WO2014136667A1 - Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element - Google Patents
Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element Download PDFInfo
- Publication number
- WO2014136667A1 WO2014136667A1 PCT/JP2014/055040 JP2014055040W WO2014136667A1 WO 2014136667 A1 WO2014136667 A1 WO 2014136667A1 JP 2014055040 W JP2014055040 W JP 2014055040W WO 2014136667 A1 WO2014136667 A1 WO 2014136667A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- meth
- acrylate
- sealing agent
- crystal dropping
- Prior art date
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 174
- 238000000034 method Methods 0.000 title claims abstract description 102
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 100
- 238000007789 sealing Methods 0.000 title claims abstract description 99
- 239000004020 conductor Substances 0.000 title abstract 2
- -1 oxime ester compound Chemical class 0.000 claims abstract description 95
- 150000001875 compounds Chemical class 0.000 claims abstract description 92
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 239000003999 initiator Substances 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000010419 fine particle Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 11
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- BEUGBYXJXMVRFO-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-phenylmethanone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=CC=C1 BEUGBYXJXMVRFO-UHFFFAOYSA-N 0.000 claims description 4
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 claims description 3
- LOCXTTRLSIDGPS-FVDSYPCUSA-N [(z)-[1-oxo-1-(4-phenylsulfanylphenyl)octan-2-ylidene]amino] benzoate Chemical compound C=1C=C(SC=2C=CC=CC=2)C=CC=1C(=O)C(/CCCCCC)=N\OC(=O)C1=CC=CC=C1 LOCXTTRLSIDGPS-FVDSYPCUSA-N 0.000 claims description 2
- 238000011109 contamination Methods 0.000 abstract description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 200
- 239000003822 epoxy resin Substances 0.000 description 92
- 229920000647 polyepoxide Polymers 0.000 description 92
- 239000004593 Epoxy Substances 0.000 description 42
- 239000000565 sealant Substances 0.000 description 37
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 36
- 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 34
- 239000000758 substrate Substances 0.000 description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 26
- 150000002148 esters Chemical class 0.000 description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 20
- 239000000126 substance Substances 0.000 description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 16
- 239000000945 filler Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229920001187 thermosetting polymer Polymers 0.000 description 13
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 12
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 12
- 150000002009 diols Chemical class 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 12
- 239000004843 novolac epoxy resin Substances 0.000 description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 150000002513 isocyanates Chemical class 0.000 description 10
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 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 8
- 239000004925 Acrylic resin Substances 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 229940126062 Compound A Drugs 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 239000004305 biphenyl Substances 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 235000011187 glycerol Nutrition 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 7
- 208000035475 disorder Diseases 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 6
- 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 6
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 125000005577 anthracene group Chemical group 0.000 description 6
- 235000019437 butane-1,3-diol Nutrition 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-UHFFFAOYSA-N 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 4
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 4
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 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 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 2
- VLTYTTRXESKBKI-UHFFFAOYSA-N (2,4-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 VLTYTTRXESKBKI-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- PPHOVLUFQLXZRB-UHFFFAOYSA-N 1-chloro-4-propylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(CCC)=CC=C2Cl PPHOVLUFQLXZRB-UHFFFAOYSA-N 0.000 description 2
- 125000004812 1-ethylethylene group Chemical group [H]C([H])([H])C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 2
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 2
- MODNLDNPMHIXHC-UHFFFAOYSA-N 2-(2-hydroxyethoxy)anthracene-9,10-dione Chemical compound OCCOC1=CC=2C(C3=CC=CC=C3C(C=2C=C1)=O)=O MODNLDNPMHIXHC-UHFFFAOYSA-N 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
- 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- RUVNKAUVVBCURD-UHFFFAOYSA-N 2-[[4-[2-[4-(oxiran-2-ylmethoxy)-3-prop-2-enylphenyl]propan-2-yl]-2-prop-2-enylphenoxy]methyl]oxirane Chemical compound C=1C=C(OCC2OC2)C(CC=C)=CC=1C(C)(C)C(C=C1CC=C)=CC=C1OCC1CO1 RUVNKAUVVBCURD-UHFFFAOYSA-N 0.000 description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 2
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 2
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- IKVYHNPVKUNCJM-UHFFFAOYSA-N 4-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C(C)C)=CC=C2 IKVYHNPVKUNCJM-UHFFFAOYSA-N 0.000 description 2
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 2
- KSMGAOMUPSQGTB-UHFFFAOYSA-N 9,10-dibutoxyanthracene Chemical compound C1=CC=C2C(OCCCC)=C(C=CC=C3)C3=C(OCCCC)C2=C1 KSMGAOMUPSQGTB-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- PNVWNTUCFLZBSE-UHFFFAOYSA-N CC(O)COC(=O)c1ccccc1C(=O)OCCOC(=O)C=C Chemical compound CC(O)COC(=O)c1ccccc1C(=O)OCCOC(=O)C=C PNVWNTUCFLZBSE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- AFYCEAFSNDLKSX-UHFFFAOYSA-N coumarin 460 Chemical compound CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 AFYCEAFSNDLKSX-UHFFFAOYSA-N 0.000 description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 2
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-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
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910021647 smectite Inorganic materials 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- AMJYHMCHKZQLAY-UHFFFAOYSA-N tris(2-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound O=C=NC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)N=C=O)OC1=CC=CC=C1N=C=O AMJYHMCHKZQLAY-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- REUQOSNMSWLNPD-UHFFFAOYSA-N [2-(diethylamino)phenyl]-phenylmethanone Chemical compound CCN(CC)C1=CC=CC=C1C(=O)C1=CC=CC=C1 REUQOSNMSWLNPD-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- G02F1/1341—Filling or closing of cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- 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
- G02F1/1341—Filling or closing of cells
- G02F1/13415—Drop filling process
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
Definitions
- the present invention relates to a sealing agent for a liquid crystal dropping method, which is excellent in photocurability and can suppress liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which were manufactured using this sealing compound for liquid crystal dropping methods.
- a liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
- a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing.
- a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.
- the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
- the sealant is placed directly under the black matrix, so when the dripping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. As described above, when the sealant is insufficiently cured, there is a problem in that the uncured sealant component is eluted in the liquid crystal and easily causes liquid crystal contamination.
- Patent Document 3 discloses that a highly sensitive photopolymerization initiator is blended with a sealant in order to improve the light-shielding part curability. However, simply by adding a highly sensitive photopolymerization initiator, the sealant at the light shielding part could not be sufficiently photocured.
- Patent Document 4 discloses that a high-sensitivity photopolymerization initiator and a sensitizer composed of a thioxanthone compound are combined in combination. However, the use of such a sensitizer has a problem that liquid crystal contamination due to the sealing agent is likely to occur.
- An object of this invention is to provide the sealing compound for liquid crystal dropping methods which is excellent in photocurability and can suppress liquid-crystal contamination. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which were manufactured using this sealing compound for liquid crystal dropping methods.
- R 1 and R 2 represent hydrogen or a —NR 3 2 group, and at least one of R 1 and R 2 is a —NR 3 2 group.
- R 3 represents hydrogen or an alkyl group having 1 to 4 carbon atoms. Each R 3 may be the same or different. The present invention 1 will be described in detail below.
- the present inventor uses a combination of a compound having a specific structure and an oxime ester compound so as to have a specific content ratio, so that it has excellent photocurability and suppresses liquid crystal contamination.
- the present inventors have found that a sealing agent for a liquid crystal dropping method that can be obtained can be obtained, and the present invention 1 has been completed.
- the sealing agent for liquid crystal dropping method of the present invention 1 contains a photopolymerization initiator.
- the photopolymerization initiator contains a compound represented by the formula (1) and an oxime ester compound.
- the sealing agent for liquid crystal dropping method of the present invention 1 is highly sensitive and excellent in photocurability and suppresses liquid crystal contamination by using a combination of the compound represented by the above formula (1) and the oxime ester compound. Will be able to do.
- the compound represented by the above formula (1) functions not only as a photopolymerization initiator but also as a sensitizer.
- R 1 and R 2 are a —NR 3 2 group
- R 3 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
- R 3 is an alkyl group
- the alkyl group represented by R 3 is preferably a methyl group or an ethyl group.
- the compound represented by the above formula (1) is selected from the group consisting of 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, and 4- (dimethylamino) benzophenone. It is preferable that it is at least one kind.
- X represents an alkylene group having 1 to 6 carbon atoms.
- examples of the alkylene group represented by X include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a 1-methylethylene group, and a 1-ethylethylene group.
- sealant In order to prevent liquid crystal contamination due to the liquid crystal dropping method sealant, not only improve the photocurability of the sealant, but also suppress the elution of ionic substances that cause liquid crystal alignment abnormalities into the liquid crystal. Is required. Since the compound represented by the above formula (1) has an amino group in the molecule, if an excessive amount is contained in the sealant, liquid crystal contamination caused by ionicity may be caused. Therefore, the content of the compound represented by the above formula (1) needs to be adjusted appropriately.
- the content of the photopolymerization initiator is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the photopolymerization initiator is less than 0.1 parts by weight, the photopolymerization of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed.
- the content of the photopolymerization initiator exceeds 10 parts by weight, a large amount of unreacted photopolymerization initiator remains, and the weather resistance of the obtained liquid crystal dropping method sealing agent is deteriorated or the storage stability is inferior. Or liquid crystal contamination may occur.
- the minimum with more preferable content of the said photoinitiator is 0.2 weight part, and a more preferable upper limit is 8 weight part.
- the sealing agent for liquid crystal dropping method of the present invention 1 contains a curable resin.
- the curable resin preferably contains a resin having at least one (meth) acryloyl group in one molecule (hereinafter also referred to as “(meth) acrylic resin”).
- the (meth) acrylic resin preferably has two or more (meth) acryloyl groups in one molecule because of its high reactivity.
- the “(meth) acryloyl group” means acryloyl or methacryloyl
- the “(meth) acryl” means acryl or methacryl.
- Examples of the (meth) acrylic resin include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and an epoxy (meta) obtained by reacting (meth) acrylic acid with an epoxy compound.
- Urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with acrylate or isocyanate.
- epoxy (meth) acrylate is preferable from the viewpoint of ease of synthesis and the like.
- the “(meth) acrylate” means acrylate or methacrylate
- the “epoxy (meth) acrylate” means all epoxy groups in the epoxy resin and (meth) acrylic acid. It represents the reacted compound.
- Examples of the monofunctional compounds of the ester compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethylcal Tall (meth) acrylate, phen
- bifunctional ester compound examples include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth).
- ester compound having three or more functional groups examples include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylol.
- Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
- Examples of the epoxy resin used as a raw material for synthesizing the epoxy (meth) acrylate include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl 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 Novolac epoxy resin, ortho-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Emissions phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
- Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
- Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
- Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
- Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
- Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available glycidylamine epoxy resins include Epicoat 630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
- alkyl polyol type epoxy resins examples include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
- Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and Epolide PB (manufactured by Daicel Chemical Industries, Ltd.).
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
- Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032. (All manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.
- the epoxy (meth) acrylate can be produced by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
- a basic catalyst for example, 360 parts by weight of a resorcinol type epoxy resin (EX-201, manufactured by Nagase ChemteX), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and acrylic acid Resorcinol-type epoxy acrylate can be obtained by allowing 210 parts by weight to react at 90 ° C. for 5 hours while feeding air and refluxing and stirring.
- EX-201 resorcinol type epoxy resin
- p-methoxyphenol as a polymerization inhibitor
- triethylamine as a reaction catalyst
- acrylic acid Resorcinol-type epoxy acrylate can be obtained by allowing 210 parts by weight to react at 90 ° C. for 5 hours while feeding air and refluxing and stirring.
- Examples of commercially available epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRY370R ), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, Epoxy ester 200PA, Epoxy ester 80MF Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-3
- Examples of the urethane (meth) acrylate obtained by reacting the above isocyanate with a (meth) acrylic acid derivative having a hydroxyl group include, for example, a (meth) acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups. Two equivalents can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
- isocyanate examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), and hydrogenated MDI.
- Polymeric MDI 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethyl
- Examples include xylene diisocyanate and 1,6,10-undecane triisocyanate.
- isocyanate examples include, for example, a reaction between a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.
- a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.
- a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.
- the resulting chain-extended isocyanate compound
- Examples of the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
- ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol mono (meth) acrylates of trihydric alcohols such as polyethylene glycol, trimethylolethane And mono (meth) acrylate or di (meth) acrylate of a trivalent alcohol such as trimethylolpropane and glycerin, and epoxy (meth) acrylate such as bisphenol A type epoxy acrylate.
- the urethane (meth) acrylate includes, for example, 134 parts by weight of trimethylolpropane, 0.2 part by weight of BHT as a polymerization inhibitor, 0.01 part by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate.
- the mixture can be reacted at 60 ° C. for 2 hours with stirring under reflux, then 51 parts by weight of 2-hydroxyethyl acrylate is added, and the mixture is reacted at 90 ° C. for 2 hours with feeding air and stirring under reflux.
- Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700 , Art resin N-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Industrial Co., Ltd.), U-122P, U-108A, U-340P,
- the said (meth) acrylic resin may contain a partial (meth) acryl modified epoxy resin from a viewpoint of improving adhesiveness.
- the partial (meth) acryl-modified epoxy resin means a resin having one or more epoxy groups and (meth) acryloyloxy groups in one molecule, for example, two or more epoxy resins. It can be obtained by reacting a part of the epoxy group of the resin with (meth) acrylic acid.
- the curable resin preferably further contains an epoxy resin for the purpose of improving the adhesiveness of the obtained liquid crystal dropping method sealing agent.
- the epoxy resin include an epoxy resin that is a raw material for synthesizing the epoxy (meth) acrylate.
- the sealing agent for liquid crystal dropping method of the present invention 1 contains the above-mentioned partial (meth) acryl-modified epoxy resin or the above epoxy resin
- the ratio of (meth) acryloyl group to epoxy group is 50:50 to 95: 5.
- the ratio of the (meth) acryloyl group is less than 50%, a large amount of uncured epoxy resin component remains even when the polymerization is completed, and liquid crystal contamination may occur.
- the ratio of the (meth) acryloyloxy group exceeds 95%, the obtained sealing agent for liquid crystal dropping method may be inferior in adhesiveness.
- the curable resin preferably has a hydrogen bonding functional group such as —OH group, —NH— group, and —NH 2 group in order to suppress liquid crystal contamination.
- the preferable lower limit of the hydrogen bonding functional group value of the curable resin is 2 ⁇ 10 ⁇ 3 mol / g, and the preferable upper limit is 5 ⁇ 10 ⁇ 3 mol / g.
- the adhesive property of the obtained liquid crystal dropping method sealing agent may be inferior.
- the hydrogen bondable functional group value of the curable resin exceeds 5 ⁇ 10 ⁇ 3 mol / g, the obtained liquid crystal dropping method sealant may contaminate the liquid crystal.
- the said hydrogen bondable functional group value is a value computed by the following formula, when the compound which has the said hydrogen bondable functional group consists of 1 type (compound A only).
- Hydrogen bonding functional group value (H A ) (mol / g) (number of hydrogen bonding functional groups in one molecule of compound A) / (molecular weight of compound A)
- the hydrogen bondable functional group value can be calculated by distributing the content (weight fraction) per unit weight of the compound having each hydrogen bondable functional group. .
- a compound having a hydrogen-bonding functional group, Compound A, Compound B, and the hydrogen-bonding functional group value when configured from a compound C, when the weight fraction of compound alpha was P alpha It is represented by the following formula.
- Hydrogen-bonding functional group value (H ABC) H A P A + H B P B + H C P C
- the sealing agent for liquid crystal dropping method of the present invention 1 may contain a sensitizer.
- the sensitizer is preferably selected from the group consisting of a benzophenone skeleton, an anthracene skeleton, an anthraquinone skeleton, a coumarin skeleton, a thioxanthone skeleton, and a phthalocyanine skeleton because it preferably has a sufficient light absorption band in the ultraviolet / visible region.
- Examples of the compound having a benzophenone skeleton include compounds having a benzophenone skeleton other than the compound represented by the above formula (1), and examples thereof include benzophenone and 2,4-dichlorobenzophenone.
- Examples of the compound having an anthracene skeleton include 9,10-dibutoxyanthracene, 9,10-diproxyanthraquinone, and 9,10-ethoxyanthraquinone.
- Examples of the compound having an anthraquinone skeleton include 2-ethylanthraquinone, 1-methylanthraquinone, 1,4-dihydroxyanthraquinone, 2- (2-hydroxyethoxy) -anthraquinone and the like.
- Examples of the compound having a coumarin skeleton include 7-diethylamino-4-methylcoumarin.
- Examples of the compound having a thioxanthone skeleton include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and the like.
- Examples of the compound having a phthalocyanine skeleton include phthalocyanine.
- the content of the sensitizer is preferably 0.5 parts by weight and preferably 50 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.
- the content of the sensitizer is less than 0.5 parts by weight, the sensitizing effect may not be sufficiently exhibited.
- the content of the sensitizer exceeds 50 parts by weight, liquid crystal contamination may occur.
- the minimum with more preferable content of the said sensitizer is 1 weight part, and a more preferable upper limit is 40 weight part.
- the sealing agent for liquid crystal dropping method of the present invention 1 may contain a thermosetting agent.
- thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
- organic acid hydrazide examples include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
- organic acid hydrazides examples include SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like. It is done.
- the content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit.
- the content of the thermosetting agent is less than 1 part by weight, the resulting sealing agent for liquid crystal dropping method may not be sufficiently cured.
- content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability
- the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
- the sealing agent for the liquid crystal dropping method of the present invention 1 preferably contains a filler for the purpose of improving the viscosity, improving the adhesion due to the stress dispersion effect, improving the linear expansion coefficient, improving the moisture resistance of the cured product, and the like. .
- filler examples include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, water
- Organic filler such as aluminum oxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, aluminum nitride, polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, etc. Agents. These fillers may be used independently and may use 2 or more types together.
- the preferable lower limit of the content of the filler is 10 parts by weight and the preferable upper limit is 70 parts by weight with respect to 100 parts by weight of the sealing agent for liquid crystal dropping method.
- the content of the filler is less than 10 parts by weight, effects such as improvement of adhesiveness may not be sufficiently exhibited.
- content of the said filler exceeds 70 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability
- the minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
- the sealing compound for liquid crystal dropping method of this invention 1 contains a silane coupling agent.
- the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
- the silane coupling agent is excellent in the effect of improving the adhesion to the substrate and the like, and can be prevented from flowing out of the curable resin into the liquid crystal by chemically bonding with the curable resin.
- -Aminopropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane and the like are preferably used.
- These silane coupling agents may be used alone or in combination of two or more.
- the present invention 2 is a liquid crystal dropping method sealing agent containing a curable resin and a photopolymerization initiator, wherein the photopolymerization initiator contains a compound represented by the following formula (2). Sealing agent.
- the present invention 2 will be described in detail below.
- X represents an alkylene group having 1 to 6 carbon atoms.
- the present inventor obtains a sealing agent for a liquid crystal dropping method that has excellent photocurability and can suppress liquid crystal contamination by using an oxime ester-based compound having a specific structure as a photopolymerization initiator. As a result, the present invention 2 was completed.
- the sealing agent for liquid crystal dropping method of the present invention 2 contains a photopolymerization initiator.
- the photopolymerization initiator contains an oxime ester compound represented by the formula (2).
- examples of the alkylene group represented by X include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a 1-methylethylene group, and a 1-ethylethylene group.
- the content of the photopolymerization initiator is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the photopolymerization initiator is less than 0.1 parts by weight, the photopolymerization of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed.
- the content of the photopolymerization initiator exceeds 10 parts by weight, a large amount of unreacted photopolymerization initiator remains, and the weather resistance of the obtained liquid crystal dropping method sealing agent is deteriorated or the storage stability is inferior. Or liquid crystal contamination may occur.
- the minimum with more preferable content of the said photoinitiator is 0.2 weight part, and a more preferable upper limit is 5 weight part.
- the sealing agent for liquid crystal dropping method of the present invention 2 contains a curable resin.
- the curable resin preferably contains a resin having at least one (meth) acryloyl group in one molecule (hereinafter also referred to as “(meth) acrylic resin”).
- the (meth) acrylic resin preferably has two or more (meth) acryloyl groups in one molecule because of its high reactivity.
- the “(meth) acryloyl group” means acryloyl or methacryloyl
- the “(meth) acryl” means acryl or methacryl.
- Examples of the (meth) acrylic resin include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and an epoxy (meta) obtained by reacting (meth) acrylic acid with an epoxy compound.
- Urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with acrylate or isocyanate.
- epoxy (meth) acrylate is preferable from the viewpoint of ease of synthesis and the like.
- the “(meth) acrylate” means acrylate or methacrylate
- the “epoxy (meth) acrylate” means all epoxy groups in the epoxy resin and (meth) acrylic acid. It represents the reacted compound.
- Examples of the monofunctional compounds of the ester compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethylcal Tall (meth) acrylate, phen
- bifunctional ester compound examples include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth).
- ester compound having three or more functional groups examples include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylol.
- Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
- Examples of the epoxy resin used as a raw material for synthesizing the epoxy (meth) acrylate include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl 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 Novolac epoxy resin, ortho-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Emissions phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
- Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
- Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
- Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
- Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
- Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available glycidylamine epoxy resins include Epicoat 630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
- alkyl polyol type epoxy resins examples include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
- Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and Epolide PB (manufactured by Daicel Chemical Industries, Ltd.).
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
- Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032. (All manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.
- the epoxy (meth) acrylate can be produced by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
- a basic catalyst for example, 360 parts by weight of a resorcinol type epoxy resin (EX-201, manufactured by Nagase ChemteX), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and acrylic acid Resorcinol-type epoxy acrylate can be obtained by allowing 210 parts by weight to react at 90 ° C. for 5 hours while feeding air and refluxing and stirring.
- EX-201 resorcinol type epoxy resin
- p-methoxyphenol as a polymerization inhibitor
- triethylamine as a reaction catalyst
- acrylic acid Resorcinol-type epoxy acrylate can be obtained by allowing 210 parts by weight to react at 90 ° C. for 5 hours while feeding air and refluxing and stirring.
- Examples of commercially available epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRY370R ), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, Epoxy ester 200PA, Epoxy ester 80MF Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-3
- Examples of the urethane (meth) acrylate obtained by reacting the above isocyanate with a (meth) acrylic acid derivative having a hydroxyl group include, for example, a (meth) acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups. Two equivalents can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
- isocyanate examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), and hydrogenated MDI.
- Polymeric MDI 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethyl
- Examples include xylene diisocyanate and 1,6,10-undecane triisocyanate.
- isocyanate examples include, for example, a reaction between a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.
- a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.
- a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.
- the resulting chain-extended isocyanate compound
- Examples of the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
- ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol mono (meth) acrylates of trihydric alcohols such as polyethylene glycol, trimethylolethane And mono (meth) acrylate or di (meth) acrylate of a trivalent alcohol such as trimethylolpropane and glycerin, and epoxy (meth) acrylate such as bisphenol A type epoxy acrylate.
- the urethane (meth) acrylate includes, for example, 134 parts by weight of trimethylolpropane, 0.2 part by weight of BHT as a polymerization inhibitor, 0.01 part by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate.
- the mixture can be reacted at 60 ° C. for 2 hours with stirring under reflux, then 51 parts by weight of 2-hydroxyethyl acrylate is added, and the mixture is reacted at 90 ° C. for 2 hours with feeding air and stirring under reflux.
- Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700 , Art resin N-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Industrial Co., Ltd.), U-122P, U-108A, U-340P,
- the said (meth) acrylic resin may contain a partial (meth) acryl modified epoxy resin from a viewpoint of improving adhesiveness.
- the partial (meth) acryl-modified epoxy resin means a resin having one or more epoxy groups and (meth) acryloyloxy groups in one molecule, for example, two or more epoxy resins. It can be obtained by reacting a part of the epoxy group of the resin with (meth) acrylic acid.
- the curable resin preferably further contains an epoxy resin for the purpose of improving the adhesiveness of the obtained liquid crystal dropping method sealing agent.
- the epoxy resin include an epoxy resin that is a raw material for synthesizing the epoxy (meth) acrylate.
- the sealing agent for liquid crystal dropping method of the present invention 2 contains the above-mentioned partial (meth) acryl-modified epoxy resin or the above epoxy resin
- the ratio of (meth) acryloyl group to epoxy group is 50:50 to 95: 5.
- the ratio of the (meth) acryloyl group is less than 50%, a large amount of uncured epoxy resin component remains even when the polymerization is completed, and liquid crystal contamination may occur.
- the ratio of the (meth) acryloyloxy group exceeds 95%, the obtained sealing agent for liquid crystal dropping method may be inferior in adhesiveness.
- the curable resin preferably has a hydrogen bonding functional group such as —OH group, —NH— group, and —NH 2 group in order to suppress liquid crystal contamination.
- the preferable lower limit of the hydrogen bonding functional group value of the curable resin is 2 ⁇ 10 ⁇ 3 mol / g, and the preferable upper limit is 5 ⁇ 10 ⁇ 3 mol / g.
- the adhesive property of the obtained liquid crystal dropping method sealing agent may be inferior.
- the hydrogen bondable functional group value of the curable resin exceeds 5 ⁇ 10 ⁇ 3 mol / g, the obtained liquid crystal dropping method sealant may contaminate the liquid crystal.
- the said hydrogen bondable functional group value is a value computed by the following formula, when the compound which has the said hydrogen bondable functional group consists of 1 type (compound A only).
- Hydrogen bonding functional group value (H A ) (mol / g) (number of hydrogen bonding functional groups in one molecule of compound A) / (molecular weight of compound A)
- the hydrogen bondable functional group value is the content per unit weight of the compound having each hydrogen bondable functional group ( (Weight fraction) can be distributed and calculated.
- the hydrogen bondable functional group value when the compound having a hydrogen bondable functional group is composed of the compound A, the compound B, and the compound C is represented by the following formula.
- Hydrogen-bonding functional group value (H ABC) H A P A + H B P B + H C P C (Note that P ⁇ represents the weight fraction of compound ⁇ .)
- the sealing compound for liquid crystal dropping method of this invention 2 contains a sensitizer. By containing the sensitizer, it is possible to obtain a sealing agent for a liquid crystal dropping method that has higher sensitivity and excellent photocurability.
- the sensitizer is preferably selected from the group consisting of a benzophenone skeleton, an anthracene skeleton, an anthraquinone skeleton, a coumarin skeleton, a thioxanthone skeleton, and a phthalocyanine skeleton because it preferably has a sufficient light absorption band in the ultraviolet / visible region. It is preferable to contain a compound having at least one skeleton, and it is more preferable to contain a compound having at least one skeleton selected from the group consisting of an anthracene skeleton, an anthraquinone skeleton, and a thioxanthone skeleton.
- Examples of the compound having a benzophenone skeleton include benzophenone, 2,4-dichlorobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and 4- (dimethylamino) benzophenone.
- Examples of the compound having an anthracene skeleton include 9,10-dibutoxyanthracene, 9,10-diproxyanthraquinone, and 9,10-ethoxyanthraquinone.
- Examples of the compound having an anthraquinone skeleton include 2-ethylanthraquinone, 1-methylanthraquinone, 1,4-dihydroxyanthraquinone, 2- (2-hydroxyethoxy) -anthraquinone and the like.
- Examples of the compound having a coumarin skeleton include 7-diethylamino-4-methylcoumarin.
- Examples of the compound having a thioxanthone skeleton include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and the like.
- the compound having a phthalocyanine skeleton examples include phthalocyanine.
- the resulting liquid crystal dropping method sealant is particularly excellent in light-curing part curability, so that 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis At least one selected from the group consisting of (diethylamino) benzophenone and 4- (dimethylamino) benzophenone is preferred.
- the content of the sensitizer is such that a preferred lower limit is 2 parts by weight and a preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.
- a preferred lower limit is 2 parts by weight
- a preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.
- the sensitization effect may not be sufficiently exhibited.
- the content of the sensitizer exceeds 50 parts by weight, liquid crystal contamination may occur.
- the minimum with more preferable content of the said sensitizer is 5 weight part, and a more preferable upper limit is 40 weight part.
- the content of the sensitizer is preferably 0.01% by weight and preferably 2% by weight with respect to the entire sealing agent for liquid crystal dropping method.
- the content of the sensitizer is less than 0.01% by weight, the sensitizing effect may not be sufficiently exhibited. If the content of the sensitizer exceeds 2% by weight, liquid crystal contamination may occur.
- a more preferable lower limit of the content of the sensitizer is 0.03% by weight, a more preferable upper limit is 1.5% by weight, and a still more preferable lower limit is 0.05% by weight.
- the sealing compound for liquid crystal dropping method of this invention 2 contains a thermosetting agent.
- the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
- organic acid hydrazide examples include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
- organic acid hydrazides examples include SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like. It is done.
- the content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit.
- the content of the thermosetting agent is less than 1 part by weight, the resulting sealing agent for liquid crystal dropping method may not be sufficiently cured.
- content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability
- the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
- the sealing agent for the liquid crystal dropping method of the present invention 2 contains a filler for the purpose of improving the viscosity, improving the adhesion due to the stress dispersion effect, improving the linear expansion coefficient, and further improving the moisture resistance of the cured product. Is preferred.
- filler examples include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, water
- Organic filler such as aluminum oxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, aluminum nitride, polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, etc. Agents. These fillers may be used independently and may use 2 or more types together.
- the preferable lower limit of the content of the filler is 10 parts by weight and the preferable upper limit is 70 parts by weight with respect to 100 parts by weight of the sealing agent for liquid crystal dropping method.
- the content of the filler is less than 10 parts by weight, effects such as improvement of adhesiveness may not be sufficiently exhibited.
- content of the said filler exceeds 70 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability
- the minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
- the sealing agent for the liquid crystal dropping method of the present invention 2 preferably contains a silane coupling agent.
- the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
- the silane coupling agent is excellent in the effect of improving the adhesion to the substrate and the like, and can be prevented from flowing out of the curable resin into the liquid crystal by chemically bonding with the curable resin.
- -Aminopropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane and the like are preferably used.
- These silane coupling agents may be used alone or in combination of two or more.
- Examples of the method for producing the sealing agent for the liquid crystal dropping method of the present invention 1 and the present invention 2 include, for example, homodispers, homomixers, A method of mixing a curable resin, a photopolymerization initiator, and an additive such as a silane coupling agent, if necessary, using a mixer such as a universal mixer, planetarium mixer, kneader, or three roll Is mentioned.
- the preferred lower limit of the viscosity measured at 25 ° C. and 1 rpm using an E-type viscometer is 50,000 Pa ⁇ s
- the preferred upper limit is 500,000 Pa ⁇ s.
- a more preferable upper limit of the viscosity is 400,000 Pa ⁇ s.
- a vertical conduction material can be produced by blending conductive fine particles with the sealant for the liquid crystal dropping method of the present invention.
- Such a vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
- the conductive fine particles a metal ball, a resin fine particle formed with a conductive metal layer on the surface, or the like can be used.
- the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
- the liquid crystal display element manufactured using the sealing agent for liquid crystal dropping methods of this invention or the vertical conduction material of this invention is also one of this invention.
- the sealing agent for the liquid crystal dropping method of the present invention is applied to one of two transparent substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate.
- the process of forming a rectangular seal pattern by screen printing, dispenser application, etc., the liquid crystal drop method sealing agent of the present invention is uncured, and liquid crystal microdrops are dropped on the entire surface of the transparent substrate and applied immediately.
- a step of superimposing another substrate on the substrate, a step of irradiating the seal pattern portion of the sealant for the liquid crystal dropping method of the present invention with light such as ultraviolet rays, and the step of pre-curing the sealant, and a pre-cured sealant The method etc. which have the process of heating and carrying out a main curing are mentioned.
- the sealing compound for liquid crystal dropping methods which can be excellent in photocurability and can suppress liquid crystal contamination can be provided.
- the vertical conduction material and liquid crystal display element which were manufactured using this sealing compound for liquid crystal dropping methods can be provided.
- Examples 1 to 10, Comparative Examples 1 to 12 According to the mixing ratios described in Tables 1 and 2, after mixing each material using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), by further mixing using three rolls Sealants for liquid crystal dropping method of Examples 1 to 10 and Comparative Examples 1 to 12 were prepared.
- the “compound represented by the formula (3)” and the “compound represented by the formula (4)” described in Tables 1 and 2 are represented by the following formulas (3) and (4), respectively. Means a compound.
- Parts are dispersed, and the sealant is applied to the central part of the substrate A (the boundary between the chromium vapor deposition part and the non-deposition part), and after the substrate B is bonded together, the sealant is sufficiently crushed and the metal halide is applied from the substrate A side.
- a 100 mW / cm 2 ultraviolet ray was irradiated for 30 seconds using a lamp. Thereafter, the substrates A and B are peeled off using a cutter, and the spectrum of the sealant on the point (place 2) 50 ⁇ m away from the position of the ultraviolet direct irradiator (place 1) and the ultraviolet direct irradiator is measured by microscopic IR method.
- Liquid crystal contamination 1 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SI-H050”) is dispersed in 100 parts by weight of the sealing agent for each liquid crystal dropping method obtained in Examples 1 to 10 and Comparative Examples 1 to 12.
- a sealing agent for the liquid crystal dropping method it was applied with a dispenser to one of two rubbed alignment films and a substrate with a transparent electrode so that the line width of the sealing agent was 1 mm.
- liquid droplets (manufactured by Chisso Corp., “JC-5004LA”) are dropped onto the entire surface of the sealing agent frame of the substrate with the transparent electrode, and the other color filter substrate with the transparent electrode is immediately bonded to the seal.
- the agent part was cured by irradiating with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp, and further heated at 120 ° C. for 1 hour to obtain a liquid crystal display element.
- the liquid crystal display element controls the application position of the sealant with a dispenser so that 50% of the line width is applied to the liquid crystal display element (without the light shielding part) where the sealant is completely exposed to light and the black matrix of the color filter substrate.
- the orientation disorder is determined from the color unevenness of the display part.
- “ ⁇ ” indicates that there is no color unevenness
- “ ⁇ ” indicates that there is slight color unevenness, and color unevenness.
- the liquid crystal contamination property was evaluated with “ ⁇ ” when there was a little, and “ ⁇ ” when there was considerable color unevenness. Note that the liquid crystal display elements with the evaluations “ ⁇ ” and “ ⁇ ” are at a level that causes no problem in practical use.
- each material was mixed using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Nertaro ”), and then mixed using three rolls.
- the sealing agents for the liquid crystal dropping method of 11 to 20 and Comparative Examples 13 and 14 were prepared.
- “compound represented by formula (3)”, “compound represented by formula (4)”, “compound represented by formula (5)”, and “formula ( “Compound represented by 6)” means compounds represented by the following formulas (3), (4), (5) and (6), respectively.
- ⁇ indicates that the peak derived from the acryloyl group has decreased by 93% or more after light irradiation
- “O” indicates that the peak derived from the acryloyl group has decreased by 85% or more but less than 93% after light irradiation
- Photocurability was evaluated as “ ⁇ ” when the peak was decreased by 75% or more and less than 85%
- “X” when the decrease in the peak derived from the acryloyl group after light irradiation was less than 75%.
- Liquid crystal contamination 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SI-H050”) is dispersed in 100 parts by weight of the sealant for each liquid crystal dropping method obtained in Examples 11 to 20 and Comparative Examples 13 and 14.
- a sealing agent for the liquid crystal dropping method it was applied with a dispenser to one of two rubbed alignment films and a substrate with a transparent electrode so that the line width of the sealing agent was 1 mm.
- liquid droplets manufactured by Chisso Corp., “JC-5004LA”
- JC-5004LA liquid droplets
- the agent part was cured by irradiating with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp, and further heated at 120 ° C. for 1 hour to obtain a liquid crystal display element.
- the liquid crystal display element controls the application position of the sealant with a dispenser, and the liquid crystal display element (no light blocking part) where the sealant is completely exposed to light, and the sealant has 50% of the line width on the black matrix of the color filter substrate.
- the sealing compound for liquid crystal dropping methods which can be excellent in photocurability and can suppress liquid crystal contamination can be provided.
- the vertical conduction material and liquid crystal display element which were manufactured using this sealing compound for liquid crystal dropping methods can be provided.
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Liquid Crystal (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
滴下工法では、まず、2枚の電極付き透明基板の一方に、ディスペンスにより長方形状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下し、すぐに他方の透明基板を重ね合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、液晶アニール時に加熱して本硬化を行い、液晶表示素子を作製する。基板の貼り合わせを減圧下で行うようにすれば、極めて高い効率で液晶表示素子を製造することができ、現在この滴下工法が液晶表示素子の製造方法の主流となっている。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin and a light as disclosed in
In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.
以下に本発明1を詳述する。 In formula (1), R 1 and R 2 represent hydrogen or a —NR 3 2 group, and at least one of R 1 and R 2 is a —NR 3 2 group. R 3 represents hydrogen or an alkyl group having 1 to 4 carbon atoms. Each R 3 may be the same or different.
The
上記光重合開始剤は、上記式(1)で表される化合物とオキシムエステル系化合物とを含有する。本発明1の液晶滴下工法用シール剤は、上記式(1)で表される化合物とオキシムエステル系化合物とを組み合わせて用いることにより、高感度で光硬化性に優れ、かつ、液晶汚染を抑制することができるものとなる。上記式(1)で表される化合物は、光重合開始剤としてだけでなく、増感剤としても機能する。 The sealing agent for liquid crystal dropping method of the
The photopolymerization initiator contains a compound represented by the formula (1) and an oxime ester compound. The sealing agent for liquid crystal dropping method of the
上記R3がアルキル基である場合、上記R3で表されるアルキル基は、メチル基又はエチル基であることが好ましい。 In formula (1), at least one of R 1 and R 2 is a —NR 3 2 group, and R 3 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
When R 3 is an alkyl group, the alkyl group represented by R 3 is preferably a methyl group or an ethyl group.
上記式(1)で表される化合物と上記オキシムエステル系化合物との含有割合は、重量比で、式(1)で表される化合物:オキシムエステル系化合物=1:3~1:100である。上記式(1)で表される化合物と上記オキシムエステル系化合物との含有割合がこの範囲であることにより、得られる液晶滴下工法用シール剤が、高感度で光硬化性に優れ、かつ、液晶汚染を抑制することができるものとなる。上記式(1)で表される化合物と上記オキシムエステル系化合物との含有割合は、重量比で、式(1)で表される化合物:オキシムエステル系化合物=1:4~1:75であることが好ましく、1:5~1:50であることがより好ましい。 In order to prevent liquid crystal contamination due to the liquid crystal dropping method sealant, not only improve the photocurability of the sealant, but also suppress the elution of ionic substances that cause liquid crystal alignment abnormalities into the liquid crystal. Is required. Since the compound represented by the above formula (1) has an amino group in the molecule, if an excessive amount is contained in the sealant, liquid crystal contamination caused by ionicity may be caused. Therefore, the content of the compound represented by the above formula (1) needs to be adjusted appropriately.
The content ratio of the compound represented by the formula (1) and the oxime ester compound is a weight ratio of the compound represented by the formula (1): the oxime ester compound = 1: 3 to 1: 100. . When the content ratio of the compound represented by the formula (1) and the oxime ester-based compound is within this range, the obtained liquid crystal dropping method sealing agent is highly sensitive and excellent in photocurability, and liquid crystal. Contamination can be suppressed. The content ratio of the compound represented by the formula (1) and the oxime ester compound is a weight ratio of the compound represented by the formula (1): the oxime ester compound = 1: 4 to 1:75. It is more preferable that the ratio is 1: 5 to 1:50.
上記硬化性樹脂は、1分子中に少なくとも1つの(メタ)アクリロイル基を有する樹脂(以下、「(メタ)アクリル樹脂」ともいう)を含有することが好ましい。上記(メタ)アクリル樹脂は、反応性の高さから、1分子中に(メタ)アクリロイル基を2個以上有することが好ましい。
なお、本明細書において、上記「(メタ)アクリロイル基」とは、アクリロイル又はメタクリロイルを意味し、上記「(メタ)アクリル」とは、アクリル又はメタクリルを意味する。 The sealing agent for liquid crystal dropping method of the
The curable resin preferably contains a resin having at least one (meth) acryloyl group in one molecule (hereinafter also referred to as “(meth) acrylic resin”). The (meth) acrylic resin preferably has two or more (meth) acryloyl groups in one molecule because of its high reactivity.
In the present specification, the “(meth) acryloyl group” means acryloyl or methacryloyl, and the “(meth) acryl” means acryl or methacryl.
なお、本明細書において、上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味し、上記「エポキシ(メタ)アクリレート」とは、エポキシ樹脂中の全てのエポキシ基を(メタ)アクリル酸と反応させた化合物のことを表す。 Examples of the (meth) acrylic resin include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and an epoxy (meta) obtained by reacting (meth) acrylic acid with an epoxy compound. ) Urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with acrylate or isocyanate. Of these, epoxy (meth) acrylate is preferable from the viewpoint of ease of synthesis and the like.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate, and the “epoxy (meth) acrylate” means all epoxy groups in the epoxy resin and (meth) acrylic acid. It represents the reacted compound.
上記ビスフェノールF型エポキシ樹脂のうち市販されているものとしては、例えば、エピコート806、エピコート4004(いずれも三菱化学社製)等が挙げられる。
上記ビスフェノールS型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA1514(DIC社製)等が挙げられる。
上記2,2’-ジアリルビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、RE-810NM(日本化薬社製)等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA7015(DIC社製)等が挙げられる。
上記プロピレンオキシド付加ビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4000S(ADEKA社製)等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、EX-201(ナガセケムテックス社製)等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、エピコートYX-4000H(三菱化学社製)等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-50TE(新日鉄住金化学社製)等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-80DE(新日鉄住金化学社製)等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4088S(ADEKA社製)等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP4032、エピクロンEXA-4700(いずれもDIC社製)等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-770(DIC社製)等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-670-EXP-S(DIC社製)等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP7200(DIC社製)等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、NC-3000P(日本化薬社製)等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ESN-165S(新日鉄住金化学社製)等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、エピコート630(三菱化学社製)、エピクロン430(DIC社製)、TETRAD-X(三菱ガス化学社製)等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ZX-1542(新日鉄住金化学社製)、エピクロン726(DIC社製)、エポライト80MFA(共栄社化学社製)、デナコールEX-611(ナガセケムテックス社製)等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、YR-450、YR-207(いずれも新日鉄住金化学社製)、エポリードPB(ダイセル化学工業社製)等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールEX-147(ナガセケムテックス社製)等が挙げられる。
上記エポキシ樹脂のうちその他に市販されているものとしては、例えば、YDC-1312、YSLV-80XY、YSLV-90CR(いずれも新日鉄住金化学社製)、XAC4151(旭化成社製)、エピコート1031、エピコート1032(いずれも三菱化学社製)、EXA-7120(DIC社製)、TEPIC(日産化学社製)等が挙げられる。 As what is marketed among the said bisphenol A type epoxy resin, Epicoat 828EL, Epicoat 1004 (all are the Mitsubishi Chemical company make), Epiklon 850 (made by DIC company), etc. are mentioned, for example.
As what is marketed among the said bisphenol F type epoxy resins, Epicoat 806, Epicoat 4004 (all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include Epicoat YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine epoxy resins include Epicoat 630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and Epolide PB (manufactured by Daicel Chemical Industries, Ltd.).
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032. (All manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.
なお、本明細書において上記部分(メタ)アクリル変性エポキシ樹脂とは、1分子中にエポキシ基と(メタ)アクリロイルオキシ基とをそれぞれ1つ以上有する樹脂を意味し、例えば、2つ以上のエポキシ樹脂の一部分のエポキシ基を(メタ)アクリル酸と反応させることによって得ることができる。 The said (meth) acrylic resin may contain a partial (meth) acryl modified epoxy resin from a viewpoint of improving adhesiveness.
In the present specification, the partial (meth) acryl-modified epoxy resin means a resin having one or more epoxy groups and (meth) acryloyloxy groups in one molecule, for example, two or more epoxy resins. It can be obtained by reacting a part of the epoxy group of the resin with (meth) acrylic acid.
なお、本明細書において上記水素結合性官能基価とは、上記水素結合性官能基を有する化合物が1種類(化合物Aのみ)からなる場合には、下記式により算出される値である。
水素結合性官能基価(HA)(mol/g)=(化合物Aの1分子中の水素結合性官能基数)/(化合物Aの分子量)
また、複数の樹脂の混合物の場合、上記水素結合性官能基価は、各々の水素結合性官能基を有する化合物の単位重量あたりの含有量(重量分率)により分配して算出することができる。例えば、水素結合性官能基を有する化合物が、化合物A、化合物B、及び、化合物Cから構成されている場合の水素結合性官能基価は、化合物αの重量分率をPαとしたとき、下記式で表される。
水素結合性官能基価(HABC)=HAPA+HBPB+HCPC The preferable lower limit of the hydrogen bonding functional group value of the curable resin is 2 × 10 −3 mol / g, and the preferable upper limit is 5 × 10 −3 mol / g. When the hydrogen bonding functional group value of the curable resin is less than 2 × 10 −3 mol / g, the adhesive property of the obtained liquid crystal dropping method sealing agent may be inferior. When the hydrogen bondable functional group value of the curable resin exceeds 5 × 10 −3 mol / g, the obtained liquid crystal dropping method sealant may contaminate the liquid crystal.
In addition, in this specification, the said hydrogen bondable functional group value is a value computed by the following formula, when the compound which has the said hydrogen bondable functional group consists of 1 type (compound A only).
Hydrogen bonding functional group value (H A ) (mol / g) = (number of hydrogen bonding functional groups in one molecule of compound A) / (molecular weight of compound A)
In the case of a mixture of a plurality of resins, the hydrogen bondable functional group value can be calculated by distributing the content (weight fraction) per unit weight of the compound having each hydrogen bondable functional group. . For example, a compound having a hydrogen-bonding functional group, Compound A, Compound B, and the hydrogen-bonding functional group value when configured from a compound C, when the weight fraction of compound alpha was P alpha, It is represented by the following formula.
Hydrogen-bonding functional group value (H ABC) = H A P A + H B P B + H C P C
上記増感剤は、紫外・可視領域に充分な光吸収帯を有することが好ましいことから、ベンゾフェノン骨格、アントラセン骨格、アントラキノン骨格、クマリン骨格、チオキサントン骨格、及び、フタロシアニン骨格からなる群より選択される少なくとも一種の骨格を有する化合物を含有することが好ましく、アントラセン骨格、及び、アントラキノン骨格、チオキサントン骨格からなる群より選択される少なくとも一種の骨格を有する化合物を含有することがより好ましい。 The sealing agent for liquid crystal dropping method of the
The sensitizer is preferably selected from the group consisting of a benzophenone skeleton, an anthracene skeleton, an anthraquinone skeleton, a coumarin skeleton, a thioxanthone skeleton, and a phthalocyanine skeleton because it preferably has a sufficient light absorption band in the ultraviolet / visible region. It is preferable to contain a compound having at least one skeleton, and it is more preferable to contain a compound having at least one skeleton selected from the group consisting of an anthracene skeleton, an anthraquinone skeleton, and a thioxanthone skeleton.
上記アントラセン骨格を有する化合物としては、例えば、9,10-ジブトキシアントラセン、9,10-ジプロキシアントラキノン、9,10-エトキシアントラキノン等が挙げられる。
上記アントラキノン骨格を有する化合物としては、例えば、2-エチルアントラキノン、1-メチルアントラキノン、1,4-ジヒドロキシアントラキノン、2-(2-ヒドロキシエトキシ)-アントラキノン等が挙げられる。
上記クマリン骨格を有する化合物としては、例えば、7-ジエチルアミノ-4-メチルクマリン等が挙げられる。
上記チオキサントン骨格を有する化合物としては、例えば、2,4-ジエチルチオキサントン、2-クロロチオキサントン、4-イソプロピルチオキサントン、1-クロロ-4-プロピルチオキサントン等が挙げられる。
上記フタロシアニン骨格を有する化合物としては、例えば、フタロシアニン等が挙げられる。 Examples of the compound having a benzophenone skeleton include compounds having a benzophenone skeleton other than the compound represented by the above formula (1), and examples thereof include benzophenone and 2,4-dichlorobenzophenone.
Examples of the compound having an anthracene skeleton include 9,10-dibutoxyanthracene, 9,10-diproxyanthraquinone, and 9,10-ethoxyanthraquinone.
Examples of the compound having an anthraquinone skeleton include 2-ethylanthraquinone, 1-methylanthraquinone, 1,4-dihydroxyanthraquinone, 2- (2-hydroxyethoxy) -anthraquinone and the like.
Examples of the compound having a coumarin skeleton include 7-diethylamino-4-methylcoumarin.
Examples of the compound having a thioxanthone skeleton include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and the like.
Examples of the compound having a phthalocyanine skeleton include phthalocyanine.
上記熱硬化剤としては、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。 The sealing agent for liquid crystal dropping method of the
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、SDH、ADH(いずれも大塚化学社製)、アミキュアVDH、アミキュアVDH-J、アミキュアUDH(いずれも味の素ファインテクノ社製)等が挙げられる。 Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of commercially available organic acid hydrazides include SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like. It is done.
以下に本発明2を詳述する。 The
The
上記光重合開始剤は、上記式(2)で表されるオキシムエステル系化合物を含有する。上記式(2)で表されるオキシムエステル系化合物を用いることにより、高感度で光硬化性に優れる液晶滴下工法用シール剤を得ることができ、かつ、液晶汚染を抑制することができる。 The sealing agent for liquid crystal dropping method of the
The photopolymerization initiator contains an oxime ester compound represented by the formula (2). By using the oxime ester compound represented by the above formula (2), it is possible to obtain a sealing agent for liquid crystal dropping method having high sensitivity and excellent photocurability, and to suppress liquid crystal contamination.
上記硬化性樹脂は、1分子中に少なくとも1つの(メタ)アクリロイル基を有する樹脂(以下、「(メタ)アクリル樹脂」ともいう)を含有することが好ましい。上記(メタ)アクリル樹脂は、反応性の高さから1分子中に(メタ)アクリロイル基を2個以上有することが好ましい。
なお、本明細書において、上記「(メタ)アクリロイル基」とは、アクリロイル又はメタクリロイルを意味し、上記「(メタ)アクリル」とは、アクリル又はメタクリルを意味する。 The sealing agent for liquid crystal dropping method of the
The curable resin preferably contains a resin having at least one (meth) acryloyl group in one molecule (hereinafter also referred to as “(meth) acrylic resin”). The (meth) acrylic resin preferably has two or more (meth) acryloyl groups in one molecule because of its high reactivity.
In the present specification, the “(meth) acryloyl group” means acryloyl or methacryloyl, and the “(meth) acryl” means acryl or methacryl.
なお、本明細書において、上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味し、上記「エポキシ(メタ)アクリレート」とは、エポキシ樹脂中の全てのエポキシ基を(メタ)アクリル酸と反応させた化合物のことを表す。 Examples of the (meth) acrylic resin include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and an epoxy (meta) obtained by reacting (meth) acrylic acid with an epoxy compound. ) Urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with acrylate or isocyanate. Of these, epoxy (meth) acrylate is preferable from the viewpoint of ease of synthesis and the like.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate, and the “epoxy (meth) acrylate” means all epoxy groups in the epoxy resin and (meth) acrylic acid. It represents the reacted compound.
上記ビスフェノールF型エポキシ樹脂のうち市販されているものとしては、例えば、エピコート806、エピコート4004(いずれも三菱化学社製)等が挙げられる。
上記ビスフェノールS型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA1514(DIC社製)等が挙げられる。
上記2,2’-ジアリルビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、RE-810NM(日本化薬社製)等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA7015(DIC社製)等が挙げられる。
上記プロピレンオキシド付加ビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4000S(ADEKA社製)等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、EX-201(ナガセケムテックス社製)等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、エピコートYX-4000H(三菱化学社製)等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-50TE(新日鉄住金化学社製)等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-80DE(新日鉄住金化学社製)等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4088S(ADEKA社製)等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP4032、エピクロンEXA-4700(いずれもDIC社製)等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-770(DIC社製)等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-670-EXP-S(DIC社製)等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP7200(DIC社製)等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、NC-3000P(日本化薬社製)等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ESN-165S(新日鉄住金化学社製)等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、エピコート630(三菱化学社製)、エピクロン430(DIC社製)、TETRAD-X(三菱ガス化学社製)等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ZX-1542(新日鉄住金化学社製)、エピクロン726(DIC社製)、エポライト80MFA(共栄社化学社製)、デナコールEX-611(ナガセケムテックス社製)等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、YR-450、YR-207(いずれも新日鉄住金化学社製)、エポリードPB(ダイセル化学工業社製)等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールEX-147(ナガセケムテックス社製)等が挙げられる。
上記エポキシ樹脂のうちその他に市販されているものとしては、例えば、YDC-1312、YSLV-80XY、YSLV-90CR(いずれも新日鉄住金化学社製)、XAC4151(旭化成社製)、エピコート1031、エピコート1032(いずれも三菱化学社製)、EXA-7120(DIC社製)、TEPIC(日産化学社製)等が挙げられる。 As what is marketed among the said bisphenol A type epoxy resin, Epicoat 828EL, Epicoat 1004 (all are the Mitsubishi Chemical company make), Epiklon 850 (made by DIC company), etc. are mentioned, for example.
As what is marketed among the said bisphenol F type epoxy resins, Epicoat 806, Epicoat 4004 (all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include Epicoat YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine epoxy resins include Epicoat 630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and Epolide PB (manufactured by Daicel Chemical Industries, Ltd.).
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032. (All manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.
なお、本明細書において上記部分(メタ)アクリル変性エポキシ樹脂とは、1分子中にエポキシ基と(メタ)アクリロイルオキシ基とをそれぞれ1つ以上有する樹脂を意味し、例えば、2つ以上のエポキシ樹脂の一部分のエポキシ基を(メタ)アクリル酸と反応させることによって得ることができる。 The said (meth) acrylic resin may contain a partial (meth) acryl modified epoxy resin from a viewpoint of improving adhesiveness.
In the present specification, the partial (meth) acryl-modified epoxy resin means a resin having one or more epoxy groups and (meth) acryloyloxy groups in one molecule, for example, two or more epoxy resins. It can be obtained by reacting a part of the epoxy group of the resin with (meth) acrylic acid.
なお、本明細書において上記水素結合性官能基価とは、上記水素結合性官能基を有する化合物が1種類(化合物Aのみ)からなる場合には、下記式により算出される値である。
水素結合性官能基価(HA)(mol/g)=(化合物Aの1分子中の水素結合性官能基数)/(化合物Aの分子量)
また、上記水素結合性官能基価は、上記水素結合性官能基を有する化合物が複数の樹脂の混合物からなる場合には、各々の水素結合性官能基を有する化合物の単位重量あたりの含有量(重量分率)により分配して算出することができる。例えば、水素結合性官能基を有する化合物が、化合物A、化合物B、及び、化合物Cから構成されている場合の水素結合性官能基価は、下記式で表される。
水素結合性官能基価(HABC)=HAPA+HBPB+HCPC
(なお、Pαは化合物αの重量分率を表す。) The preferable lower limit of the hydrogen bonding functional group value of the curable resin is 2 × 10 −3 mol / g, and the preferable upper limit is 5 × 10 −3 mol / g. When the hydrogen bonding functional group value of the curable resin is less than 2 × 10 −3 mol / g, the adhesive property of the obtained liquid crystal dropping method sealing agent may be inferior. When the hydrogen bondable functional group value of the curable resin exceeds 5 × 10 −3 mol / g, the obtained liquid crystal dropping method sealant may contaminate the liquid crystal.
In addition, in this specification, the said hydrogen bondable functional group value is a value computed by the following formula, when the compound which has the said hydrogen bondable functional group consists of 1 type (compound A only).
Hydrogen bonding functional group value (H A ) (mol / g) = (number of hydrogen bonding functional groups in one molecule of compound A) / (molecular weight of compound A)
In addition, when the compound having the hydrogen bondable functional group is composed of a mixture of a plurality of resins, the hydrogen bondable functional group value is the content per unit weight of the compound having each hydrogen bondable functional group ( (Weight fraction) can be distributed and calculated. For example, the hydrogen bondable functional group value when the compound having a hydrogen bondable functional group is composed of the compound A, the compound B, and the compound C is represented by the following formula.
Hydrogen-bonding functional group value (H ABC) = H A P A + H B P B + H C P C
(Note that P α represents the weight fraction of compound α.)
上記増感剤を含有することにより、更に高感度で光硬化性に優れる液晶滴下工法用シール剤を得ることができる。 It is preferable that the sealing compound for liquid crystal dropping method of this
By containing the sensitizer, it is possible to obtain a sealing agent for a liquid crystal dropping method that has higher sensitivity and excellent photocurability.
上記アントラセン骨格を有する化合物としては、例えば、9,10-ジブトキシアントラセン、9,10-ジプロキシアントラキノン、9,10-エトキシアントラキノン等が挙げられる。
上記アントラキノン骨格を有する化合物としては、例えば、2-エチルアントラキノン、1-メチルアントラキノン、1,4-ジヒドロキシアントラキノン、2-(2-ヒドロキシエトキシ)-アントラキノン等が挙げられる。
上記クマリン骨格を有する化合物としては、例えば、7-ジエチルアミノ-4-メチルクマリン等が挙げられる。
上記チオキサントン骨格を有する化合物としては、例えば、2,4-ジエチルチオキサントン、2-クロロチオキサントン、4-イソプロピルチオキサントン、1-クロロ-4-プロピルチオキサントン等が挙げられる。
上記フタロシアニン骨格を有する化合物としては、例えば、フタロシアニン等が挙げられる。
これらの増感剤のなかでも、得られる液晶滴下工法用シール剤が遮光部の硬化性に特に優れるものとなることから、4,4’-ビス(ジメチルアミノ)ベンゾフェノン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、及び、4-(ジメチルアミノ)ベンゾフェノンからなる群より選択される少なくとも1種が好ましい。 Examples of the compound having a benzophenone skeleton include benzophenone, 2,4-dichlorobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and 4- (dimethylamino) benzophenone. Etc.
Examples of the compound having an anthracene skeleton include 9,10-dibutoxyanthracene, 9,10-diproxyanthraquinone, and 9,10-ethoxyanthraquinone.
Examples of the compound having an anthraquinone skeleton include 2-ethylanthraquinone, 1-methylanthraquinone, 1,4-dihydroxyanthraquinone, 2- (2-hydroxyethoxy) -anthraquinone and the like.
Examples of the compound having a coumarin skeleton include 7-diethylamino-4-methylcoumarin.
Examples of the compound having a thioxanthone skeleton include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and the like.
Examples of the compound having a phthalocyanine skeleton include phthalocyanine.
Among these sensitizers, the resulting liquid crystal dropping method sealant is particularly excellent in light-curing part curability, so that 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis At least one selected from the group consisting of (diethylamino) benzophenone and 4- (dimethylamino) benzophenone is preferred.
上記熱硬化剤としては、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。 It is preferable that the sealing compound for liquid crystal dropping method of this
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、SDH、ADH(いずれも大塚化学社製)、アミキュアVDH、アミキュアVDH-J、アミキュアUDH(いずれも味の素ファインテクノ社製)等が挙げられる。 Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of commercially available organic acid hydrazides include SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like. It is done.
表1、2に記載された配合比に従い、各材料を、遊星式撹拌機(シンキー社製、「あわとり練太郎」)を用いて混合した後、更に3本ロールを用いて混合することにより実施例1~10、比較例1~12の液晶滴下工法用シール剤を調製した。
なお、表1、2中に記載した、「式(3)で表される化合物」及び「式(4)で表される化合物」は、それぞれ下記式(3)及び(4)で表される化合物を意味する。 (Examples 1 to 10, Comparative Examples 1 to 12)
According to the mixing ratios described in Tables 1 and 2, after mixing each material using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), by further mixing using three rolls Sealants for liquid crystal dropping method of Examples 1 to 10 and Comparative Examples 1 to 12 were prepared.
The “compound represented by the formula (3)” and the “compound represented by the formula (4)” described in Tables 1 and 2 are represented by the following formulas (3) and (4), respectively. Means a compound.
実施例1~10、比較例1~12で得られた各液晶滴下工法用シール剤について以下の評価を行った。結果を表1、2に示した。 <Evaluation>
The following evaluations were performed on the sealing agents for liquid crystal dropping methods obtained in Examples 1 to 10 and Comparative Examples 1 to 12. The results are shown in Tables 1 and 2.
まず、厚さ0.7mmのコーニングガラスの半面をクロム蒸着した基板(A)と、前面をクロム蒸着した基板(B)とを別途準備した。次に、実施例1~10、比較例1~12で得られた各液晶滴下工法用シール剤100重量部にスペーサ微粒子(積水化学工業社製、「ミクロパールSI-H050」、5μm)1重量部を分散させ、該シール剤を基板Aの中央部(クロム蒸着部と非蒸着部との境界)に塗布し、基板Bを貼り合わせてからシール剤を充分に押し潰し、基板A側からメタルハライドランプを用いて100mW/cm2の紫外線を30秒照射した。
その後、カッターを用いて基板A及びBを剥がし、顕微IR法によって紫外線直接照射部(場所1)と紫外線直接照射部の際から50μm離れた点(場所2)上のシール剤のスペクトルを測定し、それぞれのスペクトルからシール剤中のアクリロイル基の転化率を以下の方法により求めた。即ち、815~800cm-1のピーク面積をアクリロイル基のピーク面積とし、845~820cm-1のピーク面積をリファレンスピーク面積として、下記式によりアクリロイル基の転化率を算出した。
アクリロイル基の転化率={1-(紫外線照射後のアクリロイル基のピーク面積/紫外線照射後のリファレンスピーク面積)/(紫外線照射前のアクリロイル基のピーク面積/紫外線照射前のリファレンスピーク面積)}×100 (Photo-curing)
First, a substrate (A) on which a half surface of a 0.7 mm thick Corning glass was vapor-deposited and a substrate (B) in which the front surface was vapor-deposited with chromium were separately prepared. Next, 100 parts by weight of each of the liquid crystal dropping method sealing agents obtained in Examples 1 to 10 and Comparative Examples 1 to 12 was added 1 weight of spacer fine particles (“Micropearl SI-H050”, 5 μm, manufactured by Sekisui Chemical Co., Ltd.). Parts are dispersed, and the sealant is applied to the central part of the substrate A (the boundary between the chromium vapor deposition part and the non-deposition part), and after the substrate B is bonded together, the sealant is sufficiently crushed and the metal halide is applied from the substrate A side. A 100 mW / cm 2 ultraviolet ray was irradiated for 30 seconds using a lamp.
Thereafter, the substrates A and B are peeled off using a cutter, and the spectrum of the sealant on the point (place 2) 50 μm away from the position of the ultraviolet direct irradiator (place 1) and the ultraviolet direct irradiator is measured by microscopic IR method. From the respective spectra, the conversion of acryloyl groups in the sealant was determined by the following method. That is, the conversion area of acryloyl groups was calculated by the following formula using the peak area of 815 to 800 cm −1 as the peak area of acryloyl group and the peak area of 845 to 820 cm −1 as the reference peak area.
Conversion ratio of acryloyl group = {1- (peak area of acryloyl group after UV irradiation / reference peak area after UV irradiation) / (peak area of acryloyl group before UV irradiation / reference peak area before UV irradiation)} × 100
実施例1~10、比較例1~12で得られた各液晶滴下工法用シール剤100重量部にスペーサ微粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を分散させ、液晶滴下工法用シール剤として、2枚のラビング済み配向膜及び透明電極付き基板の一方にシール剤の線幅が1mmになるようにディスペンサーで塗布した。
続いて液晶(チッソ社製、「JC-5004LA」)の微小滴を透明電極付き基板のシール剤の枠内全面に滴下塗布し、すぐにもう一方の透明電極付きカラーフィルター基板を貼り合わせ、シール剤部分にメタルハライドランプを用いて100mW/cm2の紫外線を30秒照射して硬化させ、更に、120℃で1時間加熱して液晶表示素子を得た。
液晶表示素子は、ディスペンサーでシール剤の塗布位置をコントロールし、シール剤に完全に光が当たる液晶表示素子(遮光部なし)と、カラーフィルター基板のブラックマトリックスに線幅の50%がかかるようにシール剤を塗布した液晶表示素子(遮光部あり)の2種類を作製した。図1に示すように、シール剤1に遮光部がないものは完全にシール剤1が光に当たる状態であり、一方、シール剤1に遮光部がある液晶表示素子は、図2に示すように、液晶3と接する部分のシール剤1は、ブラックマトリックス2で遮蔽されて全く光が当たらない。
得られた液晶表示素子について、80℃で1000時間電圧印加状態とした後のシール剤付近の液晶配向乱れを目視によって確認した。
配向乱れは表示部の色むらより判断しており、色むらの程度に応じて、色むらが全くなかった場合を「◎」、色むらが微かにあった場合を「○」、色むらが少しあった場合を「△」、色むらがかなりあった場合を「×」として液晶汚染性を評価した。
なお、評価が「◎」、「○」の液晶表示素子は実用に全く問題のないレベルである。 (Liquid crystal contamination 1)
1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SI-H050”) is dispersed in 100 parts by weight of the sealing agent for each liquid crystal dropping method obtained in Examples 1 to 10 and Comparative Examples 1 to 12. As a sealing agent for the liquid crystal dropping method, it was applied with a dispenser to one of two rubbed alignment films and a substrate with a transparent electrode so that the line width of the sealing agent was 1 mm.
Subsequently, liquid droplets (manufactured by Chisso Corp., “JC-5004LA”) are dropped onto the entire surface of the sealing agent frame of the substrate with the transparent electrode, and the other color filter substrate with the transparent electrode is immediately bonded to the seal. The agent part was cured by irradiating with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp, and further heated at 120 ° C. for 1 hour to obtain a liquid crystal display element.
The liquid crystal display element controls the application position of the sealant with a dispenser so that 50% of the line width is applied to the liquid crystal display element (without the light shielding part) where the sealant is completely exposed to light and the black matrix of the color filter substrate. Two types of liquid crystal display elements (with a light shielding part) coated with a sealant were prepared. As shown in FIG. 1, when the sealing
About the obtained liquid crystal display element, the liquid crystal orientation disorder of the sealant vicinity after making it into a voltage application state at 80 degreeC for 1000 hours was confirmed visually.
The orientation disorder is determined from the color unevenness of the display part. Depending on the degree of color unevenness, “◎” indicates that there is no color unevenness, “○” indicates that there is slight color unevenness, and color unevenness. The liquid crystal contamination property was evaluated with “△” when there was a little, and “×” when there was considerable color unevenness.
Note that the liquid crystal display elements with the evaluations “◎” and “で” are at a level that causes no problem in practical use.
上記「(液晶汚染性1)」と同様にして、実施例1~10、比較例1~12で得られた各液晶滴下工法用シール剤を用いて、カラーフィルター基板のブラックマトリックスに線幅の50%がかかるようにシール剤を塗布した液晶表示素子(遮光部あり)を作製した。
得られた液晶表示素子について、90℃乾燥雰囲気下で1000時間電圧印加状態とした後のシール剤付近の液晶配向乱れを目視によって確認した。
「(液晶汚染性2)」は、「(液晶汚染性1)」と比べて加熱条件が過酷なため、イオン性物質の流動性が高まることにより、液晶配向乱れがより生じやすくなると考えられる。
配向乱れは表示部の色むらより判断しており、色むらの程度に応じて、色むらが全くなかった場合を「◎」、色むらが微かにあった場合を「○」、色むらが少しあった場合を「△」、色むらがかなりあった場合を「×」として液晶汚染性を評価した。
なお、評価が「◎」、「○」の液晶表示素子は実用に全く問題のないレベルである。 (Liquid crystal contamination 2)
In the same manner as in “(Liquid crystal contamination 1)”, the line width of the black matrix of the color filter substrate was adjusted using the sealing agents for liquid crystal dropping methods obtained in Examples 1 to 10 and Comparative Examples 1 to 12. A liquid crystal display element (with a light-shielding portion) coated with a sealant so as to take 50% was produced.
About the obtained liquid crystal display element, the liquid crystal orientation disorder of the sealant vicinity after making it into a voltage application state for 1000 hours in 90 degreeC dry atmosphere was confirmed visually.
Since “(liquid crystal contamination 2)” has a severer heating condition than “(liquid crystal contamination 1)”, it is considered that liquid crystal alignment disorder is more likely to occur due to an increase in fluidity of the ionic substance.
The orientation disorder is determined from the color unevenness of the display part. Depending on the degree of color unevenness, “◎” indicates that there is no color unevenness, “○” indicates that there is slight color unevenness, and color unevenness. The liquid crystal contamination property was evaluated with “△” when there was a little, and “×” when there was considerable color unevenness.
Note that the liquid crystal display elements with the evaluations “◎” and “で” are at a level that causes no problem in practical use.
表3に記載された配合比に従い、各材料を、遊星式撹拌機(シンキー社製、「あわとり練太郎」)を用いて混合した後、更に3本ロールを用いて混合することにより実施例11~20、比較例13、14の液晶滴下工法用シール剤を調製した。
なお、表3中に記載した、「式(3)で表される化合物」、「式(4)で表される化合物」、「式(5)で表される化合物」、及び、「式(6)で表される化合物」は、それぞれ下記式(3)、(4)、(5)、及び、(6)で表される化合物を意味する。 (Examples 11 to 20, Comparative Examples 13 and 14)
In accordance with the blending ratio described in Table 3, each material was mixed using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Nertaro ”), and then mixed using three rolls. The sealing agents for the liquid crystal dropping method of 11 to 20 and Comparative Examples 13 and 14 were prepared.
In addition, “compound represented by formula (3)”, “compound represented by formula (4)”, “compound represented by formula (5)”, and “formula ( “Compound represented by 6)” means compounds represented by the following formulas (3), (4), (5) and (6), respectively.
実施例11~20、比較例13、14で得られた各液晶滴下工法用シール剤について以下の評価を行った。結果を表3に示した。 <Evaluation>
The following evaluations were performed on the sealing agents for liquid crystal dropping methods obtained in Examples 11 to 20 and Comparative Examples 13 and 14. The results are shown in Table 3.
実施例11~20、比較例13、14で得られた各液晶滴下工法用シール剤をガラス基板上に約5μm塗布し、その基板に同サイズのガラス基板を重ね合わせ、次に、メタルハライドランプを用いて100mW/cm2の光を10秒照射した。赤外分光装置(BIORAD社製、「FTS3000」)を用い、アクリロイル基由来ピークの光照射前後での変化量を測定することで光硬化性の評価を行った。光照射後にアクリロイル基由来のピークが93%以上減少した場合を「◎」、光照射後にアクリロイル基由来のピークが85%以上93%未満減少した場合を「○」、光照射後にアクリロイル基由来のピークが75%以上85%未満減少した場合を「△」、光照射後のアクリロイル基由来のピークの減少が75%未満であった場合を「×」として光硬化性を評価した。 (Photo-curing)
Each of the liquid crystal dropping method sealing agents obtained in Examples 11 to 20 and Comparative Examples 13 and 14 was applied to a glass substrate by about 5 μm, and the same size glass substrate was superposed on the substrate, and then a metal halide lamp was mounted. A light of 100 mW / cm 2 was used for 10 seconds. Photocurability was evaluated by measuring the amount of change of the acryloyl group-derived peak before and after light irradiation using an infrared spectroscopic apparatus (manufactured by BIORAD, “FTS3000”). “◎” indicates that the peak derived from the acryloyl group has decreased by 93% or more after light irradiation, “O” indicates that the peak derived from the acryloyl group has decreased by 85% or more but less than 93% after light irradiation, Photocurability was evaluated as “Δ” when the peak was decreased by 75% or more and less than 85%, and “X” when the decrease in the peak derived from the acryloyl group after light irradiation was less than 75%.
実施例11~20、比較例13、14で得られた各液晶滴下工法用シール剤100重量部にスペーサ微粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を分散させ、液晶滴下工法用シール剤として、2枚のラビング済み配向膜及び透明電極付き基板の一方にシール剤の線幅が1mmになるようにディスペンサーで塗布した。
続いて液晶(チッソ社製、「JC-5004LA」)の微小滴を透明電極付き基板のシール剤の枠内全面に滴下塗布し、すぐにもう一方の透明電極付きカラーフィルター基板を貼り合わせ、シール剤部分にメタルハライドランプを用いて100mW/cm2の紫外線を30秒照射して硬化させ、更に、120℃で1時間加熱して液晶表示素子を得た。
液晶表示素子は、ディスペンサーでシール剤の塗布位置をコントロールし、シール剤に完全に光が当たる液晶表示素子(遮光部なし)と、シール剤がカラーフィルター基板のブラックマトリックスに線幅の50%がかかるように塗布した液晶表示素子(遮光部あり)の2種類を作製した。図1に示すように、シール剤1に遮光部がないものは完全にシール剤1が光に当たる状態であり、一方、シール剤1に遮光部がある液晶表示素子は、図2に示すように、液晶3と接する部分のシール剤1は、ブラックマトリックス2で遮蔽されて全く光が当たらない。
得られた液晶表示素子について、80℃で1000時間電圧印加状態とした後のシール剤付近の液晶配向乱れを目視によって確認した。
配向乱れは表示部の色むらより判断しており、色むらの程度に応じて、色むらが全くなかった場合を「◎」、色むらが微かにあった場合を「○」、色むらが少しあった場合を「△」、色むらがかなりあった場合を「×」として液晶汚染性を評価した。
なお、評価が「◎」、「○」の液晶表示素子は実用に全く問題のないレベルである。 (Liquid crystal contamination)
1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SI-H050”) is dispersed in 100 parts by weight of the sealant for each liquid crystal dropping method obtained in Examples 11 to 20 and Comparative Examples 13 and 14. As a sealing agent for the liquid crystal dropping method, it was applied with a dispenser to one of two rubbed alignment films and a substrate with a transparent electrode so that the line width of the sealing agent was 1 mm.
Subsequently, liquid droplets (manufactured by Chisso Corp., “JC-5004LA”) are dropped onto the entire surface of the sealing agent frame of the substrate with the transparent electrode, and the other color filter substrate with the transparent electrode is immediately bonded to the seal. The agent part was cured by irradiating with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp, and further heated at 120 ° C. for 1 hour to obtain a liquid crystal display element.
The liquid crystal display element controls the application position of the sealant with a dispenser, and the liquid crystal display element (no light blocking part) where the sealant is completely exposed to light, and the sealant has 50% of the line width on the black matrix of the color filter substrate. Two types of liquid crystal display elements (with light-shielding portions) coated in this way were produced. As shown in FIG. 1, when the sealing
About the obtained liquid crystal display element, the liquid crystal orientation disorder of the sealant vicinity after making it into a voltage application state at 80 degreeC for 1000 hours was confirmed visually.
The orientation disorder is determined from the color unevenness of the display part. Depending on the degree of color unevenness, “◎” indicates that there is no color unevenness, “○” indicates that there is slight color unevenness, and color unevenness. The liquid crystal contamination property was evaluated with “△” when there was a little, and “×” when there was considerable color unevenness.
Note that the liquid crystal display elements with the evaluations “◎” and “で” are at a level that causes no problem in practical use.
2 ブラックマトリックス
3 液晶 1
Claims (8)
- 硬化性樹脂と光重合開始剤とを含有する液晶滴下工法用シール剤であって、
前記光重合開始剤は、下記式(1)で表される化合物とオキシムエステル系化合物とを含有し、かつ、
前記式(1)で表される化合物と前記オキシムエステル系化合物との含有割合が、重量比で、式(1)で表される化合物:オキシムエステル系化合物=1:3~1:100である
ことを特徴とする液晶滴下工法用シール剤。
The photopolymerization initiator contains a compound represented by the following formula (1) and an oxime ester compound, and
The content ratio of the compound represented by the formula (1) and the oxime ester compound is a weight ratio of the compound represented by the formula (1): the oxime ester compound = 1: 3 to 1: 100. A sealing agent for liquid crystal dropping method.
- 式(1)で表される化合物は、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、4,4’-ビス(ジメチルアミノ)ベンゾフェノン、及び、4-(ジメチルアミノ)ベンゾフェノンからなる群より選択される少なくとも一種であることを特徴とする請求項1記載の液晶滴下工法用シール剤。 The compound represented by the formula (1) is selected from the group consisting of 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, and 4- (dimethylamino) benzophenone. The sealing agent for liquid crystal dropping method according to claim 1, wherein the sealing agent is at least one kind.
- オキシムエステル系化合物は、1-[4-(フェニルチオ)フェニル]-1,2-オクタンジオン2-(O-ベンゾイルオキシム)、及び、下記式(2)で表される化合物の少なくともいずれかであることを特徴とする請求項1又は2記載の液晶滴下工法用シール剤。
- 硬化性樹脂は、1分子中に少なくとも1つの(メタ)アクリロイル基を有する樹脂を含有し、かつ、水素結合性官能基価が2×10-3~5×10-3mol/gであることを特徴とする請求項1、2又は3記載の液晶滴下工法用シール剤。 The curable resin contains a resin having at least one (meth) acryloyl group in one molecule and has a hydrogen bondable functional group value of 2 × 10 −3 to 5 × 10 −3 mol / g. The sealing agent for liquid crystal dropping method according to claim 1, 2, or 3.
- 硬化性樹脂と光重合開始剤とを含有する液晶滴下工法用シール剤であって、
前記光重合開始剤は、下記式(2)で表される化合物を含有することを特徴とする液晶滴下工法用シール剤。
The said photoinitiator contains the compound represented by following formula (2), The sealing compound for liquid crystal dropping methods characterized by the above-mentioned.
- 増感剤を含有することを特徴とする請求項5記載の液晶滴下工法用シール剤。 A sensitizer is contained, The sealing compound for liquid crystal dropping methods of Claim 5 characterized by the above-mentioned.
- 請求項1、2、3、4、5又は6記載の液晶滴下工法用シール剤と、導電性微粒子とを含有することを特徴とする上下導通材料。 A vertical conduction material comprising the sealing agent for a liquid crystal dropping method according to claim 1, 2, 3, 4, 5, or 6, and conductive fine particles.
- 請求項1、2、3、4、5若しくは6記載の液晶滴下工法用シール剤又は請求項7記載の上下導通材料を用いて製造されることを特徴とする液晶表示素子。 A liquid crystal display element manufactured using the sealing agent for liquid crystal dropping method according to claim 1, 2, 3, 4, 5, or 6, or the vertical conduction material according to claim 7.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014511672A JP5735704B2 (en) | 2013-03-06 | 2014-02-28 | Sealant for liquid crystal dropping method |
CN201480006723.0A CN104981732B (en) | 2013-03-06 | 2014-02-28 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
KR1020157015114A KR101569332B1 (en) | 2013-03-06 | 2014-02-28 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013044418 | 2013-03-06 | ||
JP2013-044418 | 2013-03-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014136667A1 true WO2014136667A1 (en) | 2014-09-12 |
Family
ID=51491186
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/055040 WO2014136667A1 (en) | 2013-03-06 | 2014-02-28 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
Country Status (5)
Country | Link |
---|---|
JP (4) | JP5735704B2 (en) |
KR (2) | KR101569333B1 (en) |
CN (3) | CN107255893A (en) |
TW (2) | TWI509059B (en) |
WO (1) | WO2014136667A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015152030A1 (en) * | 2014-03-31 | 2015-10-08 | 積水化学工業株式会社 | Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element |
JP2017102291A (en) * | 2015-12-02 | 2017-06-08 | 協立化学産業株式会社 | Sealant for liquid crystal display device |
WO2017169986A1 (en) * | 2016-03-30 | 2017-10-05 | 日本ゼオン株式会社 | Photocurable sealant composition, commodity, and organic solar cell |
JP2020023678A (en) * | 2018-07-27 | 2020-02-13 | 日本化薬株式会社 | Electronic component sealant |
JP6703650B1 (en) * | 2018-07-10 | 2020-06-03 | 積水化学工業株式会社 | Liquid crystal element sealant, vertical conduction material, and liquid crystal element |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017061255A1 (en) * | 2015-10-09 | 2017-04-13 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
WO2017094572A1 (en) * | 2015-12-01 | 2017-06-08 | シャープ株式会社 | Sealant for liquid crystal sealing, and liquid crystal display device |
KR102467952B1 (en) * | 2016-12-16 | 2022-11-16 | 세키스이가가쿠 고교가부시키가이샤 | Polymerizable compound, sealant for liquid crystal display element, top and bottom conduction material, and liquid crystal display element |
KR102128235B1 (en) * | 2018-03-28 | 2020-06-30 | 세키스이가가쿠 고교가부시키가이샤 | Composition for electronic materials, sealing agent for liquid crystal display elements, upper and lower conductive materials, and liquid crystal display elements |
WO2019198631A1 (en) * | 2018-04-11 | 2019-10-17 | 積水化学工業株式会社 | Photopolymerization initiator, sealant for display elements, vertical conduction material, display element, and compound |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010121069A (en) * | 2008-11-20 | 2010-06-03 | Jsr Corp | Curable composition, liquid crystal sealing agent, and liquid crystal display element |
JP2011132215A (en) * | 2009-11-27 | 2011-07-07 | Adeka Corp | Oxime ester compound and photopolymerization initiator containing the same |
WO2012002028A1 (en) * | 2010-06-28 | 2012-01-05 | 株式会社Adeka | Curable resin composition |
JP5337318B1 (en) * | 2012-11-22 | 2013-11-06 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007135962A1 (en) * | 2006-05-18 | 2007-11-29 | Mitsubishi Chemical Corporation | Curable composition, cured product, color filter, and liquid crystal display device |
JP4224526B1 (en) * | 2007-07-06 | 2009-02-18 | 三井化学株式会社 | Liquid crystal sealing agent, (meth) acrylic acid ester compound used therefor, and method for producing the same |
WO2009119688A1 (en) * | 2008-03-26 | 2009-10-01 | 積水化学工業株式会社 | Sealing material for liquid-crystal dropping process, vertical-conduction material, and liquid-crystal display element |
JP2012532334A (en) * | 2009-07-02 | 2012-12-13 | 東友ファインケム株式会社 | Colored photosensitive resin composition for producing a color filter of a solid-state imaging device using an ultrashort wavelength exposure device of 300 nm or less, a color filter using the same, and a solid-state imaging device including the same |
KR20110060597A (en) * | 2009-11-30 | 2011-06-08 | 금호석유화학 주식회사 | Curing resin composition for liquid crystal dropping method and method for manufacturing the same |
CN102516916B (en) * | 2011-12-12 | 2013-08-14 | 东莞市派乐玛新材料技术开发有限公司 | Liquid crystal sealant composition |
-
2014
- 2014-02-28 KR KR1020157015137A patent/KR101569333B1/en active IP Right Grant
- 2014-02-28 CN CN201710271068.7A patent/CN107255893A/en active Pending
- 2014-02-28 CN CN201510463891.9A patent/CN105062400A/en active Pending
- 2014-02-28 CN CN201480006723.0A patent/CN104981732B/en active Active
- 2014-02-28 KR KR1020157015114A patent/KR101569332B1/en active IP Right Grant
- 2014-02-28 WO PCT/JP2014/055040 patent/WO2014136667A1/en active Application Filing
- 2014-02-28 JP JP2014511672A patent/JP5735704B2/en active Active
- 2014-03-04 TW TW104122133A patent/TWI509059B/en active
- 2014-03-04 TW TW103107133A patent/TWI525181B/en active
-
2015
- 2015-03-11 JP JP2015048634A patent/JP2015163964A/en active Pending
- 2015-03-11 JP JP2015048635A patent/JP5736096B1/en active Active
- 2015-04-16 JP JP2015084410A patent/JP2015180938A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010121069A (en) * | 2008-11-20 | 2010-06-03 | Jsr Corp | Curable composition, liquid crystal sealing agent, and liquid crystal display element |
JP2011132215A (en) * | 2009-11-27 | 2011-07-07 | Adeka Corp | Oxime ester compound and photopolymerization initiator containing the same |
WO2012002028A1 (en) * | 2010-06-28 | 2012-01-05 | 株式会社Adeka | Curable resin composition |
JP5337318B1 (en) * | 2012-11-22 | 2013-11-06 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015152030A1 (en) * | 2014-03-31 | 2015-10-08 | 積水化学工業株式会社 | Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element |
JP2017102291A (en) * | 2015-12-02 | 2017-06-08 | 協立化学産業株式会社 | Sealant for liquid crystal display device |
WO2017169986A1 (en) * | 2016-03-30 | 2017-10-05 | 日本ゼオン株式会社 | Photocurable sealant composition, commodity, and organic solar cell |
CN108884377A (en) * | 2016-03-30 | 2018-11-23 | 日本瑞翁株式会社 | Photocurable composition, article and organic system solar battery |
JPWO2017169986A1 (en) * | 2016-03-30 | 2019-02-07 | 日本ゼオン株式会社 | Photocurable sealing agent composition, article and organic solar cell |
JP6703650B1 (en) * | 2018-07-10 | 2020-06-03 | 積水化学工業株式会社 | Liquid crystal element sealant, vertical conduction material, and liquid crystal element |
JP2020023678A (en) * | 2018-07-27 | 2020-02-13 | 日本化薬株式会社 | Electronic component sealant |
JP7266484B2 (en) | 2018-07-27 | 2023-04-28 | 日本化薬株式会社 | Sealant for electronic parts |
Also Published As
Publication number | Publication date |
---|---|
CN104981732B (en) | 2017-05-24 |
CN105062400A (en) | 2015-11-18 |
KR101569333B1 (en) | 2015-11-13 |
JP5735704B2 (en) | 2015-06-17 |
KR20150081452A (en) | 2015-07-14 |
TWI509059B (en) | 2015-11-21 |
TW201538698A (en) | 2015-10-16 |
JP5736096B1 (en) | 2015-06-17 |
JP2015180938A (en) | 2015-10-15 |
TWI525181B (en) | 2016-03-11 |
JPWO2014136667A1 (en) | 2017-02-09 |
CN107255893A (en) | 2017-10-17 |
JP2015163964A (en) | 2015-09-10 |
TW201443210A (en) | 2014-11-16 |
KR20150088267A (en) | 2015-07-31 |
KR101569332B1 (en) | 2015-11-13 |
JP2015163965A (en) | 2015-09-10 |
CN104981732A (en) | 2015-10-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5736096B1 (en) | Sealant for liquid crystal dropping method | |
JP5759638B1 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
JP6434901B2 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
WO2019198631A1 (en) | Photopolymerization initiator, sealant for display elements, vertical conduction material, display element, and compound | |
JP6454217B2 (en) | Modified dialkylaminobenzoic acid-based compound, modified thioxanthone derivative, photocurable resin composition, liquid crystal display element sealing agent, vertical conduction material, and liquid crystal display element | |
JP6408983B2 (en) | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element | |
JP5340502B2 (en) | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element | |
JP6460797B2 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
JP6216260B2 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
JP6126756B1 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
JP5337318B1 (en) | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element | |
WO2016194871A1 (en) | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element | |
JP5337294B1 (en) | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element | |
JP6378970B2 (en) | Curable resin composition, liquid crystal display element sealing agent, vertical conduction material, and liquid crystal display element | |
JP2014013382A (en) | Sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element | |
JP7295798B2 (en) | liquid crystal display element | |
JP6609396B1 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
JP6031215B1 (en) | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element | |
JP2017003989A (en) | Sealant for liquid crystal display elements, vertical conduction material, and liquid crystal display element | |
JP2017132863A (en) | Oxime ester initiator, curable resin composition, sealant for liquid crystal display elements, vertical conduction material, and liquid crystal display element |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2014511672 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14761207 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20157015114 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14761207 Country of ref document: EP Kind code of ref document: A1 |