KR20180100473A - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents
Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element Download PDFInfo
- Publication number
- KR20180100473A KR20180100473A KR1020177035070A KR20177035070A KR20180100473A KR 20180100473 A KR20180100473 A KR 20180100473A KR 1020177035070 A KR1020177035070 A KR 1020177035070A KR 20177035070 A KR20177035070 A KR 20177035070A KR 20180100473 A KR20180100473 A KR 20180100473A
- Authority
- KR
- South Korea
- Prior art keywords
- liquid crystal
- crystal display
- display element
- meth
- acrylate
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 111
- 239000000565 sealant Substances 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 82
- 239000004593 Epoxy Substances 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 239000010419 fine particle Substances 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 13
- 238000011109 contamination Methods 0.000 abstract description 13
- 230000003449 preventive effect Effects 0.000 abstract description 8
- -1 acryl Chemical group 0.000 description 49
- 239000003822 epoxy resin Substances 0.000 description 48
- 229920000647 polyepoxide Polymers 0.000 description 48
- 239000000758 substrate Substances 0.000 description 18
- 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 16
- 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 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 13
- 239000010936 titanium Substances 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 13
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- 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 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 229920003986 novolac Polymers 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000002542 deteriorative effect Effects 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
- 239000010408 film Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 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 3
- 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 3
- 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 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 2
- DPBYCORQBMMFJZ-UHFFFAOYSA-N 20-episilicine Natural products O=C1CC2C(CC)CN(C)CC2CC2=C1NC1=CC=CC=C21 DPBYCORQBMMFJZ-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-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
- 239000000654 additive Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 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
- 239000006229 carbon black Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 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
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
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- 239000007788 liquid Substances 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
- 239000011707 mineral Substances 0.000 description 2
- ZCIJAGHWGVCOHJ-UHFFFAOYSA-N naphthalene phenol Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)O ZCIJAGHWGVCOHJ-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 230000002829 reductive effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
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- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
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- 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
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- NKVCQMYWYHDOOF-UHFFFAOYSA-N 1-phenoxyethane-1,2-diol Chemical compound OCC(O)OC1=CC=CC=C1 NKVCQMYWYHDOOF-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
- 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
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0647—Polyepoxides
Abstract
본 발명은, 도포성, 투습 방지성, 및, 접착성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제를 제공하는 것을 목적으로 한다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공하는 것을 목적으로 한다.
본 발명은, 경화성 수지와, 라디칼 중합 개시제 및/또는 열 경화제를 함유하는 액정 표시 소자용 시일제로서, 상기 경화성 수지는, 하기 식 (1) 로 나타내는 화합물을 함유하고, 액정 표시 소자용 시일제 중에 있어서의 상기 식 (1) 로 나타내는 화합물의 함유량이 1 중량％ 이상 30 중량％ 미만인 액정 표시 소자용 시일제이다.
식 (1) 중, R1 은 수소 또는 메틸기이고, m 및 n 은 각각 0 ∼ 6 이다.It is an object of the present invention to provide a sealant for a liquid crystal display element which is excellent in coating property, moisture permeation preventive property and adhesion property and can suppress liquid crystal contamination. It is another object of the present invention to provide a liquid crystal display element and a liquid crystal display element using the liquid crystal display element sealant.
The present invention relates to a sealant for a liquid crystal display element containing a curable resin and a radical polymerization initiator and / or a thermosetting agent, wherein the curable resin contains a compound represented by the following formula (1) Wherein the content of the compound represented by the formula (1) in the liquid crystal display element is in the range of 1 wt% to less than 30 wt%.
In the formula (1), R 1 is hydrogen or a methyl group, and m and n are each 0 to 6.
Description
본 발명은, 도포성, 투습 방지성, 및, 접착성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제에 관한 것이다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자에 관한 것이다.The present invention relates to a sealant for a liquid crystal display element which is excellent in coating property, moisture permeation preventive property and adhesion property and can suppress liquid crystal contamination. The present invention also relates to an upper and lower conductive material and a liquid crystal display element using the liquid crystal display element sealant.
최근, 액정 표시 소자의 제조 방법으로는, 택트 타임 단축, 사용 액정량의 최적화와 같은 관점에서, 특허문헌 1, 특허문헌 2 에 개시되어 있는 바와 같은, 경화성 수지와 광 중합 개시제와 열 경화제를 함유하는 광열 병용 경화형의 시일제를 사용한 적하 공법이라고 불리는 액정 적하 방식이 사용되고 있다.In recent years, as a method of manufacturing a liquid crystal display element, there has been proposed a method of manufacturing a liquid crystal display element in which a curable resin, a photopolymerization initiator and a thermosetting agent are contained, as disclosed in Patent Documents 1 and 2, A liquid dropping method called a dropping method using a curing type sealant for photothermal junction is used.
적하 공법에서는, 먼저, 2 장의 전극이 부착된 투명 기판의 일방에, 디스펜스에 의해 장방형상의 시일 패턴을 형성한다. 이어서, 시일제가 미경화인 상태에서 액정의 미소적 (微小滴) 을 투명 기판의 프레임 내 전체면에 적하하고, 곧바로 타방의 투명 기판을 중첩하고, 시일부에 자외선 등의 광을 조사하여 임시 경화를 실시한다. 그 후, 가열하여 본경화를 실시하여, 액정 표시 소자를 제조한다. 기판의 첩합을 감압하에서 실시함으로써 매우 높은 효율로 액정 표시 소자를 제조할 수 있어, 현재 이 적하 공법이 액정 표시 소자의 제조 방법의 주류로 되어 있다.In the dropping method, a rectangular-shaped seal pattern is formed by dispensing on one side of a transparent substrate to which two electrodes are attached. Subsequently, micro-droplets of the liquid crystal are dropped onto the entire surface in the frame of the transparent substrate in the state where the sealant is uncured, the other transparent substrate is immediately superimposed, light is irradiated to the seal portion such as ultraviolet light, Conduct. After that, the liquid crystal display device is manufactured by heating and final curing. The liquid crystal display element can be manufactured with a very high efficiency by bonding the substrate under a reduced pressure, and this dropping method has become the mainstream of the liquid crystal display element manufacturing method at present.
그런데, 휴대 전화, 휴대 게임기 등, 각종 액정 패널이 부착된 모바일 기기가 보급되고 있는 현대에 있어서, 장치의 소형화는 가장 요구되고 있는 과제이다. 장치의 소형화의 수법으로는, 액정 표시부의 프레임 협소화를 들 수 있으며, 예를 들어, 시일부의 위치를 블랙 매트릭스하에 배치하는 것이 실시되고 있다 (이하, 프레임 협소 설계라고도 한다).[0004] However, in the modern age in which a mobile device with various liquid crystal panels such as a mobile phone, a portable game machine, and the like is spreading, miniaturization of the device is a most demanded problem. As a method of downsizing the apparatus, there is a frame narrowing of the liquid crystal display part. For example, the position of the seal part is arranged under the black matrix (hereinafter also referred to as frame narrowing design).
그러나, 프레임 협소 설계에서는 시일제가 블랙 매트릭스의 바로 아래에 배치되기 때문에, 적하 공법을 실시하면, 시일제를 광 경화시킬 때에 조사한 광이 차단되고, 시일제의 내부까지 광이 도달하지 않아 경화가 불충분해진다는 문제가 있었다. 이와 같이 시일제의 경화가 불충분해지면, 미경화의 시일제 성분이 액정 중에 용출되고, 용출된 시일제 성분에 의한 경화 반응이 액정 중에서 진행됨으로써 액정 오염이 발생한다는 문제가 있었다.However, in the frame narrowing design, since the sealant is disposed directly below the black matrix, when the dropping method is used, light irradiated when the sealant is photo-cured is blocked, light does not reach the interior of the sealant, There was a problem of becoming. When the curing of the sealant becomes insufficient, there arises a problem that the uncured sealant component elutes into the liquid crystal and the cured reaction by the eluted sealant component progresses in the liquid crystal, thereby causing liquid crystal contamination.
본 발명은, 도포성, 투습 방지성, 및, 접착성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제를 제공하는 것을 목적으로 한다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a sealant for a liquid crystal display element which is excellent in coating property, moisture permeation preventive property and adhesion property and can suppress liquid crystal contamination. It is another object of the present invention to provide a liquid crystal display element and a liquid crystal display element using the liquid crystal display element sealant.
본 발명은, 경화성 수지와, 라디칼 중합 개시제 및/또는 열 경화제를 함유하는 액정 표시 소자용 시일제로서, 상기 경화성 수지는, 하기 식 (1) 로 나타내는 화합물을 함유하고, 액정 표시 소자용 시일제 중에 있어서의 상기 식 (1) 로 나타내는 화합물의 함유량이 1 중량％ 이상 30 중량％ 미만인 액정 표시 소자용 시일제이다.The present invention relates to a sealant for a liquid crystal display element containing a curable resin and a radical polymerization initiator and / or a thermosetting agent, wherein the curable resin contains a compound represented by the following formula (1) Wherein the content of the compound represented by the formula (1) in the liquid crystal display element is in the range of 1 wt% to less than 30 wt%.
[화학식 1][Chemical Formula 1]
식 (1) 중, R1 은 수소 또는 메틸기이고, m 및 n 은 각각 0 ∼ 6 이다.In the formula (1), R 1 is hydrogen or a methyl group, and m and n are each 0 to 6.
이하에 본 발명을 상세하게 서술한다.Hereinafter, the present invention will be described in detail.
본 발명자는, 경화성 수지로서 접착성이 우수하고, 또한 액정 오염성이 낮은 비스페놀 S 형 에폭시 수지를 배합하는 것을 검토하였다. 그러나, 비스페놀 S 형 에폭시 수지를 사용한 경우에도, 액정 오염을 억제하는 효과가 충분하지 않았거나, 얻어지는 액정 표시 소자용 시일제가 도포성이나 투습 방지성이 떨어지는 것이 되거나 한다는 문제가 있었다.The present inventors have studied the blending of a bisphenol S type epoxy resin having excellent adhesiveness as a curable resin and low liquid stain resistance. However, even when a bisphenol S type epoxy resin is used, there is a problem that the effect of suppressing liquid crystal contamination is insufficient, or that the resulting sealant for a liquid crystal display element is poor in coating property and moisture permeation preventive property.
그래서 본 발명자들은, 비스페놀 S 형 구조를 갖는 특정한 화합물을 특정량 배합함으로써, 도포성, 투습 방지성, 및, 접착성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제를 얻을 수 있는 것을 알아내어, 본 발명을 완성시키기에 이르렀다.Thus, the present inventors have found that when a specific amount of a specific compound having a bisphenol S-type structure is blended, a sealing agent for a liquid crystal display element which is excellent in coating properties, moisture-proofing and adhesion properties and can suppress liquid crystal contamination is obtained The present invention has been accomplished on the basis of these findings.
본 발명의 액정 표시 소자용 시일제는, 경화성 수지를 함유한다.The liquid crystal display element sealant of the present invention contains a curable resin.
상기 경화성 수지는, 상기 식 (1) 로 나타내는 화합물을 함유한다. 상기 식 (1) 로 나타내는 화합물을 함유함으로써, 본 발명의 액정 표시 소자용 시일제는, 접착성 및 액정 오염을 억제하는 효과가 우수한 것이 된다.The curable resin contains the compound represented by the formula (1). By containing the compound represented by the above formula (1), the liquid crystal display element sealant of the present invention is excellent in the adhesive property and the effect of suppressing liquid crystal contamination.
상기 식 (1) 중, m 및 n 은 각각 0 ∼ 6 이다. 상기 m 및 n 은 각각 1 ∼ 6 인 것이 바람직하고, 각각 1 ∼ 3 인 것이 보다 바람직하다.In the above formula (1), m and n are each 0 to 6. M and n are each preferably 1 to 6, more preferably 1 to 3.
또한, 상기 식 (1) 및 후술하는 식 (2) 에 있어서의 m 및 n 의 값은 평균값이다. 또, m 이나 n 이 0 인 경우란, m 이나 n 이 부여된 에틸렌옥사이드 구조 부분이 결합손이 되는 것을 의미한다.The values of m and n in the formula (1) and the formula (2) described later are an average value. When m or n is 0, it means that the ethylene oxide structural moiety to which m or n is attached is bonded.
상기 식 (1) 로 나타내는 화합물을 제조하는 방법으로는, 예를 들어, 비스페놀 S 또는 에틸렌옥사이드 부가 비스페놀 S 와 에피클로르하이드린을 반응시킴으로써, 하기 식 (2) 로 나타내는 화합물을 제조하고, 얻어진 식 (2) 로 나타내는 화합물의 일방의 에폭시기를 (메트)아크릴산과 반응시키는 방법 등을 들 수 있다.As a method for producing the compound represented by the above formula (1), for example, a compound represented by the following formula (2) is prepared by reacting bisphenol S or an ethylene oxide-added bisphenol S with epichlorohydrin, A method of reacting one epoxy group of the compound represented by the formula (2) with (meth) acrylic acid, and the like.
또한, 본 명세서에 있어서 상기「(메트)아크릴」이란, 아크릴 또는 메타크릴을 의미한다.In the present specification, the term "(meth) acryl" means acryl or methacryl.
[화학식 2](2)
식 (2) 중, m 및 n 은 각각 0 ∼ 6 이다.In the formula (2), m and n are each 0 to 6.
본 발명의 액정 표시 소자용 시일제 중에 있어서의 상기 식 (1) 로 나타내는 화합물의 함유량은, 1 중량％ 이상 30 중량％ 미만이다. 상기 식 (1) 로 나타내는 화합물의 함유량이 1 중량％ 미만이면, 얻어지는 액정 표시 소자용 시일제가 접착성이 떨어지는 것이 되기 쉬워진다. 상기 식 (1) 로 나타내는 화합물의 함유량이 30 중량％ 이상이면, 얻어지는 표시 소자용 봉지제가 도포성이나 투습 방지성이 떨어지는 것이 된다. 상기 식 (1) 로 나타내는 화합물의 함유량의 바람직한 하한은 5 중량％, 바람직한 상한은 25 중량％, 보다 바람직한 하한은 10 중량％, 보다 바람직한 상한은 20 중량％, 더욱 바람직한 상한은 15 중량％ 이다.The content of the compound represented by the formula (1) in the liquid crystal display element sealant of the present invention is 1 wt% or more and less than 30 wt%. If the content of the compound represented by the above formula (1) is less than 1% by weight, the obtained liquid crystal display element sealant tends to have poor adhesiveness. When the content of the compound represented by the above formula (1) is 30 wt% or more, the resultant encapsulant for a display element becomes poor in coating property and moisture permeation preventive property. The lower limit of the content of the compound represented by the formula (1) is preferably 5% by weight, more preferably 25% by weight, still more preferably 10% by weight, still more preferably 20% by weight and still more preferably 15% by weight.
상기 경화성 수지는, 상기 식 (1) 로 나타내는 화합물에 더하여, 그 밖의 경화성 수지를 함유하는 것이 바람직하다.It is preferable that the curable resin contains other curable resin in addition to the compound represented by the formula (1).
상기 그 밖의 경화성 수지로는, 예를 들어, 상기 식 (1) 로 나타내는 화합물 이외의, (메트)아크릴 화합물이나 에폭시 화합물 등을 들 수 있다. 그 중에서도, 상기 (메트)아크릴 화합물로서 후술하는 에폭시(메트)아크릴레이트를 함유하는 것이 바람직하고, 레조르시놀형 에폭시(메트)아크릴레이트를 함유하는 것이 보다 바람직하다.Examples of the other curable resin include a (meth) acrylic compound and an epoxy compound other than the compound represented by the formula (1). Among them, it is preferable that the (meth) acrylic compound contains an epoxy (meth) acrylate described below, and more preferably a resorcinol-type epoxy (meth) acrylate.
또한, 본 명세서에 있어서 상기「(메트)아크릴레이트」란, 아크릴레이트 또는 메타크릴레이트를 의미하고,「에폭시(메트)아크릴레이트」란, 에폭시 화합물 중의 모든 에폭시기를 (메트)아크릴산과 반응시킨 화합물을 나타낸다.In the present specification, the term "(meth) acrylate" means acrylate or methacrylate, and "epoxy (meth) acrylate" means a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) .
상기 그 밖의 경화성 수지인 (메트)아크릴 화합물로는, 예를 들어, (메트)아크릴산과 에폭시 화합물을 반응시킴으로써 얻어지는 에폭시(메트)아크릴레이트, (메트)아크릴산에 수산기를 갖는 화합물을 반응시킴으로써 얻어지는 (메트)아크릴산에스테르 화합물, 이소시아네이트 화합물에 수산기를 갖는 (메트)아크릴산 유도체를 반응시킴으로써 얻어지는 우레탄(메트)아크릴레이트 등을 들 수 있고, 상기 서술한 바와 같이, 에폭시(메트)아크릴레이트가 바람직하다. 또, 상기 (메트)아크릴 화합물은, 반응성의 높음으로부터 분자 중에 (메트)아크릴로일기를 2 개 이상 갖는 것이 바람직하다.Examples of the (meth) acrylic compound as the other curable resin include epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with an epoxy compound, and (meth) acrylic acid obtained by reacting (Meth) acrylate ester compound obtained by reacting a (meth) acrylic acid ester compound having a hydroxyl group with an isocyanate compound and a (meth) acrylic acid derivative having a hydroxyl group in the isocyanate compound. As described above, epoxy (meth) acrylate is preferable. It is preferable that the (meth) acrylic compound has two or more (meth) acryloyl groups in the molecule because of high reactivity.
상기 에폭시(메트)아크릴레이트로는, 예를 들어, 에폭시 화합물과 (메트)아크릴산을, 통상적인 방법에 따라 염기성 촉매의 존재하에서 반응시킴으로써 얻어지는 것 등을 들 수 있다.The epoxy (meth) acrylate includes, for example, those obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
상기 에폭시(메트)아크릴레이트를 합성하기 위한 원료가 되는 에폭시 화합물로는, 예를 들어, 비스페놀 A 형 에폭시 수지, 비스페놀 F 형 에폭시 수지, 비스페놀 E 형 에폭시 수지, 비스페놀 S 형 에폭시 수지, 2,2'-디알릴비스페놀 A 형 에폭시 수지, 수소 첨가 비스페놀형 에폭시 수지, 프로필렌옥사이드 부가 비스페놀 A 형 에폭시 수지, 레조르시놀형 에폭시 수지, 비페닐형 에폭시 수지, 술파이드형 에폭시 수지, 디페닐에테르형 에폭시 수지, 디시클로펜타디엔형 에폭시 수지, 나프탈렌형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 오르토 크레졸 노볼락형 에폭시 수지, 디시클로펜타디엔 노볼락형 에폭시 수지, 비페닐 노볼락형 에폭시 수지, 나프탈렌페놀 노볼락형 에폭시 수지, 글리시딜아민형 에폭시 수지, 알킬폴리올형 에폭시 수지, 고무 변성형 에폭시 수지, 글리시딜에스테르 화합물 등을 들 수 있다. 그 중에서도, 레조르시놀형 에폭시 수지가 바람직하다.Examples of the epoxy compound to be a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2 '-Dialyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin , Dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalene phenol novolak Alkoxypolyol type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, There may be mentioned resins, glycidyl ester compounds. Among them, a resorcinol-type epoxy resin is preferable.
상기 비스페놀 A 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, jER828EL, jER1004 (모두 미츠비시 화학사 제조), 에피클론 850CRP (DIC 사 제조) 등을 들 수 있다.Examples of commercially available bisphenol A type epoxy resins include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation) and Epiclon 850CRP (manufactured by DIC Corporation).
상기 비스페놀 F 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, jER806, jER4004 (모두 미츠비시 화학사 제조) 등을 들 수 있다.Examples of commercially available bisphenol F type epoxy resins include, for example, jER806 and jER4004 (all manufactured by Mitsubishi Chemical Corporation).
상기 비스페놀 E 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, R710 (프린텍사 제조) 등을 들 수 있다.Commercially available examples of the bisphenol E type epoxy resin include R710 (manufactured by PRINTEC Co., Ltd.) and the like.
상기 비스페놀 S 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, 에피클론 EXA1514 (DIC 사 제조) 등을 들 수 있다.Examples of commercially available bisphenol S epoxy resins include Epiclon EXA1514 (manufactured by DIC Corporation) and the like.
상기 2,2'-디알릴비스페놀 A 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, RE-810NM (닛폰 화약사 제조) 등을 들 수 있다.Examples of commercially available 2,2'-diallyl bisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Yakusho Co., Ltd.) and the like.
상기 수소 첨가 비스페놀형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, 에피클론 EXA7015 (DIC 사 제조) 등을 들 수 있다.Examples of the hydrogenated bisphenol-type epoxy resin commercially available include Epiclon EXA7015 (manufactured by DIC Corporation) and the like.
상기 프로필렌옥사이드 부가 비스페놀 A 형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, EP-4000S (ADEKA 사 제조) 등을 들 수 있다.Examples of the propylene oxide-added bisphenol A type epoxy resin commercially available include EP-4000S (manufactured by ADEKA) and the like.
상기 레조르시놀형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, EX-201 (나가세 켐텍스사 제조) 등을 들 수 있다.Examples of commercially available resorcinol-type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation) and the like.
상기 비페닐형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, jER YX-4000H (미츠비시 화학사 제조) 등을 들 수 있다.Examples of commercially available biphenyl type epoxy resins include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
상기 술파이드형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, YSLV-50TE (신닛테츠 스미킨 화학사 제조) 등을 들 수 있다.Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.) and the like.
상기 디페닐에테르형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, YSLV-80DE (신닛테츠 스미킨 화학사 제조) 등을 들 수 있다.Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Shinnitetsu Sumikin Chemical Industry Co., Ltd.) and the like.
상기 디시클로펜타디엔형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, EP-4088S (ADEKA 사 제조) 등을 들 수 있다.Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA) and the like.
상기 나프탈렌형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, 에피클론 HP4032, 에피클론 EXA-4700 (모두 DIC 사 제조) 등을 들 수 있다.Examples of commercially available naphthalene type epoxy resins include Epiclon HP4032 and Epiclon EXA-4700 (both manufactured by DIC).
상기 페놀 노볼락형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, 에피클론 N-770 (DIC 사 제조) 등을 들 수 있다.Examples of commercially available phenol novolak epoxy resins include Epiclon N-770 (manufactured by DIC Corporation) and the like.
상기 오르토 크레졸 노볼락형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, 에피클론 N-670-EXP-S (DIC 사 제조) 등을 들 수 있다.Examples of the commercially available orthocresol novolak type epoxy resin include Epiclon N-670-EXP-S (manufactured by DIC Corporation) and the like.
상기 디시클로펜타디엔 노볼락형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, 에피클론 HP7200 (DIC 사 제조) 등을 들 수 있다.Examples of commercially available dicyclopentadiene novolak type epoxy resins include Epiclon HP7200 (manufactured by DIC Corporation) and the like.
상기 비페닐 노볼락형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, NC-3000P (닛폰 화약사 제조) 등을 들 수 있다.Commercially available examples of the biphenyl novolak type epoxy resin include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.
상기 나프탈렌페놀 노볼락형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, ESN-165S (신닛테츠 스미킨 화학사 제조) 등을 들 수 있다.Examples of commercially available naphthalene phenol novolak type epoxy resins include ESN-165S (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.).
상기 글리시딜아민형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, jER630 (미츠비시 화학사 제조), 에피클론 430 (DIC 사 제조), TETRAD-X (미츠비시 가스 화학사 제조) 등을 들 수 있다.Examples of commercially available glycidylamine type epoxy resins include jER 630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Company).
상기 알킬폴리올형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, ZX-1542 (신닛테츠 스미킨 화학사 제조), 에피클론 726 (DIC 사 제조), 에포라이트 80MFA (쿄에이샤 화학사 제조), 데나콜 EX-611 (나가세 켐텍스사 제조) 등을 들 수 있다.Examples of commercially available products of the alkyl polyol type epoxy resin include ZX-1542 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), Epiclon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyowa Chemical Industry Co., Ltd.) Cole EX-611 (manufactured by Nagase ChemteX Corporation), and the like.
상기 고무 변성형 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, YR-450, YR-207 (모두 신닛테츠 스미킨 화학사 제조), 에포리드 PB (다이셀사 제조) 등을 들 수 있다.Examples of the commercially available rubber-modified epoxy resin include YR-450 and YR-207 (all manufactured by Shinnitetsu Sumikin Chemical Industry Co., Ltd.) and Epolide PB (manufactured by Daicel Chemical Industries, Ltd.).
상기 글리시딜에스테르 화합물 중 시판되고 있는 것으로는, 예를 들어, 데나콜 EX-147 (나가세 켐텍스사 제조) 등을 들 수 있다.Examples of commercially available glycidyl ester compounds include, for example, Denacol EX-147 (manufactured by Nagase ChemteX).
상기 에폭시 화합물 중 그 밖에 시판되고 있는 것으로는, 예를 들어, YDC-1312, YSLV-80XY, YSLV-90CR (모두 신닛테츠 스미킨 화학사 제조), XAC4151 (아사히 화성사 제조), jER1031, jER1032 (모두 미츠비시 화학사 제조), EXA-7120 (DIC 사 제조), TEPIC (닛산 화학사 제조) 등을 들 수 있다.Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 EXA-7120 (manufactured by DIC Corporation), and TEPIC (manufactured by Nissan Chemical Industries, Ltd.).
상기 에폭시(메트)아크릴레이트 중 시판되고 있는 것으로는, 예를 들어, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 (모두 다이셀·올넥스사 제조), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (모두 신나카무라 화학 공업사 제조), 에폭시에스테르 M-600A, 에폭시에스테르 40EM, 에폭시에스테르 70PA, 에폭시에스테르 200PA, 에폭시에스테르 80MFA, 에폭시에스테르 3002M, 에폭시에스테르 3002A, 에폭시에스테르 1600A, 에폭시에스테르 3000M, 에폭시에스테르 3000A, 에폭시에스테르 200EA, 에폭시에스테르 400EA (모두 쿄에이샤 화학사 제조), 데나콜아크릴레이트 DA-141, 데나콜아크릴레이트 DA-314, 데나콜아크릴레이트 DA-911 (모두 나가세 켐텍스사 제조) 등을 들 수 있다.Examples of the epoxy (meth) acrylate commercially available include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYLRDX63182 Epoxy ester M-600A, Epoxy ester 40EM, Epoxy ester 70PA, Epoxy ester 70PA, Epoxy resin 70PA, Epoxy resin 70PA, Epoxy ester 200AA, Epoxy ester 80MFA, Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyowa Chemical Industry Co., Ltd.), Denacol acrylate DA- 141, Denacol acrylate DA-314, Denacol acrylate DA-911 (all manufactured by Nagase Chemtech), and the like.
상기 (메트)아크릴산에스테르 화합물 중 단관능의 것으로는, 예를 들어, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, t-부틸(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, n-옥틸(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 이소노닐(메트)아크릴레이트, 이소데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 이소미리스틸(메트)아크릴레이트, 스테아릴(메트)아크릴레이트, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 비시클로펜테닐(메트)아크릴레이트, 벤질(메트)아크릴레이트, 2-메톡시에틸(메트)아크릴레이트, 2-에톡시에틸(메트)아크릴레이트, 2-부톡시에틸(메트)아크릴레이트, 2-페녹시에틸(메트)아크릴레이트, 메톡시에틸렌글리콜(메트)아크릴레이트, 메톡시폴리에틸렌글리콜(메트)아크릴레이트, 페녹시디에틸렌글리콜(메트)아크릴레이트, 페녹시폴리에틸렌글리콜(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, 에틸카르비톨(메트)아크릴레이트, 2,2,2-트리플루오로에틸(메트)아크릴레이트, 2,2,3,3-테트라플루오로프로필(메트)아크릴레이트, 1H,1H,5H-옥타플루오로펜틸(메트)아크릴레이트, 이미드(메트)아크릴레이트, 디메틸아미노에틸(메트)아크릴레이트, 디에틸아미노에틸(메트)아크릴레이트, 2-(메트)아크릴로일옥시에틸숙신산, 2-(메트)아크릴로일옥시에틸헥사하이드로프탈산, 2-(메트)아크릴로일옥시에틸2-하이드록시프로필프탈레이트, 2-(메트)아크릴로일옥시에틸포스페이트, 글리시딜(메트)아크릴레이트 등을 들 수 있다.Examples of monofunctional (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) (Meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isohexyl (meth) acrylate, (Meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl ) Acrylate, benzyl (meth) acrylate (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxyethyleneglycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl Acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (Meth) acrylate, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acrylate, diethylaminoethyl (meth) (Meth) acryloyloxyethyl (meth) acryloyloxyethylhexahydrophthalic acid, 2- 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, and the like.
또, 상기 (메트)아크릴산에스테르 화합물 중 2 관능의 것으로는, 예를 들어, 1,3-부탄디올디(메트)아크릴레이트, 1,4-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 1,9-노난디올디(메트)아크릴레이트, 1,10-데칸디올디(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 테트라에틸렌글리콜디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 2-n-부틸-2-에틸-1,3-프로판디올디(메트)아크릴레이트, 디프로필렌글리콜디(메트)아크릴레이트, 트리프로필렌글리콜디(메트)아크릴레이트, 폴리프로필렌글리콜디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 에틸렌옥사이드 부가 비스페놀 A 디(메트)아크릴레이트, 프로필렌옥사이드 부가 비스페놀 A 디(메트)아크릴레이트, 에틸렌옥사이드 부가 비스페놀 F 디(메트)아크릴레이트, 디메틸올디시클로펜타디에닐디(메트)아크릴레이트, 에틸렌옥사이드 변성 이소시아누르산디(메트)아크릴레이트, 2-하이드록시-3-(메트)아크릴로일옥시프로필(메트)아크릴레이트, 카보네이트디올디(메트)아크릴레이트, 폴리에테르디올디(메트)아크릴레이트, 폴리에스테르디올디(메트)아크릴레이트, 폴리카프로락톤디올디(메트)아크릴레이트, 폴리부타디엔디올디(메트)아크릴레이트 등을 들 수 있다.Examples of the bifunctional (meth) acrylate ester compound include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Acrylate such as di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, dipropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 2-ethylhexyl (Meth) acrylate, ethylene oxide adduct bisphenol A di (meth) acrylate, propylene oxide di (meth) acrylate, neopentyl glycol di A di (meth) acrylate, (Meth) acrylate, ethylene oxide modified diisocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl di (Meth) acrylate, polycaprolactone diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di Diol di (meth) acrylate, and the like.
또, 상기 (메트)아크릴산에스테르 화합물 중 3 관능 이상의 것으로는, 예를 들어, 트리메틸올프로판트리(메트)아크릴레이트, 에틸렌옥사이드 부가 트리메틸올프로판트리(메트)아크릴레이트, 프로필렌옥사이드 부가 트리메틸올프로판트리(메트)아크릴레이트, 에틸렌옥사이드 부가 이소시아누르산트리(메트)아크릴레이트, 글리세린트리(메트)아크릴레이트, 프로필렌옥사이드 부가 글리세린트리(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 트리스(메트)아크릴로일옥시에틸포스페이트, 디트리메틸올프로판테트라(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트 등을 들 수 있다.Examples of the trifunctional or higher functional group in the (meth) acrylic acid ester compound include trimethylolpropane tri (meth) acrylate, ethylene oxide addition trimethylolpropane tri (meth) acrylate, and propylene oxide addition trimethylolpropane tri (Meth) acrylate, ethylene oxide adduct isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide addition glycerin tri (meth) acrylate, pentaerythritol tri (Meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Acrylate, and the like.
상기 우레탄(메트)아크릴레이트로는, 예를 들어, 2 개의 이소시아네이트기를 갖는 이소시아네이트 화합물 1 당량에 대해 수산기를 갖는 (메트)아크릴산 유도체 2 당량을, 촉매량의 주석계 화합물 존재하에서 반응시킴으로써 얻을 수 있다.The urethane (meth) acrylate can be obtained, for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with one equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin compound.
상기 우레탄(메트)아크릴레이트의 원료가 되는 이소시아네이트 화합물로는, 예를 들어, 이소포론디이소시아네이트, 2,4-톨릴렌디이소시아네이트, 2,6-톨릴렌 디이소시아네이트, 헥사메틸렌디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트, 디페닐메탄-4,4'-디이소시아네이트 (MDI), 수소 첨가 MDI, 폴리메릭 MDI, 1,5-나프탈렌디이소시아네이트, 노르보르난디이소시아네이트, 톨리딘디이소시아네이트, 자일릴렌디이소시아네이트 (XDI), 수소 첨가 XDI, 리신디이소시아네이트, 트리페닐메탄트리이소시아네이트, 트리스(이소시아네이트페닐)티오포스페이트, 테트라메틸자일렌디이소시아네이트, 1,6,11-운데칸트리이소시아네이트 등을 들 수 있다.Examples of the isocyanate compound as a raw material of the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene Diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornadiisocyanate, tolylidine diisocyanate, xylylene diisocyanate (XDI) , Hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethyl xylene diisocyanate, and 1,6,11-undecane triisocyanate.
또, 상기 우레탄(메트)아크릴레이트의 원료가 되는 이소시아네이트 화합물로는, 예를 들어, 에틸렌글리콜, 프로필렌글리콜, 글리세린, 소르비톨, 트리메틸올프로판, 카보네이트디올, 폴리에테르디올, 폴리에스테르디올, 폴리카프로락톤디올 등의 폴리올과 과잉의 이소시아네이트 화합물의 반응에 의해 얻어지는 사슬 연장된 이소시아네이트 화합물도 사용할 수 있다.Examples of the isocyanate compound as a raw material of the urethane (meth) acrylate include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylol propane, carbonate diol, polyether diol, polyester diol, polycaprolactone A chain extended isocyanate compound obtained by reacting a polyol such as diol with an excess of an isocyanate compound may also be used.
상기 우레탄(메트)아크릴레이트의 원료가 되는, 수산기를 갖는 (메트)아크릴산 유도체로는, 예를 들어, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트 등의 하이드록시알킬(메트)아크릴레이트나, 에틸렌글리콜, 프로필렌글리콜, 1,3-프로판디올, 1,3-부탄디올, 1,4-부탄디올, 폴리에틸렌글리콜 등의 2 가의 알코올의 모노(메트)아크릴레이트나, 트리메틸올에탄, 트리메틸올프로판, 글리세린 등의 3 가의 알코올의 모노(메트)아크릴레이트 또는 디(메트)아크릴레이트나, 비스페놀 A 형 에폭시아크릴레이트 등의 에폭시(메트)아크릴레이트 등을 들 수 있다.Examples of the (meth) acrylic acid derivative having a hydroxyl group which is a raw material of the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, and hydroxyalkyl (meth) acrylates such as ethylene glycol, propylene glycol, , Mono (meth) acrylate of a dihydric alcohol such as 1,4-butanediol and polyethylene glycol, mono (meth) acrylate or di (meth) acrylate of a trihydric alcohol such as trimethylolethane, trimethylolpropane, Epoxy (meth) acrylates such as bisphenol A type epoxy acrylate, and the like.
상기 우레탄(메트)아크릴레이트 중 시판되고 있는 것으로는, 예를 들어, M-1100, M-1200, M-1210, M-1600 (모두 토아 합성사 제조), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 (모두 다이셀·올넥스사 제조), 아트 레진 UN-330, 아트 레진 SH-500B, 아트 레진 UN-1200TPK, 아트 레진 UN-1255, 아트 레진 UN-3320HB, 아트 레진 UN-7100, 아트 레진 UN-9000A, 아트 레진 UN-9000H (모두 네가미 공업사 제조), 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 (모두 신나카무라 화학 공업사 제조), AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (모두 쿄에이샤 화학사 제조) 등을 들 수 있다.Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210 and M-1600 (all manufactured by TOAGOSEI CO., LTD.), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 (all manufactured by Daicel Alnex), ARTICLE UN-330, ARTICLE SH- U-2HA, U-3HA, U-3HA, Urethane UN-9000A, Art Resin UN-9000A (all manufactured by Negami Industrial Co., Ltd.) U-340H, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, UA-W2A (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA- (All manufactured by Kyoeisha Chemical Co., Ltd.), AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA- Division), and the like.
상기 그 밖의 경화성 수지인 에폭시 화합물로는, 예를 들어, 상기 에폭시(메트)아크릴레이트를 합성하기 위한 원료가 되는 에폭시 화합물이나, 식 (1) 로 나타내는 화합물 이외의 부분 (메트)아크릴 변성 에폭시 수지 등을 들 수 있다.Examples of the other epoxy compound which is a curable resin include an epoxy compound which is a raw material for synthesizing the epoxy (meth) acrylate, a partial (meth) acryl-modified epoxy resin other than the compound represented by the formula And the like.
또한, 본 명세서에 있어서 상기 부분 (메트)아크릴 변성 에폭시 수지란, 1 분자 중에 에폭시기와 (메트)아크릴로일기를 각각 1 개 이상 갖는 화합물을 의미하고, 예를 들어, 2 개 이상의 에폭시 화합물의 일부분의 에폭시기를 (메트)아크릴산과 반응시킴으로써 얻을 수 있다.In the present specification, the partial (meth) acrylic modified epoxy resin means a compound having at least one epoxy group and at least one (meth) acryloyl group in one molecule. For example, a part of two or more epoxy compounds Can be obtained by reacting an epoxy group of (meth) acrylic acid.
상기 부분 (메트)아크릴 변성 에폭시 수지 중 시판되고 있는 것으로는, 예를 들어, UVACURE1561 (다이셀·올넥스사 제조) 등을 들 수 있다.Examples of commercially available partial (meth) acrylic-modified epoxy resins include UVACURE 1561 (manufactured by Daicel Alnex Co., Ltd.).
상기 그 밖의 경화성 수지를 함유하는 경우, 경화성 수지 전체 100 중량부 중에 있어서의 상기 식 (1) 로 나타내는 화합물의 함유량의 바람직한 하한은 5 중량부, 바람직한 상한은 25 중량부이다. 상기 식 (1) 로 나타내는 화합물의 함유량이 이 범위임으로써, 얻어지는 액정 표시 소자용 시일제가 도포성, 접착성, 투습 방지성, 및, 액정 오염을 억제하는 효과가 보다 우수한 것이 된다. 상기 식 (1) 로 나타내는 화합물의 함유량의 보다 바람직한 하한은 10 중량부, 보다 바람직한 상한은 20 중량부이다.When the other curable resin is contained, the preferable lower limit of the content of the compound represented by the formula (1) in 100 parts by weight of the entire curable resin is 5 parts by weight, and the preferable upper limit is 25 parts by weight. When the content of the compound represented by the above formula (1) is within this range, the resulting sealant for a liquid crystal display element is more excellent in the coating property, the adhesive property, the moisture permeation preventive property, and the effect of suppressing liquid crystal contamination. A more preferable lower limit of the content of the compound represented by the formula (1) is 10 parts by weight, and a more preferable upper limit is 20 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 경화성 수지 중의 (메트)아크릴로일기와 에폭시기의 함유 비율을 몰비로 50 : 50 ∼ 95 : 5 로 하는 것이 바람직하다.In the liquid crystal display element sealant of the present invention, the content ratio of the (meth) acryloyl group and the epoxy group in the curable resin is preferably 50:50 to 95: 5 in a molar ratio.
본 발명의 액정 표시 소자용 시일제는, 라디칼 중합 개시제 및/또는 열 경화제를 함유한다.The liquid crystal display element sealant of the present invention contains a radical polymerization initiator and / or a thermosetting agent.
상기 라디칼 중합 개시제로는, 광 조사에 의해 라디칼을 발생시키는 광 라디칼 중합 개시제나, 가열에 의해 라디칼을 발생시키는 열 라디칼 중합 개시제 등을 들 수 있다.Examples of the radical polymerization initiator include a photo-radical polymerization initiator that generates radicals by light irradiation, and a thermal radical polymerization initiator that generates radicals by heating.
상기 광 라디칼 중합 개시제로는, 예를 들어, 벤조페논계 화합물, 아세토페논계 화합물, 아실포스핀옥사이드계 화합물, 티타노센계 화합물, 옥심에스테르계 화합물, 벤조인에테르계 화합물, 티오크산톤계 화합물 등을 들 수 있다.Examples of the photo radical polymerization initiator include a benzophenone compound, an acetophenone compound, an acylphosphine oxide compound, a titanocene compound, an oxime ester compound, a benzoin ether compound, a thioxanthone compound, etc. .
상기 광 라디칼 중합 개시제 중 시판되고 있는 것으로는, 예를 들어, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, 루시린 TPO (모두 BASF 사 제조), NCI-930 (ADEKA 사 제조), SPEEDCURE EMK (니혼 시베르헤그너사 제조), 벤소인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르 (모두 토쿄 화성 공업사 제조) 등을 들 수 있다.IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, lucylline TPO (all manufactured by BASF), and the like, NCI-930 (manufactured by ADEKA), SPEEDCURE EMK (manufactured by Nippon Shokubera Co., Ltd.), benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.).
상기 열 라디칼 중합 개시제로는, 예를 들어, 아조 화합물, 유기 과산화물 등으로 이루어지는 것을 들 수 있다. 그 중에서도, 고분자 아조 화합물로 이루어지는 개시제 (이하,「고분자 아조 개시제」라고도 한다) 가 바람직하다.Examples of the thermal radical polymerization initiator include azo compounds, organic peroxides, and the like. Among them, an initiator comprising a polymeric azo compound (hereinafter also referred to as a " polymeric azo initiator ") is preferred.
또한, 본 명세서에 있어서 고분자 아조 화합물이란, 아조기를 갖고, 열에 의해 (메트)아크릴로일기를 경화시킬 수 있는 라디칼을 생성하는, 수평균 분자량이 300 이상인 화합물을 의미한다.In the present specification, the polymer azo compound means a compound having an azo group and having a number average molecular weight of 300 or more, which generates a radical capable of curing the (meth) acryloyl group by heat.
상기 고분자 아조 개시제의 수평균 분자량의 바람직한 하한은 1000, 바람직한 상한은 30 만이다. 상기 고분자 아조 개시제의 수평균 분자량이 이 범위임으로써, 액정 오염을 억제하면서, 경화성 수지와 용이하게 혼합할 수 있다. 상기 고분자 아조 개시제의 수평균 분자량의 보다 바람직한 하한은 5000, 보다 바람직한 상한은 10 만이고, 더욱 바람직한 하한은 1 만, 더욱 바람직한 상한은 9 만이다.The preferred lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferred upper limit is 300,000. When the number average molecular weight of the polymeric azo initiator is within this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination. A more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, a more preferable upper limit is 100,000, a more preferable lower limit is 10,000, and a more preferable upper limit is 90,000.
또한, 본 명세서에 있어서, 상기 수평균 분자량은, 겔 퍼미에이션 크로마토그래피 (GPC) 로 측정을 실시하여, 폴리스티렌 환산에 의해 구해지는 값이다. GPC 에 의해 폴리스티렌 환산에 의한 수평균 분자량을 측정할 때의 칼럼으로는, 예를 들어, Shodex LF-804 (쇼와 전공사 제조) 등을 들 수 있다.Further, in the present specification, the number average molecular weight is a value obtained by performing measurement by gel permeation chromatography (GPC) and calculating by polystyrene conversion. As a column for measuring the number average molecular weight by polystyrene conversion by GPC, for example, Shodex LF-804 (manufactured by Showa Denko K.K.) can be mentioned.
상기 고분자 아조 개시제로는, 예를 들어, 아조기를 개재하여 폴리알킬렌옥사이드나 폴리디메틸실록산 등의 유닛이 복수 결합한 구조를 갖는 것을 들 수 있다.Examples of the polymeric azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded through an azo group.
상기 아조기를 개재하여 폴리알킬렌옥사이드 등의 유닛이 복수 결합한 구조를 갖는 고분자 아조 개시제로는, 폴리에틸렌옥사이드 구조를 갖는 것이 바람직하다. 이와 같은 고분자 아조 개시제로는, 예를 들어, 4,4'-아조비스(4-시아노펜탄산) 과 폴리알킬렌글리콜의 중축합물이나, 4,4'-아조비스(4-시아노펜탄산) 과 말단 아미노기를 갖는 폴리디메틸실록산의 중축합물 등을 들 수 있고, 구체적으로는 예를 들어, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (모두 와코 순약 공업사 제조) 등을 들 수 있다.As the polymeric azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded through the azo group, it is preferable that the polymeric azo initiator has a polyethylene oxide structure. Examples of such a polymeric azo initiator include polycondensation products of 4,4'-azobis (4-cyanopentanoic acid) and polyalkylene glycol, 4,4'-azobis (4-cyanopentanoic acid) VPE-0201, VPE-0401, VPE-0601, VPS-0501 and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.), and polycondensates of polydimethylsiloxane having terminal amino groups. And the like.
또, 고분자가 아닌 아조 화합물의 예로는, V-65, V-501 (모두 와코 순약 공업사 제조) 등을 들 수 있다.Examples of the azo compound which is not a polymer include V-65 and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.).
상기 유기 과산화물로는, 예를 들어, 케톤퍼옥사이드, 퍼옥시케탈, 하이드로퍼옥사이드, 디알킬퍼옥사이드, 퍼옥시에스테르, 디아실퍼옥사이드, 퍼옥시디카보네이트 등을 들 수 있다.Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, peroxydicarbonate, and the like.
상기 라디칼 중합 개시제의 함유량은, 경화성 수지 100 중량부에 대해, 바람직한 하한이 0.01 중량부, 바람직한 상한이 10 중량부이다. 상기 라디칼 중합 개시제의 함유량이 이 범위임으로써, 얻어지는 액정 표시 소자용 시일제가 액정 오염을 억제하면서, 보존 안정성이나 경화성이 보다 우수한 것이 된다. 상기 라디칼 중합 개시제의 함유량의 보다 바람직한 하한은 0.1 중량부, 보다 바람직한 상한은 5 중량부이다.The content of the radical polymerization initiator is preferably 0.01 part by weight, and more preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the radical polymerization initiator is within the above range, the resulting liquid crystal display element sealant exhibits excellent storage stability and curability while suppressing liquid crystal contamination. A more preferable lower limit of the content of the radical polymerization initiator is 0.1 part by weight, and a more preferable upper limit is 5 parts by weight.
상기 열 경화제로는, 예를 들어, 유기산 히드라지드, 이미다졸 유도체, 아민 화합물, 다가 페놀계 화합물, 산 무수물 등을 들 수 있다. 그 중에서도, 유기산 히드라지드가 바람직하게 사용된다.Examples of the heat curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, and acid anhydrides. Among them, organic acid hydrazide is preferably used.
상기 유기산 히드라지드로는, 예를 들어, 세바크산디히드라지드, 이소프탈산디히드라지드, 아디프산디히드라지드, 말론산디히드라지드 등을 들 수 있다.The organic acid hydrazide includes, for example, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide.
상기 유기산 히드라지드 중 시판되고 있는 것으로는, 예를 들어, SDH, ADH (모두 오오츠카 화학사 제조), 아미큐어 VDH, 아미큐어 VDH-J, 아미큐어 UDH, 아미큐어 UDH-J (모두 아지노모토 파인테크노사 제조) 등을 들 수 있다.Examples of the organic acid hydrazide which is commercially available include SDH, ADH (all manufactured by Otsuka Chemical), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all available from Ajinomoto Fine Techno Co., And the like.
상기 열 경화제의 함유량은, 상기 경화성 수지 100 중량부에 대해, 바람직한 하한이 1 중량부, 바람직한 상한이 50 중량부이다. 상기 열 경화제의 함유량이 이 범위임으로써, 얻어지는 액정 표시 소자용 시일제의 도포성 등을 악화시키지 않고, 보다 열 경화성이 우수한 것으로 할 수 있다. 상기 열 경화제의 함유량의 보다 바람직한 상한은 30 중량부이다.The content of the thermosetting agent is preferably 1 part by weight, and more preferably 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the thermosetting agent is in this range, the thermosetting property can be further improved without deteriorating the coatability and the like of the resultant liquid crystal display element sealant. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 점도의 향상, 응력 분산 효과에 의한 접착성의 개선, 선팽창률의 개선, 경화물의 투습 방지성의 향상 등을 목적으로 하여 충전제를 함유하는 것이 바람직하다.The sealing agent for a liquid crystal display element of the present invention preferably contains a filler for the purpose of improving viscosity, improving adhesiveness by stress dispersion effect, improving linear expansion rate, improving moisture permeability of a cured product, and the like.
상기 충전제로는, 예를 들어, 실리카, 탤크, 유리 비즈, 석면, 석고, 규조토, 스멕타이트, 벤토나이트, 몬모릴로나이트, 세리사이트, 활성 백토, 알루미나, 산화아연, 산화철, 산화마그네슘, 산화주석, 산화티탄, 탄산칼슘, 탄산마그네슘, 수산화마그네슘, 수산화알루미늄, 질화알루미늄, 질화규소, 황산바륨, 규산칼슘 등의 무기 충전제나, 폴리에스테르 미립자, 폴리우레탄 미립자, 비닐 중합체 미립자, 아크릴 중합체 미립자 등의 유기 충전제를 들 수 있다.Examples of the filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, Inorganic fillers such as calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate and calcium silicate; and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles and acrylic polymer fine particles have.
본 발명의 액정 표시 소자용 시일제 중에 있어서의 상기 충전제의 함유량의 바람직한 하한은 10 중량％, 바람직한 상한은 70 중량％ 이다. 상기 충전제의 함유량이 이 범위임으로써, 도포성 등을 악화시키지 않고, 접착성의 개선 등의 효과가 보다 우수한 것이 된다. 상기 충전제의 함유량의 보다 바람직한 하한은 20 중량％, 보다 바람직한 상한은 60 중량％ 이다.The preferable lower limit of the content of the filler in the liquid crystal display element sealant of the present invention is 10% by weight, and the preferable upper limit is 70% by weight. When the content of the filler is in this range, the effects such as improvement in adhesiveness are more excellent without deteriorating coatability and the like. A more preferable lower limit of the content of the filler is 20% by weight, and a more preferable upper limit is 60% by weight.
본 발명의 액정 표시 소자용 시일제는, 실란 커플링제를 함유하는 것이 바람직하다. 상기 실란 커플링제는, 주로 시일제와 기판 등을 양호하게 접착하기 위한 접착 보조제로서의 역할을 갖는다.The liquid crystal display element sealant of the present invention preferably contains a silane coupling agent. The silane coupling agent serves mainly as an adhesion assisting agent for favorably bonding a sealant and a substrate.
상기 실란 커플링제로는, 기판 등과의 접착성을 향상시키는 효과가 우수하고, 경화성 수지와 화학 결합함으로써 액정 중으로의 경화성 수지의 유출을 억제할 수 있는 점에서, 예를 들어, 3-아미노프로필트리메톡시실란, 3-메르캅토프로필트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-이소시아네이트프로필트리메톡시실란 등이 바람직하게 사용된다.Examples of the silane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, etc. In view of being excellent in the effect of improving adhesiveness with a substrate and the like and being capable of inhibiting the outflow of the curable resin into the liquid crystal by chemical bonding with the curable resin, Methoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane and the like are preferably used.
본 발명의 액정 표시 소자용 시일제 중에 있어서의 상기 실란 커플링제의 함유량의 바람직한 하한은 0.1 중량％, 바람직한 상한은 10 중량％ 이다. 상기 실란 커플링제의 함유량이 이 범위임으로써, 액정 오염의 발생을 억제하면서, 접착성을 향상시키는 효과가 보다 우수한 것이 된다. 상기 실란 커플링제의 함유량의 보다 바람직한 하한은 0.3 중량％, 보다 바람직한 상한은 5 중량％ 이다.The lower limit of the content of the silane coupling agent in the liquid crystal display element sealant of the present invention is 0.1 wt%, and the upper limit is preferably 10 wt%. When the content of the silane coupling agent is in this range, the effect of improving adhesion is further improved while suppressing the occurrence of liquid crystal contamination. A more preferable lower limit of the content of the silane coupling agent is 0.3 wt%, and a more preferable upper limit is 5 wt%.
본 발명의 액정 표시 소자용 시일제는, 차광제를 함유해도 된다. 상기 차광제를 함유함으로써, 본 발명의 액정 표시 소자용 시일제는, 차광 시일제로서 바람직하게 사용할 수 있다.The liquid crystal display element sealant of the present invention may contain a light shielding agent. By containing the above-mentioned light-shielding agent, the liquid crystal display element-sealing agent of the present invention can be preferably used as a light-shielding sealant.
상기 차광제로는, 예를 들어, 산화철, 티탄 블랙, 아닐린 블랙, 시아닌 블랙, 플러렌, 카본 블랙, 수지 피복형 카본 블랙 등을 들 수 있다. 그 중에서도 티탄 블랙이 바람직하다.Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferable.
상기 티탄 블랙은, 파장 300 ∼ 800 ㎚ 의 광에 대한 평균 투과율과 비교하여, 자외선 영역 부근, 특히 파장 370 ∼ 450 ㎚ 의 광에 대한 투과율이 높아지는 물질이다. 즉, 상기 티탄 블랙은, 가시광 영역의 파장의 광을 충분히 차폐함으로써 본 발명의 액정 표시 소자용 시일제에 차광성을 부여하는 한편, 자외선 영역 부근의 파장의 광은 투과시키는 성질을 갖는 차광제이다. 본 발명의 액정 표시 소자용 시일제에 함유되는 차광제로는, 절연성이 높은 물질이 바람직하고, 절연성이 높은 차광제로서도 티탄 블랙이 바람직하다.The titanium black is a material having a higher transmittance to light in the vicinity of the ultraviolet ray region, particularly in the wavelength range of 370 to 450 nm, as compared with the average transmittance in the wavelength range of 300 to 800 nm. That is, the titanium black is a light-shielding agent having a property of shielding light for a liquid crystal display element of the present invention by sufficiently shielding light having a wavelength in the visible light region while transmitting light having a wavelength in the vicinity of the ultraviolet ray region . As the light shielding agent contained in the sealing agent for a liquid crystal display element of the present invention, a substance having high insulating property is preferable, and titanium black is preferable as a light shielding agent having high insulating property.
상기 티탄 블랙은, 표면 처리되어 있지 않은 것이어도 충분한 효과를 발휘하지만, 표면이 커플링제 등의 유기 성분으로 처리되어 있는 것이나, 산화규소, 산화티탄, 산화게르마늄, 산화알루미늄, 산화지르코늄, 산화마그네슘 등의 무기 성분으로 피복되어 있는 것 등, 표면 처리된 티탄 블랙을 사용할 수도 있다. 그 중에서도, 유기 성분으로 처리되어 있는 것은, 보다 절연성을 향상시킬 수 있는 점에서 바람직하다.The titanium black exhibits a sufficient effect even if it is not surface-treated. However, the titanium black may be one having a surface treated with an organic component such as a coupling agent, or a titanium oxide such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide Or a titanium black coated with an inorganic component such as titanium black. Among them, it is preferable that the organic component is treated because it can further improve the insulating property.
또, 차광제로서 상기 티탄 블랙을 함유하는 본 발명의 액정 표시 소자용 시일제를 사용하여 제조한 액정 표시 소자는, 충분한 차광성을 갖기 때문에, 광의 누출이 없어 높은 콘트라스트를 갖고, 우수한 화상 표시 품질을 갖는 액정 표시 소자를 실현할 수 있다.Further, the liquid crystal display element manufactured by using the liquid crystal display element sealant of the present invention containing the titanium black as the light shielding agent has sufficient light shielding property, and therefore has no high leakage of light and has excellent contrast, The liquid crystal display device can be realized.
상기 티탄 블랙 중 시판되고 있는 것으로는, 예를 들어, 12S, 13M, 13M-C, 13R-N, 14M-C (모두 미츠비시 머테리얼사 제조), 틸락 D (아코 화성사 제조) 등을 들 수 있다.Examples of commercially available titanium black include 12S, 13M, 13M-C, 13R-N and 14M-C (both manufactured by Mitsubishi Materials Corporation) and Tilac D have.
상기 티탄 블랙의 비표면적의 바람직한 하한은 13 ㎡/g, 바람직한 상한은 30 ㎡/g 이고, 보다 바람직한 하한은 15 ㎡/g, 보다 바람직한 상한은 25 ㎡/g 이다.The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, and the upper limit is preferably 30 m 2 / g, more preferably 15 m 2 / g, and still more preferably 25 m 2 / g.
또, 상기 티탄 블랙의 체적 저항의 바람직한 하한은 0.5 Ω·㎝, 바람직한 상한은 3 Ω·㎝ 이고, 보다 바람직한 하한은 1 Ω·㎝, 보다 바람직한 상한은 2.5 Ω·㎝ 이다.The lower limit of the volume resistivity of the titanium black is 0.5 Ω · cm, and the upper limit is preferably 3 Ω · cm, more preferably 1 Ω · cm, and still more preferably 2.5 Ω · cm.
상기 차광제의 1 차 입자경은, 액정 표시 소자의 기판 사이의 거리 이하이면 특별히 한정되지 않지만, 바람직한 하한은 1 ㎚, 바람직한 상한은 5000 ㎚ 이다. 상기 차광제의 1 차 입자경이 이 범위임으로써, 얻어지는 액정 표시 소자용 시일제의 도포성 등을 악화시키지 않고 차광성이 보다 우수한 것으로 할 수 있다. 상기 차광제의 1 차 입자경의 보다 바람직한 하한은 5 ㎚, 보다 바람직한 상한은 200 ㎚, 더욱 바람직한 하한은 10 ㎚, 더욱 바람직한 상한은 100 ㎚ 이다.The primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element, but the lower limit is preferably 1 nm and the upper limit is preferably 5000 nm. When the primary particle size of the light-shielding agent is within this range, the light-shielding property can be made more excellent without deteriorating the coatability and the like of the resulting liquid crystal display element sealant. A more preferable lower limit of the primary particle size of the light-shielding agent is 5 nm, a more preferable upper limit is 200 nm, a still more preferable lower limit is 10 nm, and a more preferable upper limit is 100 nm.
또한, 상기 차광제의 1 차 입자경은, NICOMP 380ZLS (PARTICLE SIZING SYSTEMS 사 제조) 를 사용하여, 상기 차광제를 용매 (물, 유기 용매 등) 에 분산시켜 측정할 수 있다.The primary particle size of the light-shielding agent can be measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
본 발명의 액정 표시 소자용 시일제 중에 있어서의 상기 차광제의 함유량의 바람직한 하한은 5 중량％, 바람직한 상한은 80 중량％ 이다. 상기 차광제의 함유량이 이 범위임으로써, 얻어지는 액정 표시 소자용 시일제의 기판에 대한 밀착성이나 경화 후의 강도나 묘화성을 저하시키지 않고 보다 우수한 차광성을 발휘할 수 있다. 상기 차광제의 함유량의 보다 바람직한 하한은 10 중량％, 보다 바람직한 상한은 70 중량％ 이고, 더욱 바람직한 하한은 30 중량％, 더욱 바람직한 상한은 60 중량％ 이다.The content of the light-shielding agent in the liquid crystal display element sealant of the present invention is preferably 5% by weight, and more preferably 80% by weight. When the content of the light-shielding agent is within this range, it is possible to exhibit more excellent light-shielding properties without deteriorating the adhesion of the obtained liquid crystal display element sealant to the substrate, the strength and the rendering property after curing. A more preferable lower limit of the content of the light shielding agent is 10% by weight, and a more preferable upper limit is 70% by weight. A more preferable lower limit is 30% by weight, and a more preferable upper limit is 60% by weight.
본 발명의 액정 표시 소자용 시일제는, 추가로, 필요에 따라 응력 완화제, 반응성 희석제, 요변제, 스페이서, 경화 촉진제, 소포제, 레벨링제, 중합 금지제, 기타 첨가제 등을 함유해도 된다.The liquid crystal display element sealant of the present invention may further contain a stress relieving agent, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, a defoaming agent, a leveling agent, a polymerization inhibitor and other additives as necessary.
본 발명의 액정 표시 소자용 시일제를 제조하는 방법으로는, 예를 들어, 호모 디스퍼, 호모 믹서, 만능 믹서, 플레네터리 믹서, 니더, 3 본롤 등의 혼합기를 사용하여, 경화성 수지와, 중합 개시제 및/또는 열 경화제와, 필요에 따라 첨가하는 실란 커플링제 등의 첨가제를 혼합하는 방법 등을 들 수 있다.As a method for producing the sealant for a liquid crystal display element of the present invention, there can be used a method of producing a sealant for a liquid crystal display element by using a mixer such as homodisperse, homomixer, universal mixer, planetary mixer, kneader, A method of mixing additives such as a polymerization initiator and / or a thermosetting agent, and a silane coupling agent added as needed, and the like.
본 발명의 액정 표시 소자용 시일제는, E 형 점도계를 사용하여 25 ℃, 1 rpm 의 조건에서 측정한 점도의 바람직한 하한이 5 만 m㎩·s, 바람직한 상한이 70 만 m㎩·s 이다. 상기 점도가 이 범위임으로써, 얻어지는 액정 표시 소자용 시일제가 도포성이 우수한 것이 된다. 상기 점도의 보다 바람직한 하한은 10 만 m㎩·s, 보다 바람직한 상한은 50 만 m㎩·s 이다.The sealant for a liquid crystal display element of the present invention preferably has a viscosity lower limit of 50,000 mPa · s and a preferable upper limit of 700,000 mPa · s at 25 ° C and 1 rpm using an E-type viscometer. When the viscosity is in this range, the liquid crystal display element sealant obtained is excellent in coating property. A more preferred lower limit of the viscosity is 100,000 mPa s, and a more preferable upper limit is 500000 mPa s.
또한, 상기 E 형 점도계로는, 예를 들어, 5XHBDV-III+CP (브룩필드사 제조, 로터 No.CP-51) 등을 사용할 수 있다.As the E-type viscometer, for example, 5XHBDV-III + CP (manufactured by Brookfield Company, rotor No. CP-51) can be used.
본 발명의 액정 표시 소자용 시일제에, 도전성 미립자를 배합함으로써, 상하 도통 재료를 제조할 수 있다. 이와 같은 본 발명의 액정 표시 소자용 시일제와 도전성 미립자를 함유하는 상하 도통 재료 또한, 본 발명 중 하나이다.By mixing conductive fine particles in the liquid crystal display element-sealing material of the present invention, the upper and lower conductive materials can be produced. The liquid crystal display element sealant of the present invention and the upper and lower conductive material containing the conductive fine particles are also one of the present invention.
상기 도전성 미립자로는, 금속 볼, 수지 미립자의 표면에 도전 금속층을 형성한 것 등을 사용할 수 있다. 그 중에서도, 수지 미립자의 표면에 도전 금속층을 형성한 것은, 수지 미립자의 우수한 탄성에 의해, 투명 기판 등을 손상시키지 않고 도전 접속이 가능한 점에서 바람직하다.As the conductive fine particles, a metal ball, a resin fine particle having a conductive metal layer formed on its surface, or the like can be used. Among them, it is preferable that the conductive metal layer is formed on the surface of the resin fine particles because of the excellent elasticity of the resin fine particles in that conductive connection is possible without damaging the transparent substrate and the like.
본 발명의 액정 표시 소자용 시일제 또는 본 발명의 상하 도통 재료를 사용하여 이루어지는 액정 표시 소자 또한, 본 발명 중 하나이다.The liquid crystal display element using the liquid crystal display element sealing material of the present invention or the vertical conduction material of the present invention is also one of the present invention.
본 발명의 액정 표시 소자를 제조하는 방법으로는, 액정 적하 공법이 바람직하게 사용된다. 구체적으로는 예를 들어, ITO 박막 등의 전극이 부착된 유리 기판이나 폴리에틸렌테레프탈레이트 기판 등의 2 장의 기판의 일방에, 본 발명의 액정 표시 소자용 시일제를, 스크린 인쇄, 디스펜서 도포 등에 의해 도포하여 프레임상의 시일 패턴을 형성하는 공정, 본 발명의 액정 표시 소자용 시일제가 미경화인 상태에서 액정의 미소적을 기판의 시일 패턴의 프레임 내에 적하 도포하고, 진공하에서 다른 기판을 중첩하는 공정, 및, 본 발명의 액정 표시 소자용 시일제의 시일 패턴 부분에 자외선 등의 광을 조사하여 시일제를 임시 경화시키는 공정, 및, 임시 경화시킨 시일제를 가열하여 본경화시키는 공정을 갖는 방법 등을 들 수 있다.As a method for producing the liquid crystal display element of the present invention, a liquid crystal dropping method is preferably used. Specifically, for example, the liquid crystal display element sealant of the present invention is applied to one of two substrates, such as a glass substrate or an electrode substrate having an electrode such as an ITO thin film, or a polyethylene terephthalate substrate by screen printing, dispenser application, Forming a seal pattern on a frame, a step of dropping and applying a small amount of liquid crystal in a frame of a seal pattern of the substrate in the state that the sealant for a liquid crystal display element of the present invention is uncured, and overlapping another substrate under vacuum, A method of temporarily curing the sealant by irradiating light such as ultraviolet rays to the seal pattern portion of the sealant for a liquid crystal display element of the present invention and a method of temporarily curing the temporarily cured sealant to finally cure the sealant .
본 발명에 의하면, 도포성, 투습 방지성, 및, 접착성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제를 제공할 수 있다. 또, 본 발명에 의하면, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공할 수 있다.According to the present invention, it is possible to provide a sealant for a liquid crystal display element which is excellent in coating property, moisture permeation preventive property, adhesive property, and can suppress liquid crystal contamination. According to the present invention, the upper and lower conductive materials and the liquid crystal display element using the liquid crystal display element sealant can be provided.
이하에 실시예를 들어 본 발명을 더욱 상세하게 설명하지만, 본 발명은 이들 실시예에만 한정되지 않는다.Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
(식 (1) 로 나타내는 화합물 (R1 이 H, m ＝ n ＝ 0) 의 제조)(Preparation of a compound represented by the formula (1) (R 1 is H, m = n = 0)
비스페놀 S 디글리시딜에테르 1000 중량부, 중합 금지제로서 p-메톡시페놀 2 중량부, 반응 촉매로서 트리에틸아민 2 중량부, 및, 아크릴산 200 중량부를, 공기를 송입하면서 90 ℃ 에서 5 시간 환류 교반하여 반응시켰다. 얻어진 수지 100 중량부를, 반응물 중의 이온성 불순물을 흡착시키기 위해 쿼츠와 카올린의 천연 결합물 (호프먼 미네랄사 제조,「실리틴 V85」) 10 중량부가 충전된 칼럼에서 여과하여, 식 (1) 로 나타내는 화합물 (R1 이 H, m ＝ n ＝ 0) 을 얻었다. 또한, 얻어진 화합물이 식 (1) 로 나타내는 화합물 (R1 이 H, m ＝ n ＝ 0) 인 것은, 1H-NMR, 13C-NMR, 및, IR 에 의해 확인하였다.1000 parts by weight of bisphenol S diglycidyl ether, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid, The reaction was carried out by stirring under reflux. 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural bond of quartz and kaolin (manufactured by Hoffman Minerals, " Silicin V85 ") to adsorb ionic impurities in the reaction product, To obtain a compound (R 1 is H, m = n = 0). It was confirmed by 1 H-NMR, 13 C-NMR, and IR that the obtained compound was a compound represented by the formula (1) (R 1 is H, m = n = 0).
(식 (1) 로 나타내는 화합물 (R1 이 H, m ＝ n ＝ 1 (평균값)) 의 제조)(Preparation of a compound represented by the formula (1) (R 1 is H, m = n = 1 (average value)) [
온도계, 적하 로트, 냉각관, 및, 교반기를 부착한 플라스크에 4,4'-비스(2-하이드록시에틸옥시)디페닐술폰 169 중량부, 에피클로르하이드린 370 중량부, 디메틸술폭사이드 185 중량부, 및, 테트라메틸암모늄클로라이드 5 중량부를 첨가하여 교반하에서 용해시키고, 50 ℃ 까지 승온시켰다. 이어서, 플레이크상의 수산화나트륨 60 중량부를 100 분에 걸쳐 분할 첨가한 후, 다시 50 ℃ 에서 3 시간, 후반응을 실시하였다. 반응 종료 후, 물 400 중량부를 첨가하여 수세를 실시하고, 로터리 이베퍼레이터를 사용하여, 130 ℃, 감압하에서, 유층으로부터 과잉의 에피클로르하이드린 등을 증류 제거하였다. 잔류물에 메틸이소부틸케톤 450 중량부를 첨가하여 용해시키고, 70 ℃ 까지 승온시켰다. 교반하에서 30 ％ 의 수산화나트륨 수용액 10 중량부를 첨가하고, 1 시간 반응을 실시한 후, 수세를 3 회 실시하고, 로터리 이베퍼레이터를 사용하여, 180 ℃, 감압하에서, 메틸이소부틸케톤을 증류 제거하였다. 얻어진 반응물 1100 중량부, 중합 금지제로서 p-메톡시페놀 2 중량부, 반응 촉매로서 트리에틸아민 2 중량부, 및, 아크릴산 200 중량부를, 공기를 송입하면서 90 ℃ 에서 5 시간 환류 교반하여 반응시켰다. 얻어진 수지 100 중량부를, 반응물 중의 이온성 불순물을 흡착시키기 위해 쿼츠와 카올린의 천연 결합물 (호프먼 미네랄사 제조,「실리틴 V85」) 10 중량부가 충전된 칼럼에서 여과하여, 식 (1) 로 나타내는 화합물 (R1 이 H, m ＝ n ＝ 1 (평균값)) 을 얻었다. 또한, 얻어진 화합물이 식 (1) 로 나타내는 화합물 (R1 이 H, m ＝ n ＝ 1 (평균값)) 인 것은, 1H-NMR, 13C-NMR, 및, IR 에 의해 확인하였다.169 parts by weight of 4,4'-bis (2-hydroxyethyloxy) diphenyl sulfone, 370 parts by weight of epichlorohydrin, 185 parts by weight of dimethylsulfoxide, And 5 parts by weight of tetramethylammonium chloride were added and dissolved under stirring, and the temperature was raised to 50 占 폚. Subsequently, 60 parts by weight of sodium hydroxide on the flakes was added in portions over 100 minutes, followed by post-reaction at 50 占 폚 for 3 hours. After completion of the reaction, 400 parts by weight of water was added to the flask and the flask was washed with water. Excess epichlorohydrin or the like was distilled off from the oil layer at 130 占 폚 using a rotary evaporator. To the residue, 450 parts by weight of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 캜. 10 parts by weight of a 30% aqueous solution of sodium hydroxide was added under stirring, and the reaction was conducted for 1 hour. Thereafter, washing with water was carried out three times, and methyl isobutyl ketone was distilled off under reduced pressure at 180 캜 using a rotary evaporator . 1100 parts by weight of the obtained reaction product, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid were reacted with reflux and stirring at 90 DEG C for 5 hours while air was blown . 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural bond of quartz and kaolin (manufactured by Hoffman Minerals, " Silicin V85 ") to adsorb ionic impurities in the reaction product, (R 1 is H, m = n = 1 (average value)). It was confirmed by 1 H-NMR, 13 C-NMR and IR that the obtained compound was a compound represented by the formula (1) (R 1 was H, m = n = 1 (average value)).
(실시예 1 ∼ 7, 및, 비교예 1 ∼ 4)(Examples 1 to 7 and Comparative Examples 1 to 4)
표 1 에 기재된 배합비에 따라, 각 재료를 유성식 교반기 (싱키사 제조,「아와토리 렌타로」) 를 사용하여 혼합한 후, 다시 3 본롤을 사용하여 혼합함으로써 실시예 1 ∼ 7, 및, 비교예 1 ∼ 4 의 액정 표시 소자용 시일제를 조제하였다.Each of the materials was mixed with a planetary mixer ("Awatolian Taro", manufactured by Singkis Co., Ltd.) according to the blending ratio shown in Table 1, The sealants for the liquid crystal display elements of Examples 1 to 4 were prepared.
＜평가＞<Evaluation>
실시예 및 비교예에서 얻어진 액정 표시 소자용 시일제에 대해 이하의 평가를 실시하였다. 결과를 표 1 에 나타내었다.The liquid crystal display element sealant obtained in Examples and Comparative Examples was evaluated as follows. The results are shown in Table 1.
(도포성)(Coating property)
디스펜서 (무사시 엔지니어링사 제조,「SHOTMASTER300」) 를 사용하여, 실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제를 유리 기판 상에 도포하였다. 디스펜스 노즐을 400 ㎛, 노즐 갭을 30 ㎛, 도출압을 300 k㎩ 로 고정시켜 도포하였을 때, 잔줄 자국이나 흘림 없이 도포할 수 있었던 경우를「◎」, 약간 잔줄 자국이나 흘림이 발생한 경우를「○」, 도포 끊김은 없지만 큰 잔줄 자국이나 흘림이 발생한 경우를「△」, 도포 끊김이 발생하거나, 전혀 도포할 수 없거나 한 경우를「×」으로 하여 도포성을 평가하였다.Each liquid crystal display element sealant obtained in Examples and Comparative Examples was coated on a glass substrate using a dispenser (SHOTMASTER 300, manufactured by Musashi Engineering Co., Ltd.). Quot ;. When the dispenser nozzle was coated with the dispenser nozzle fixed at 400 mu m, the nozzle gap at 30 mu m, and the lead-out pressure at 300 kPa, Quot ;, "? &Quot;, a case where there was no discontinuity but a large scratch mark or a discontinuity occurred was indicated as " DELTA ", and a case where discontinuity of coating occurred or not at all was evaluated as " x "
(접착성)(Adhesive property)
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제 100 중량부에 대해 평균 입자경 5 ㎛ 의 스페이서 입자 (세키스이 화학 공업사 제조,「마이크로 펄 SP-2050」) 1 중량부를 유성식 교반 장치에 의해 균일하게 분산시키고, 극미량을 코닝 유리 1737 (20 ㎜ × 50 ㎜ × 두께 0.7 ㎜) 의 중앙부에 취하고, 동형의 유리를 그 위에 중첩하여 액정 표시 소자용 시일제를 펴서 넓히고, 메탈 할라이드 램프를 사용하여 100 mW/㎠ 의 자외선을 30 초 조사한 후, 120 ℃ 에서 1 시간 가열하여 시일제를 경화시켜, 접착 시험편을 얻었다.One part by weight of spacer particles ("Micropearl SP-2050", manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 5 μm was added to 100 parts by weight of each liquid crystal display element sealant obtained in Examples and Comparative Examples, And a minute amount of the liquid crystal display element sealant was spread on the Corning glass 1737 (20 mm x 50 mm x 0.7 mm thick) at the center, and the same type of glass was superimposed thereon to stretch out the sealant for liquid crystal display element 100. Using a metal halide lamp, mW / cm < 2 > for 30 seconds, and then heated at 120 DEG C for 1 hour to cure the sealant to obtain an adhesive test piece.
얻어진 접착 시험편에 대해, 텐션 게이지를 사용하여 접착 강도를 측정하였다. 얻어진 측정값 (㎏f) 를 시일 도포 단면적 (㎠) 으로 나눈 값이, 35 ㎏f/㎠ 이상이었던 경우를「◎」, 30 ㎏f/㎠ 이상 35 ㎏f/㎠ 미만이었던 경우를「○」, 25 ㎏f/㎠ 이상 30 ㎏f/㎠ 미만이었던 경우를「△」, 25 ㎏f/㎠ 미만이었던 경우를「×」으로 하여 접착성을 평가하였다.The adhesive strength of the obtained adhesive test piece was measured using a tension gauge. The case where the value obtained by dividing the obtained measured value (kgf) by the seal coating cross-sectional area (cm 2) was 35 kgf / cm 2 or more was evaluated as " ", and the case where it was less than 30 kgf / cm 2 and 35 kgf / , And the case where it was less than 25 kgf / cm 2 and less than 30 kgf / cm 2 was evaluated as " DELTA ", and the case of less than 25 kgf / cm 2 was evaluated as " x "
(투습 방지성)(Moisture-proof property)
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제를, 평활한 이형 필름상으로 코터로 두께 200 ∼ 300 ㎛ 로 도공한 후, 메탈 할라이드 램프를 사용하여 100 mW/㎠ 의 자외선을 30 초 조사한 후, 120 ℃ 에서 1 시간 가열함으로써 투습도 측정용 경화 필름을 얻었다.Each of the sealants for liquid crystal display elements obtained in Examples and Comparative Examples was coated on a smooth release film with a coater to a thickness of 200 to 300 탆 and irradiated with ultraviolet rays of 100 mW / cm 2 for 30 seconds using a metal halide lamp Thereafter, the film was heated at 120 DEG C for 1 hour to obtain a cured film for measurement of moisture permeability.
JIS Z 0208 의 방습 포장 재료의 투습도 시험 방법 (컵법) 에 준한 방법으로 투습도 시험용 컵을 제조하고, 얻어진 투습도 측정용 경화 필름을 부착하고, 온도 80 ℃ 습도 90 ％ RH 의 항온 항습 오븐에 투입하여 투습도를 측정하였다. 얻어진 투습도의 값이 60 g/㎡·24 hr 미만이었던 경우를「◎」, 60 g/㎡·24 hr 이상 100 g/㎡·24 hr 미만이었던 경우를「○」, 100 g/㎡·24 hr 이상 120 g/㎡·24 hr 미만이었던 경우를「△」, 120 g/㎡·24 hr 이상이었던 경우를「×」으로 하여 투습 방지성을 평가하였다.A moisture permeability test cup was prepared by the method according to the moisture permeability test method (cup method) of the moisture-proof packaging material of JIS Z 0208, and the resulting cured film for moisture permeability measurement was attached and placed in a constant temperature and humidity oven at a temperature of 80 DEG C and a humidity of 90% Were measured. The results obtained when the value of the obtained water vapor permeability was less than 60 g / m 2 .24 hr were evaluated as "? &Quot;, and those in which 60 g / m 2 24 hr or more and less than 100 g / Quot; and 120 g / m < 2 > 24 hr or more was evaluated as " DELTA ", and when it was 120 g / m &
(액정 표시 소자의 표시 성능 (저액정 오염성))(Display performance of liquid crystal display element (low liquid crystal fouling property))
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제 100 중량부에 대해 평균 입자경 5 ㎛ 의 스페이서 입자 (세키스이 화학 공업사 제조,「마이크로 펄 SP-2050」) 1 중량부를 유성식 교반 장치에 의해 균일하게 분산시켜, 얻어진 시일제를 디스펜스용의 시린지 (무사시 엔지니어링사 제조,「PSY-10 E」) 에 충전하고, 탈포 처리를 실시하고 나서, 디스펜서 (무사시 엔지니어링사 제조,「SHOTMASTER300」) 로, 2 장의 ITO 박막이 부착된 투명 전극 기판의 일방에 시일제를 프레임상으로 도포하였다. 계속해서, TN 액정 (칫소사 제조,「JC-5001 LA」) 의 미소적을 액정 적하 장치로 시일제의 프레임 내에 적하 도포하고, 타방의 투명 전극 기판을, 진공 첩합 장치로 5 ㎩ 의 진공하에서 첩합하여 셀을 얻었다. 얻어진 셀에, 메탈 할라이드 램프를 사용하여 100 mW/㎠ 의 자외선을 30 초 조사한 후, 120 ℃ 에서 1 시간 가열하여 시일제를 경화시켜 액정 표시 소자를 얻었다.One part by weight of spacer particles ("Micropearl SP-2050", manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 5 μm was added to 100 parts by weight of each liquid crystal display element sealant obtained in Examples and Comparative Examples, The resulting sealant was filled in a syringe for dispensing ("PSY-10 E" manufactured by Musashi Engineering Co., Ltd.), subjected to defoaming treatment, and then subjected to defoaming treatment using a dispenser (SHOTMASTER 300 manufactured by Musashi Engineering Co., Ltd.) A sealant was applied to one side of the transparent electrode substrate with the ITO thin film in the form of a frame. Subsequently, a microdroof of a TN liquid crystal ("JC-5001 LA" manufactured by Chisso Corporation) was dropwise coated in a frame of a sealant with a liquid crystal dropping device and the other transparent electrode substrate was laminated with a vacuum bonding apparatus under a vacuum of 5 Pa The cells were combined. The resulting cell was irradiated with ultraviolet rays of 100 mW / cm < 2 > for 30 seconds using a metal halide lamp, and then heated at 120 DEG C for 1 hour to cure the sealant to obtain a liquid crystal display device.
얻어진 액정 표시 소자에 대해, 시일부 주변의 액정 (특히 코너부) 에 발생하는 표시 불균일을 육안으로 관찰하여, 표시 불균일이 확인되지 않은 경우를「◎」, 약간의 표시 불균일이 확인된 경우를「○」, 확실하게 표시 불균일이 확인된 경우를「△」, 심한 표시 불균일이 확인된 경우를「×」로 하여 액정 표시 소자의 표시 성능 (저액정 오염성) 을 평가하였다.With respect to the obtained liquid crystal display element, the display irregularities occurring in the liquid crystal (particularly at the corners) around the seal portion were visually observed, and the case where the display irregularity was not confirmed was indicated as " ", the case where slight irregularity of display was confirmed as & (Poor liquid crystal fouling property) of the liquid crystal display element was evaluated by "? &Quot;, " DELTA ", and " x " when a severe display irregularity was confirmed.
또한, 평가가「◎」,「○」인 액정 표시 소자는, 실용에 전혀 문제가 없는 레벨이다.In addition, the liquid crystal display elements whose evaluation is "? &Quot; and "? &Quot;
산업상 이용가능성Industrial availability
본 발명에 의하면, 도포성, 투습 방지성, 및, 접착성이 우수하고, 또한 액정 오염을 억제할 수 있는 액정 표시 소자용 시일제를 제공할 수 있다. 또, 본 발명에 의하면, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공할 수 있다.According to the present invention, it is possible to provide a sealant for a liquid crystal display element which is excellent in coating property, moisture permeation preventive property, adhesive property, and can suppress liquid crystal contamination. According to the present invention, the upper and lower conductive materials and the liquid crystal display element using the liquid crystal display element sealant can be provided.
Claims (4)
상기 경화성 수지는, 하기 식 (1) 로 나타내는 화합물을 함유하고,
액정 표시 소자용 시일제 중에 있어서의 상기 식 (1) 로 나타내는 화합물의 함유량이 1 중량％ 이상 30 중량％ 미만인 것을 특징으로 하는 액정 표시 소자용 시일제.
[화학식 1]
식 (1) 중, R1 은 수소 또는 메틸기이고, m 및 n 은 각각 0 ∼ 6 이다.1. A sealant for a liquid crystal display element comprising a curable resin, a radical polymerization initiator and / or a thermosetting agent,
The curable resin contains a compound represented by the following formula (1)
Wherein the content of the compound represented by the formula (1) in the sealing agent for a liquid crystal display element is 1 wt% or more and less than 30 wt%.
[Chemical Formula 1]
In the formula (1), R 1 is hydrogen or a methyl group, and m and n are each 0 to 6.
경화성 수지는, 추가로 에폭시(메트)아크릴레이트를 함유하는 것을 특징으로 하는 액정 표시 소자용 시일제.The method according to claim 1,
Wherein the curable resin further contains an epoxy (meth) acrylate.
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| JPJP-P-2016-001915 | 2016-01-07 | ||
| PCT/JP2017/000004 WO2017119406A1 (en) | 2016-01-07 | 2017-01-04 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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| KR20190121778A (en) * | 2017-03-03 | 2019-10-28 | 니혼 유피카 가부시키가이샤 | Crystalline radical polymerizable composition for electric and electronic parts, electric and electronic part molded article using the composition, and method for producing the electric and electronic part molded article |
| JP6653305B2 (en) * | 2017-11-10 | 2020-02-26 | 日本ユピカ株式会社 | Crystalline radical polymerizable composition for electric / electronic parts, molded article of electric / electronic part using the composition, and method for producing molded article of electric / electronic part |
| JP6630695B2 (en) * | 2017-03-03 | 2020-01-15 | 日本ユピカ株式会社 | Crystalline radical polymerizable composition for sealing electric and electronic parts, sealed body for electric and electronic parts using the composition, and method for producing the sealed body |
| CN111656270A (en) * | 2018-05-25 | 2020-09-11 | 积水化学工业株式会社 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN113168055A (en) * | 2018-12-07 | 2021-07-23 | 积水化学工业株式会社 | Sealing agent for display element, cured product, vertical conduction material, and display element |
| EP4119590A1 (en) * | 2021-07-16 | 2023-01-18 | Hilti Aktiengesellschaft | Epoxide-acrylate hybrid molecules and their use for chemical anchoring |
| EP4119589A1 (en) * | 2021-07-16 | 2023-01-18 | Hilti Aktiengesellschaft | Epoxy resin mixtures comprising epoxide-acrylate hybrid molecules and multicomponent reactive resin compositions therefrom |
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| JP2001133794A (en) | 1999-11-01 | 2001-05-18 | Kyoritsu Kagaku Sangyo Kk | Sealing agent for dropping process of lcd panel |
| WO2002092718A1 (en) | 2001-05-16 | 2002-11-21 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
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| JP4752131B2 (en) * | 2001-05-16 | 2011-08-17 | 味の素株式会社 | Latent curing agent for epoxy resin and curable epoxy resin composition |
| WO2006027982A1 (en) * | 2004-09-06 | 2006-03-16 | Nippon Kayaku Kabushiki Kaisha | Liquid crystal sealing material and liquid crystal display cell using same |
| KR101202370B1 (en) * | 2005-09-02 | 2012-11-16 | 디아이씨 가부시끼가이샤 | Photocurable composition for sealing agent, liquid crystal sealing agent, and liquid crystal panel |
| JPWO2011040397A1 (en) * | 2009-10-02 | 2013-02-28 | 積水化学工業株式会社 | Manufacturing method of liquid crystal display device |
| CN105283803B (en) * | 2013-06-11 | 2017-08-01 | 积水化学工业株式会社 | Sealant for liquid crystal dripping process, up and down conductive material and liquid crystal display cells |
| KR102285528B1 (en) * | 2014-05-23 | 2021-08-03 | 세키스이가가쿠 고교가부시키가이샤 | Sealant for one-drop filling process, vertically conductive material, and liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001133794A (en) | 1999-11-01 | 2001-05-18 | Kyoritsu Kagaku Sangyo Kk | Sealing agent for dropping process of lcd panel |
| WO2002092718A1 (en) | 2001-05-16 | 2002-11-21 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
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| WO2017119406A1 (en) | 2017-07-13 |
| TWI707946B (en) | 2020-10-21 |
| CN107636524A (en) | 2018-01-26 |
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| JP6798978B2 (en) | 2020-12-09 |
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