抑制劑等添加劑。The sealant for liquid crystal display elements of the present invention may further contain additives such as a stress reliever, a reactive diluent, a thixotropic agent, a gap agent, a hardening accelerator, a defoaming agent, a leveling agent, and a polymerization inhibitor as needed.
作為製造本發明之液晶顯示元件用密封劑之方法，例如可列舉：使用混合機，將硬化性樹脂、熱硬化劑、及視需要添加之自由基聚合起始劑等進行混合之方法等。作為上述混合機，例如可列舉：勻相分散機、均質攪拌機、萬能攪拌機、行星式混合機、捏合機、三輥研磨機等。Examples of a method for producing the sealing compound for a liquid crystal display element of the present invention include a method of mixing a curable resin, a thermosetting agent, and optionally a radical polymerization initiator using a mixer. Examples of the mixer include a homogeneous disperser, a homogeneous mixer, a universal mixer, a planetary mixer, a kneader, a three-roller mill, and the like.
藉由於本發明之液晶顯示元件用密封劑中摻合導電性微粒子，可製造上下導通材料。含有此種本發明之液晶顯示元件密封劑及導電性微粒子之上下導通材料亦為本發明之一。By blending conductive fine particles into the sealant for liquid crystal display elements of the present invention, upper and lower conductive materials can be produced. The upper and lower conductive materials containing the liquid crystal display element sealing agent and conductive fine particles of the present invention are also one of the present invention.
作為上述導電性微粒子，例如可使用於金屬球、樹脂微粒子之表面形成有導電金屬層者等。其中，於樹脂微粒子之表面形成有導電金屬層者由於藉由樹脂微粒子之優異之彈性，可不損傷透明基板等而導電連接，故而較佳。As the conductive fine particles, for example, metal balls, resin fine particles having a conductive metal layer formed on their surfaces, etc. can be used. Among them, those in which a conductive metal layer is formed on the surface of the resin particles are preferable because the excellent elasticity of the resin particles enables conductive connection without damaging a transparent substrate or the like.
使用本發明之液晶顯示元件用密封劑或本發明之上下導通材料而成之液晶顯示元件亦為本發明之一。 本發明之液晶顯示元件用密封劑由於對具有極性基之液晶分子之相容性較低，故而於本發明之液晶顯示元件為使用包含具有極性基之液晶分子之極性高之液晶而成者之情形時，與習知之密封劑相比，抑制顯示不良之效果變得更顯著。即，本發明之液晶顯示元件較佳為使用極性高之液晶而成，該極性高之液晶包含具有極性基之液晶分子。 作為上述液晶分子之極性基，例如可列舉氟基、氯基、氰基等。A liquid crystal display element using the sealant for liquid crystal display elements of the present invention or the upper and lower conductive materials of the present invention is also one of the present invention. Since the sealant for liquid crystal display elements of the present invention has low compatibility with liquid crystal molecules having polar groups, the liquid crystal display element of the present invention uses highly polar liquid crystals containing liquid crystal molecules having polar groups. In this case, the effect of suppressing display defects becomes more significant than that of conventional sealants. That is, the liquid crystal display element of the present invention is preferably formed using a highly polar liquid crystal containing liquid crystal molecules having polar groups. Examples of polar groups of the liquid crystal molecules include fluorine groups, chlorine groups, and cyano groups.
又，於本發明之液晶顯示元件用密封劑為使用SP值為22.0（J/cm3 ）1/2 以上且50.0（J/cm3 ）1/2 以下之液晶而成者之情形時，與習知之密封劑相比，抑制顯示不良之效果變得更顯著。 再者，上述液晶之SP值於液晶由多種液晶分子構成之情形時，意指利用各液晶分子之重量分率所得之SP值之平均值。Moreover, when the sealing compound for liquid crystal display elements of the present invention is formed using a liquid crystal with an SP value of 22.0 (J/cm 3 ) 1/2 or more and 50.0 (J/cm 3 ) 1/2 or less, it is the same as Compared with conventional sealants, the effect of suppressing display defects becomes more significant. Furthermore, when the liquid crystal is composed of a plurality of liquid crystal molecules, the SP value of the above-mentioned liquid crystal means the average SP value obtained by using the weight fraction of each liquid crystal molecule.
作為本發明之液晶顯示元件，較佳為窄邊緣設計之液晶顯示元件。具體而言，較佳為液晶顯示部之周圍之框部分之寬度為2 mm以下。 又，製造本發明之液晶顯示元件時之本發明之液晶顯示元件用密封劑之塗佈寬度較佳為1 mm以下。The liquid crystal display element of the present invention is preferably a liquid crystal display element with a narrow edge design. Specifically, it is preferable that the width of the frame portion around the liquid crystal display portion is 2 mm or less. Moreover, when manufacturing the liquid crystal display element of the present invention, the coating width of the sealant for liquid crystal display elements of the present invention is preferably 1 mm or less.
本發明之液晶顯示元件用密封劑可較佳地用於利用液晶滴下工法之液晶顯示元件之製造。 作為利用液晶滴下工法製造本發明之液晶顯示元件之方法，例如可列舉以下之方法等。 首先，進行於基板將本發明之液晶顯示元件用密封劑等利用網版印刷、分注器塗佈等形成框狀之密封圖案之步驟。繼而，進行以本發明之液晶顯示元件用密封劑等未硬化之狀態將液晶之微小滴滴下塗佈於密封圖案之框內整面，迅速重疊另一基板之步驟。此後，進行將密封劑進行加熱而使其硬化之步驟，藉由上述方法，可獲得液晶顯示元件。又，於將密封劑進行加熱而使其硬化之步驟前，亦可進行對密封圖案部分照射紫外線等光使密封劑暫時硬化之步驟。 [發明之效果]The sealant for liquid crystal display elements of the present invention can be preferably used for manufacturing liquid crystal display elements using the liquid crystal dropping process. Examples of methods for manufacturing the liquid crystal display element of the present invention using the liquid crystal dropping process include the following methods. First, a step of forming a frame-shaped sealing pattern on a substrate using the sealant for liquid crystal display elements of the present invention is performed using screen printing, dispenser coating, or the like. Next, the step of applying the sealant for liquid crystal display elements of the present invention in an uncured state to the entire surface of the frame of the seal pattern with tiny droplets of liquid crystal, and quickly overlaying the other substrate is performed. Thereafter, a step of heating and hardening the sealing agent is performed. By the above method, a liquid crystal display element can be obtained. In addition, before the step of heating and hardening the sealant, a step of irradiating the sealing pattern portion with light such as ultraviolet light to temporarily harden the sealant may be performed. [Effects of the invention]
根據本發明，可提供一種保存穩定性及硬化性優異，且即便於用於薄型之液晶顯示元件之情形時亦可抑制顯示不良之產生之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。According to the present invention, it is possible to provide a sealing compound for a liquid crystal display element that is excellent in storage stability and curability and that can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Furthermore, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element using the sealant for liquid crystal display elements.
以下揭示實施例對本發明進一步詳細地進行說明，但本發明並不僅限定於該等實施例。The following examples will be disclosed to further explain the present invention in detail, but the present invention is not limited only to these examples.
（實施例1～7、比較例1～3） 依據表1中所記載之摻合比，使用行星式攪拌機（Thinky公司製造，「去泡攪拌太郎」）將各材料進行混合後，進而使用三輥研磨機進行混合，藉此製備實施例1～7、比較例1～3之各液晶顯示元件用密封劑。(Examples 1 to 7, Comparative Examples 1 to 3) According to the blending ratio described in Table 1, each material was mixed using a planetary mixer (manufactured by Thinky Corporation, "Defoaming Mixer Taro"), and then mixed using a three-roller mill to prepare Examples 1 to 7. Sealing compound for each liquid crystal display element of Comparative Examples 1 to 3.
＜評價＞ 對實施例及比較例中所獲得之各液晶顯示元件用密封劑進行以下之評價。將結果示於表1。＜Evaluation＞ The following evaluations were performed on each sealing compound for liquid crystal display elements obtained in Examples and Comparative Examples. The results are shown in Table 1.
（保存穩定性） 針對實施例及比較例中所獲得之各液晶顯示元件用密封劑，測定剛製造後之初始黏度、及製造後於25℃、50%RH之環境下保管48小時後之黏度。將（保管後之黏度）/（初始黏度）設為增黏率，將增黏率未達1.2者設為「〇」，將1.2以上且未達1.3者設為「△」，將1.3以上者設為「×」而對保存穩定性進行評價。 再者，密封劑之黏度係使用E型黏度計（BROOK FIELD公司製造，「DV-III」），於25℃以旋轉速度1.0 rpm之條件進行測定。(storage stability) For each liquid crystal display element sealant obtained in the Examples and Comparative Examples, the initial viscosity immediately after production and the viscosity after storage in an environment of 25° C. and 50% RH for 48 hours after production were measured. Let (viscosity after storage)/(initial viscosity) be the viscosity increase rate. If the viscosity increase rate is less than 1.2, it will be "0". If it is 1.2 or more and less than 1.3, it will be "△". If it is 1.3 or more, it will be "△". The storage stability was evaluated as "×". In addition, the viscosity of the sealant was measured using an E-type viscometer (manufactured by BROOK FIELD, "DV-III") at 25°C and a rotation speed of 1.0 rpm.
（硬化性） 將實施例及比較例中所獲得之各液晶顯示元件用密封劑打點於2片透明基板之一者，並重疊另一透明基板後，使用金屬鹵化物燈照射100 mW/cm2 之紫外線30秒。此後，於120℃加熱1小時，使液晶顯示元件用密封劑熱硬化。剝下透明基板，使用紅外分光計（Agilent Technologies公司製造，「UMA600」）對殘留於透明基板上之硬化物進行測定，由所獲得之測定結果及預先測定之硬化前之測定結果按照下述式計算硬化率。 硬化率（%）＝100×（1－（硬化後之環氧基之峰面積）/（硬化前之環氧基之峰面積）） 將硬化率為90%以上者設為「〇」，將70%以上且未達90%者設為「△」，將未達70%者設為「×」而對硬化性進行評價。(Cureability) Each liquid crystal display element obtained in the Example and Comparative Example was dotted with a sealant on one of the two transparent substrates, and the other transparent substrate was overlapped, and then irradiated with a metal halide lamp at 100 mW/cm 2 UV rays for 30 seconds. Thereafter, it was heated at 120° C. for 1 hour to thermally harden the liquid crystal display element sealing compound. The transparent substrate was peeled off, and the cured material remaining on the transparent substrate was measured using an infrared spectrometer (manufactured by Agilent Technologies, "UMA600"). The obtained measurement results and the previously measured measurement results before curing were calculated according to the following formula: Calculate the hardening rate. Hardening rate (%) = 100 × (1 - (Peak area of epoxy group after hardening) / (Peak area of epoxy group before hardening)) If the hardening rate is more than 90%, set it as "0". The hardenability was evaluated by setting the value of 70% or more and less than 90% as "△" and the value of less than 70% as "×".
（液晶顯示元件之顯示性能） 於2片摩擦過之配向膜及附透明電極之基板之一者，利用分注器以描繪正方形之框之方式塗佈實施例及比較例中所獲得之各液晶顯示元件用密封劑而形成密封圖案。於所形成之密封圖案之內側打點液晶顯示元件用密封劑。 繼而，將包含具有氰基作為極性基之液晶分子（東京化成工業公司製造，「4-戊基-4-聯苯甲腈」，SP值22.4（J/cm3 ）1/2 ）的液晶之微小滴滴下塗佈於附透明電極之基板之密封劑之框內整面，於真空中重疊另一基板。解除真空後，對外框密封部分使用金屬鹵化物燈照射100 mW/cm2 之紫外線30秒。此時，於所打點之液晶顯示元件用密封劑以紫外線照射不到之方式進行遮罩。此後，於120℃進行液晶退火1小時，使液晶顯示元件用密封劑熱硬化而獲得液晶顯示元件。 針對剛製作後之液晶顯示元件，以目視確認所打點之液晶顯示元件用密封劑周邊之液晶配向紊亂。液晶配向紊亂藉由自液晶顯示元件周邊部之密封邊起未達500 μm之範圍內之色不均或亮點進行判斷。 將於自液晶顯示元件周邊部之密封邊起未達500 μm之範圍內，完全無色不均及亮點之情形設為「〇」，將觀察到少許色不均及/或亮點之情形設為「△」，將存在大量色不均及/或亮點之情形設為「×」而對液晶顯示元件之顯示性能（剛製作後）進行評價。 又，針對製作液晶顯示元件後於25℃經過24小時後之液晶顯示元件，於通電狀態下以目視確認所打點之液晶顯示元件用密封劑周邊之液晶配向紊亂。液晶配向紊亂藉由自液晶顯示元件周邊部之密封邊起未達500 μm及500 μm以上之範圍內之色不均或亮點進行判斷。 將於自密封邊起未達500 μm之範圍內，完全無色不均及亮點之情形設為「◎」，將觀察到少許色不均及/或亮點之情形設為「〇」，將存在大量色不均及/或亮點之情形設為「△」，將於自密封邊起500 μm以上之範圍內亦存在色不均及亮點之情形設為「×」而對液晶顯示元件之顯示性能（製作後經過24小時後）進行評價。(Display performance of liquid crystal display elements) Each of the liquid crystals obtained in the Examples and Comparative Examples was applied using a dispenser to draw a square frame on one of the two rubbed alignment films and the substrate with a transparent electrode. The display element uses a sealant to form a sealing pattern. A sealant for liquid crystal display elements is applied inside the formed sealing pattern. Next, a liquid crystal containing a liquid crystal molecule having a cyano group as a polar group ("4-pentyl-4-biphenylcarbonitrile" manufactured by Tokyo Chemical Industry Co., Ltd., SP value 22.4 (J/cm 3 ) 1/2 ) was Apply tiny drops of sealant to the entire surface of the frame of the substrate with the transparent electrode, and then overlap the other substrate in vacuum. After releasing the vacuum, use a metal halide lamp to irradiate the sealed part of the outer frame with ultraviolet light at 100 mW/ cm2 for 30 seconds. At this time, the dotted liquid crystal display element is masked with a sealant so as not to be exposed to ultraviolet rays. Thereafter, liquid crystal annealing was performed at 120° C. for 1 hour, the sealing compound for liquid crystal display elements was thermally cured, and a liquid crystal display element was obtained. For the liquid crystal display element that has just been produced, visually confirm the alignment disorder of the liquid crystal around the sealant for liquid crystal display element that has been applied. Liquid crystal alignment disorder is judged by color unevenness or bright spots within a range of less than 500 μm from the sealing edge at the periphery of the liquid crystal display element. The case where there is no color unevenness and bright spots within a range of less than 500 μm from the sealing edge of the periphery of the liquid crystal display element is regarded as "0", and the case where some color unevenness and/or bright spots are observed is regarded as "△", and the display performance of the liquid crystal display element (immediately after production) was evaluated as "×" when there were a large number of color unevenness and/or bright spots. In addition, after the liquid crystal display element was produced and kept at 25° C. for 24 hours, the liquid crystal alignment disorder around the applied sealant for liquid crystal display element was visually confirmed in the energized state. Liquid crystal alignment disorder is judged by color unevenness or bright spots within a range of less than 500 μm and 500 μm or more from the sealing edge at the periphery of the liquid crystal display element. In the range of less than 500 μm from the sealing edge, the situation where there is no color unevenness and bright spots is set as "◎". The case where some color unevenness and/or bright spots are observed is set as "O", and the situation where a large amount of color unevenness and/or bright spots are observed is The situation of color unevenness and/or bright spots is set as "△", and the situation of color unevenness and bright spots also existing in the range of 500 μm or more from the sealing edge is set as "×". The display performance of the liquid crystal display element ( Evaluate after 24 hours after production).
[表1]
根據本發明，可提供一種保存穩定性及硬化性優異，且即便於用於薄型之液晶顯示元件之情形時亦可抑制顯示不良之產生之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。According to the present invention, it is possible to provide a sealing compound for a liquid crystal display element that is excellent in storage stability and curability and that can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Furthermore, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element using the sealant for liquid crystal display elements.
無。without.
無。without.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP2018-093102 | 2018-05-14 | ||
| JP2018093102 | 2018-05-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201946999A TW201946999A (en) | 2019-12-16 |
| TWI815888B true TWI815888B (en) | 2023-09-21 |
Family
ID=68540345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW108116528A TWI815888B (en) | 2018-05-14 | 2019-05-14 | Sealants for liquid crystal display elements, upper and lower conductive materials, and liquid crystal display elements |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7295798B2 (en) |
| TW (1) | TWI815888B (en) |
| WO (1) | WO2019221044A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201615670A (en) * | 2011-12-21 | 2016-05-01 | 三菱麗陽股份有限公司 | Polymer powder, cured material, stress reliever and pregelatinization agent for curable resin, curable resin composition, sealing material for semiconductor, sheet-like article and sealing agent for liquid crystal display device |
| JP2017049578A (en) * | 2015-09-02 | 2017-03-09 | 積水化学工業株式会社 | Sealant for liquid crystal display elements, vertical conduction material and liquid crystal display element |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100230638A1 (en) | 2006-03-29 | 2010-09-16 | Masanori Matsuda | Sealant for One Drop Fill Process, Transfer Material, and Liquid Crystal Display Element |
-
2019
- 2019-05-13 JP JP2019529287A patent/JP7295798B2/en active Active
- 2019-05-13 WO PCT/JP2019/018871 patent/WO2019221044A1/en active Application Filing
- 2019-05-14 TW TW108116528A patent/TWI815888B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201615670A (en) * | 2011-12-21 | 2016-05-01 | 三菱麗陽股份有限公司 | Polymer powder, cured material, stress reliever and pregelatinization agent for curable resin, curable resin composition, sealing material for semiconductor, sheet-like article and sealing agent for liquid crystal display device |
| JP2017049578A (en) * | 2015-09-02 | 2017-03-09 | 積水化学工業株式会社 | Sealant for liquid crystal display elements, vertical conduction material and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019221044A1 (en) | 2019-11-21 |
| TW201946999A (en) | 2019-12-16 |
| JP7295798B2 (en) | 2023-06-21 |
| JPWO2019221044A1 (en) | 2021-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5759638B1 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
| TWI801554B (en) | Photopolymerization initiator, sealant for display elements, upper and lower conduction materials, display elements and compounds | |
| JP6408983B2 (en) | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element | |
| TW202214813A (en) | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
| WO2016181840A1 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
| JP6046868B1 (en) | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element | |
| JP6460797B2 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
| JP6126756B1 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
| WO2016194871A1 (en) | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element | |
| TWI823843B (en) | Sealants for liquid crystal display elements, upper and lower conductive materials and liquid crystal display elements | |
| TWI815888B (en) | Sealants for liquid crystal display elements, upper and lower conductive materials, and liquid crystal display elements | |
| TW202115222A (en) | Curable resin composition, sealing agent for liquid crystal display element, vertically conductive material, and liquid crystal display element | |
| TW202116838A (en) | Sealing agent for liquid crystal display elements, vertical conduction material, and liquid crystal display element | |
| TWI813686B (en) | Sealant for liquid crystal display element, upper and lower conduction material, and liquid crystal display element | |
| JP6609396B1 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
| JP6378970B2 (en) | Curable resin composition, liquid crystal display element sealing agent, vertical conduction material, and liquid crystal display element | |
| TWI827608B (en) | Sealants for liquid crystal display elements, upper and lower conductive materials, and liquid crystal display elements | |
| JP6630871B1 (en) | Composition for electronic material, sealant for liquid crystal display element, vertical conductive material, and liquid crystal display element | |
| TWI838338B (en) | Sealant for liquid crystal display element, upper and lower conductive material, and liquid crystal display element | |
| JP6031215B1 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
| TW202313920A (en) | Liquid crystal display element sealant and liquid crystal display element | |
| TW202346286A (en) | Sealing agent for display elements, sealing agent for liquid crystal display elements, and liquid crystal display element | |
| TW202313560A (en) | Hydrazide compound, curable resin composition, sealing agent for liquid crystal display elements, and liquid crystal display element | |
| JP2017003989A (en) | Sealant for liquid crystal display elements, vertical conduction material, and liquid crystal display element |