TW202005990A - Sealant for liquid crystal element, vertical conduction material, and liquid crystal element - Google Patents
Sealant for liquid crystal element, vertical conduction material, and liquid crystal element Download PDFInfo
- Publication number
- TW202005990A TW202005990A TW108124247A TW108124247A TW202005990A TW 202005990 A TW202005990 A TW 202005990A TW 108124247 A TW108124247 A TW 108124247A TW 108124247 A TW108124247 A TW 108124247A TW 202005990 A TW202005990 A TW 202005990A
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- TW
- Taiwan
- Prior art keywords
- liquid crystal
- compound
- meth
- sealant
- acrylate
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 144
- 239000000565 sealant Substances 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 10
- -1 thioxanthone compound Chemical class 0.000 claims abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 133
- 238000007789 sealing Methods 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000010419 fine particle Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 9
- 230000009974 thixotropic effect Effects 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000011109 contamination Methods 0.000 abstract description 15
- 230000035515 penetration Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 96
- 239000004593 Epoxy Substances 0.000 description 79
- 239000000126 substance Substances 0.000 description 23
- 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 17
- 239000000758 substrate Substances 0.000 description 16
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 238000003780 insertion Methods 0.000 description 10
- 230000037431 insertion Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 238000012719 thermal polymerization Methods 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 229940126062 Compound A Drugs 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 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 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 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 3
- 239000000243 solution Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QUKRJOOWAUJXJN-UHFFFAOYSA-N 1-chloro-4-methylpentane Chemical compound CC(C)CCCCl QUKRJOOWAUJXJN-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 239000004721 Polyphenylene oxide Substances 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 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
- 239000004305 biphenyl Chemical group 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 230000002542 deteriorative effect Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
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- 230000001678 irradiating effect Effects 0.000 description 2
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- 150000001451 organic peroxides Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
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- 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 1
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
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- QERNPKXJOBLNFM-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentane Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(F)F QERNPKXJOBLNFM-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
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- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- SFHURTVVCWPQSG-UHFFFAOYSA-N 2-(2-hydroxyethylsulfanyl)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(SCCO)=CC=C3C(=O)C2=C1 SFHURTVVCWPQSG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RUVNKAUVVBCURD-UHFFFAOYSA-N 2-[[4-[2-[4-(oxiran-2-ylmethoxy)-3-prop-2-enylphenyl]propan-2-yl]-2-prop-2-enylphenoxy]methyl]oxirane Chemical compound C=1C=C(OCC2OC2)C(CC=C)=CC=1C(C)(C)C(C=C1CC=C)=CC=C1OCC1CO1 RUVNKAUVVBCURD-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- DYAQXLDQUHCRBU-UHFFFAOYSA-N 2-chloroacetamide;hydrochloride Chemical compound Cl.NC(=O)CCl DYAQXLDQUHCRBU-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/30—Nitriles
- C08F222/32—Alpha-cyano-acrylic acid; Esters thereof
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
本發明係關於一種對長波長之光的深部硬化性優異、可抑制液晶向密封劑插入或由密封劑所導致之液晶污染的液晶元件用密封劑。又，本發明係關於一種使用該液晶元件用密封劑而成之上下導通材料及液晶元件。The present invention relates to a sealant for a liquid crystal element that is excellent in deep curing of long-wavelength light and can suppress insertion of liquid crystal into a sealant or contamination of liquid crystal caused by the sealant. In addition, the present invention relates to an upper and lower conduction material and a liquid crystal element formed by using the sealing agent for liquid crystal elements.
近年，作為液晶顯示單元等液晶元件之製造方法，自產距時間（tact time）縮短、使用液晶量之最佳化等觀點而言，採用如專利文獻1、專利文獻2中所揭示之利用光熱並用硬化型密封劑之稱為滴下法之液晶滴下方式。 於滴下法中，首先，於2塊附電極之透明基板之一者上藉由滴塗（dispense）形成框狀之密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微滴滴至透明基板之框內整個面，立刻與另一透明基板貼合，對密封部照射紫外線等光而進行暫時硬化。其後，於液晶退火時加熱而進行正式硬化，從而製作液晶元件。若於減壓下進行基板之貼合，則可以極高之效率製造液晶元件，該滴下法成為當前液晶元件之製造方法的主流。In recent years, as a method for manufacturing liquid crystal elements such as liquid crystal display cells, from the viewpoints of shortening the tact time and optimizing the amount of liquid crystal used, the use of light and heat as disclosed in Patent Document 1 and Patent Document 2 has been adopted. The liquid crystal dropping method called the dropping method of the hardening type sealant is also used. In the dropping method, first, a frame-like sealing pattern is formed on one of two transparent substrates with electrodes by dispense. Then, the droplets of liquid crystal are dropped onto the entire surface of the frame of the transparent substrate in a state where the sealant is not cured, and immediately bonded to another transparent substrate, and the sealing portion is irradiated with light such as ultraviolet rays to temporarily cure. After that, the liquid crystal is heated during the annealing of the liquid crystal to be completely hardened to produce a liquid crystal element. If the substrates are bonded under reduced pressure, the liquid crystal element can be manufactured with extremely high efficiency, and this dropping method has become the mainstream of current methods of manufacturing liquid crystal elements.
然而，於行動電話、攜帶型遊戲機等各種附液晶面板之移動設備普及之當代，裝置之小型化為最追求之課題。作為裝置之小型化之方法，可列舉液晶顯示部之窄邊緣化，例如將密封部之位置配置於黑矩陣下（以下亦稱為窄邊緣設計）。However, in the contemporary era in which mobile devices such as mobile phones, portable game consoles and other mobile devices with liquid crystal panels are popular, miniaturization of devices is the most sought after issue. As a method of miniaturizing the device, a narrow edge of the liquid crystal display portion can be cited, for example, the position of the sealing portion is arranged under the black matrix (hereinafter also referred to as a narrow edge design).
然而，於窄邊緣設計之情形時因密封劑配置於黑矩陣之正下方，故若進行滴下法，則存在使密封劑光硬化時所照射之光受到遮擋、光無法到達密封劑之內部從而硬化變得不充分之問題。若如此密封劑之硬化變得不充分，則存在以下問題：未硬化之密封劑成分溶出至液晶中，溶出之密封劑成分於液晶中進行硬化反應，而導致發生液晶污染。However, in the case of narrow-edge design, since the sealant is placed directly under the black matrix, if the dripping method is performed, the light irradiated when the sealant is light-hardened is blocked, and the light cannot reach the inside of the sealant to be hardened The problem becomes inadequate. If the hardening of the sealant becomes insufficient in this way, there is a problem that the uncured sealant component elutes into the liquid crystal, and the eluted sealant component undergoes a hardening reaction in the liquid crystal, resulting in liquid crystal contamination.
又，通常，作為使密封劑光硬化之方法而進行紫外線之照射，但特別是於液晶滴下法中，滴下液晶後為了使密封劑硬化而照射紫外線，因此存在液晶發生劣化之問題。對此，為了防止由紫外線所導致之液晶之劣化，摻合對可見光區域的長波長之光的反應性優異之光聚合起始劑，介隔截止濾光鏡等藉由長波長之光進行光硬化。 [先前技術文獻] [專利文獻]In addition, in general, ultraviolet light is irradiated as a method of photo-curing the sealant, but particularly in the liquid crystal dropping method, the liquid crystal is deteriorated because ultraviolet light is irradiated to harden the sealant after dropping the liquid crystal. In order to prevent the deterioration of liquid crystals caused by ultraviolet rays, a photopolymerization initiator excellent in reactivity with long-wavelength light in the visible light region is blended, and light is emitted by long-wavelength light such as a cut-off filter. hardening. [Prior Technical Literature] [Patent Literature]
專利文獻1：日本特開2001-133794號公報 專利文獻2：國際公開第02/092718號Patent Document 1: Japanese Patent Laid-Open No. 2001-133794 Patent Literature 2: International Publication No. 02/092718
[發明所欲解決之課題][Problems to be solved by the invention]
本發明之目的在於提供一種對長波長之光的深部硬化性優異、可抑制液晶向密封劑插入或由密封劑所導致之液晶污染的液晶元件用密封劑。又，本發明之目的在於提供一種使用該液晶元件用密封劑而成之上下導通材料及液晶元件。 [解決課題之技術手段]An object of the present invention is to provide a sealant for a liquid crystal element that is excellent in deep-section hardening against long-wavelength light and can suppress insertion of liquid crystal into the sealant or contamination of the liquid crystal caused by the sealant. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal element using the sealing agent for a liquid crystal element. [Technical means to solve the problem]
本發明係一種液晶元件用密封劑，其含有硬化性樹脂及光聚合起始劑，上述光聚合起始劑含有9-氧硫
近年，對裸眼3D液晶面板或液晶天線等單元間隙較大之液晶元件進行開發。於對如此單元間隙較大之液晶元件使用以往之密封劑，藉由長波長之光進行光硬化之情形時，存在以下問題：於液晶退火時等液晶插入密封劑，從而發生密封破裂而液晶漏出，或液晶受到密封劑之污染。本發明人等認為，單元間隙較大之液晶元件中發生液晶向密封劑之插入或由密封劑所導致之液晶污染之原因在於，密封劑之厚度變厚，因此即便是以往藉由可見光可充分硬化之密封劑亦無法硬化至深部。對此，本發明人等研究出將9-氧硫
本發明之液晶元件用密封劑含有光聚合起始劑。
上述光聚合起始劑含有9-氧硫
上述9-氧硫
上述9-氧硫
於上述9-氧硫
上述9-氧硫
作為上述9-氧硫
於式（1-2）中，n為1~10（平均值）。In formula (1-2), n is 1~10 (average value).
上述式（1-1）、上述式（1-2）中之芳香環之氫原子可經取代基取代。作為該取代基，例如可列舉：甲基、乙基、丙基等。The hydrogen atom of the aromatic ring in the above formula (1-1) and the above formula (1-2) may be substituted with a substituent. Examples of the substituent include methyl, ethyl, and propyl.
上述9-氧硫
上述光聚合起始劑含有肟酯化合物。藉由將上述肟酯化合物與上述9-氧硫
作為上述肟酯化合物，例如可列舉：1-(4-(苯硫基)苯基)-1,2-辛二酮2-(O-苯甲醯肟)、O-乙醯基-1-(6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基)乙酮肟、下述式（2）所表示之化合物、下述式（3）所表示之化合物等。Examples of the oxime ester compound include 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime) and O-acetoyl-1- (6-(2-methylbenzyl)-9-ethyl-9H-carbazol-3-yl)ethanone oxime, compound represented by the following formula (2), represented by the following formula (3) Represented compounds, etc.
上述式（2）、上述式（3）中之芳香環之氫原子可經取代基取代。作為該取代基，例如可列舉：甲基、乙基、丙基等。The hydrogen atom of the aromatic ring in the above formula (2) and the above formula (3) may be substituted with a substituent. Examples of the substituent include methyl, ethyl, and propyl.
上述9-氧硫
本發明之液晶元件用密封劑含有硬化性樹脂。 上述硬化性樹脂較佳為含有(甲基)丙烯酸化合物。 作為上述(甲基)丙烯酸化合物，例如可列舉：(甲基)丙烯酸酯化合物、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺酯（urethane(meth)acrylate）等。其中，較佳為環氧(甲基)丙烯酸酯。又，上述(甲基)丙烯酸化合物自反應性之觀點而言，較佳為於1分子中具有2個以上之(甲基)丙烯醯基。 再者，於本說明書中，上述「(甲基)丙烯酸基」意指丙烯酸基或甲基丙烯酸基，上述「(甲基)丙烯酸化合物」意指具有(甲基)丙烯醯基之化合物，上述「(甲基)丙烯醯基」意指丙烯醯基或甲基丙烯醯基。又，上述「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯。進而，上述「環氧(甲基)丙烯酸酯」係表示使環氧化合物中之所有環氧基與(甲基)丙烯酸反應而獲得之化合物。The sealing compound for liquid crystal elements of this invention contains curable resin. The curable resin preferably contains a (meth)acrylic compound. Examples of the (meth)acrylic compound include (meth)acrylate compounds, epoxy (meth)acrylates, and urethane (meth)acrylate. Among them, epoxy (meth)acrylate is preferred. In addition, from the viewpoint of reactivity, the (meth)acrylic compound preferably has two or more (meth)acryl acryl groups in one molecule. In addition, in this specification, the "(meth)acrylic group" means an acrylic group or a methacrylic group, and the "(meth)acrylic compound" means a compound having a (meth)acryloyl group, the above "(Meth)acryloyl" means acryloyl or methacryloyl. In addition, the "(meth)acrylate" means acrylate or methacrylate. Furthermore, the above-mentioned "epoxy (meth)acrylate" refers to a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid.
作為上述(甲基)丙烯酸酯化合物中之單官能者，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯（isobornyl(meth)acrylate）、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、醯亞胺(甲基)丙烯酸酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、琥珀酸2-(甲基)丙烯醯氧基乙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯2-羥基丙酯、磷酸2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸縮水甘油酯等。Examples of the monofunctional ones in the (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isobornyl(meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, (methyl ) 2-ethoxyethyl acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methyl Oxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate , Ethyl carbitol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (methyl ) 1H, 1H, 5H-octafluoropentyl acrylate, amide imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, succinic acid 2 -(Meth)acryloyloxyethyl, hexahydrophthalic acid 2-(meth)acryloyloxyethyl, phthalic acid 2-(meth)acryloyloxyethyl 2-hydroxy Propyl ester, 2-(meth)acryloxyethyl phosphate, glycidyl (meth)acrylate, etc.
又，作為上述(甲基)丙烯酸酯化合物中之二官能者，例如可列舉：1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、二(甲基)丙烯酸二羥甲基二環戊二烯酯、環氧乙烷改質異三聚氰酸二(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、碳酸酯二醇二(甲基)丙烯酸酯、聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己內酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。In addition, examples of the difunctional ones in the (meth)acrylate compound include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylate. , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di (Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F Di(meth)acrylate, di(meth)acrylate dimethylol dicyclopentadienyl ester, ethylene oxide modified isocyanurate di(meth)acrylate, (meth)acrylic acid 2-Hydroxy-3-(meth)acryloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth) Acrylic ester, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.
又，作為上述(甲基)丙烯酸酯化合物中之三官能以上者，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成異三聚氰酸三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、環氧丙烷加成甘油三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、磷酸三(甲基)丙烯醯氧基乙酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等。In addition, examples of the trifunctional or higher among the (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate and ethylene oxide addition trimethylolpropane tri(methyl ) Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanurate Acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, phosphate tri (meth) Acryloyloxyethyl, di-trimethylolpropane tetra(meth)acrylate, neopentyl tetraol (meth)acrylate, dipentaerythritol penta(meth)acrylate, dineopentyl Tetraol hexa (meth) acrylate, etc.
作為上述環氧(甲基)丙烯酸酯，例如可列舉藉由使環氧化合物與(甲基)丙烯酸按照常規方法於鹼性觸媒之存在下反應而獲得者等。Examples of the epoxy (meth)acrylates include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of an alkaline catalyst according to a conventional method.
關於作為用於合成上述環氧(甲基)丙烯酸酯之原料的環氧化合物，例如可列舉：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚S型環氧化合物、2,2'-二烯丙基雙酚A型環氧化合物、氫化雙酚型環氧化合物、環氧丙烷加成雙酚A型環氧化合物、間苯二酚型環氧化合物、聯苯型環氧化合物、硫醚型環氧化合物、二苯醚型環氧化合物、二環戊二烯型環氧化合物、萘型環氧化合物、苯酚酚醛清漆型環氧化合物、鄰甲酚酚醛清漆型環氧化合物、二環戊二烯酚醛清漆型環氧化合物、聯苯酚醛清漆型環氧化合物、萘酚酚醛清漆型環氧化合物、縮水甘油胺型環氧化合物、烷基多元醇型環氧化合物、橡膠改質型環氧化合物、縮水甘油酯化合物等。Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth)acrylate include bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, and bisphenol S-type epoxy compounds. 2 ,2'-diallyl bisphenol A epoxy compound, hydrogenated bisphenol epoxy compound, propylene oxide addition bisphenol A epoxy compound, resorcinol epoxy compound, biphenyl ring Oxygen compounds, thioether epoxy compounds, diphenyl ether epoxy compounds, dicyclopentadiene epoxy compounds, naphthalene epoxy compounds, phenol novolac epoxy compounds, o-cresol novolac epoxy compounds Compound, dicyclopentadiene novolac epoxy compound, biphenol novolac epoxy compound, naphthol novolac epoxy compound, glycidylamine epoxy compound, alkyl polyol epoxy compound, rubber Modified epoxy compounds, glycidyl ester compounds, etc.
作為上述雙酚A型環氧化合物中之市售者，例如可列舉：jER828EL、jER1004（均為三菱化學公司製造）、EPICLON EXA-850CRP（DIC公司製造）等。 作為上述雙酚F型環氧化合物中之市售者，例如可列舉：jER806、jER4004（均為三菱化學公司製造）等。 作為上述雙酚S型環氧化合物中之市售者，例如可列舉：EPICLON EXA1514（DIC公司製造）等。 作為上述2,2'-二烯丙基雙酚A型環氧化合物中之市售者，例如可列舉：RE-810NM（日本化藥公司製造）等。 作為上述氫化雙酚型環氧化合物中之市售者，例如可列舉：EPICLON EXA7015（DIC公司製造）等。 作為上述環氧丙烷加成雙酚A型環氧化合物中之市售者，例如可列舉：EP-4000S（ADEKA公司製造）等。 作為上述間苯二酚型環氧化合物中之市售者，例如可列舉：EX-201（長瀨化成公司製造）等。 作為上述聯苯型環氧化合物中之市售者，例如可列舉：jER YX-4000H（三菱化學公司製造）等。 作為上述硫醚型環氧化合物中之市售者，例如可列舉：YSLV-50TE（新日鐵住金化學公司製造）等。 作為上述二苯醚型環氧化合物中之市售者，例如可列舉：YSLV-80DE（新日鐵住金化學公司製造）等。 作為上述二環戊二烯型環氧化合物中之市售者，例如可列舉：EP-4088S（ADEKA公司製造）等。 作為上述萘型環氧化合物中之市售者，例如可列舉：EPICLON HP4032、EPICLON EXA-4700（均為DIC公司製造）等。 作為上述苯酚酚醛清漆型環氧化合物中之市售者，例如可列舉：EPICLON N-770（DIC公司製造）等。 作為上述鄰甲酚酚醛清漆型環氧化合物中之市售者，例如可列舉：EPICLON N-670-EXP-S（DIC公司製造）等。 作為上述二環戊二烯酚醛清漆型環氧化合物中之市售者，例如可列舉：EPICLON HP7200（DIC公司製造）等。 作為上述聯苯酚醛清漆型環氧化合物中之市售者，例如可列舉：NC-3000P（日本化藥公司製造）等。 作為上述萘酚酚醛清漆型環氧化合物中之市售者，例如可列舉：ESN-165S（新日鐵住金化學公司製造）等。 作為上述縮水甘油胺型環氧化合物中之市售者，例如可列舉：jER630（三菱化學公司製造）、EPICLON 430（DIC公司製造）、TETRAD-X（三菱瓦斯化學公司製造）等。 作為上述烷基多元醇型環氧化合物中之市售者，例如可列舉：ZX-1542（新日鐵住金化學公司製造）、EPICLON 726（DIC公司製造）、Epolight 80MFA（共榮社化學公司製造）、DENACOL EX-611（長瀨化成公司製造）等。 作為上述橡膠改質型環氧化合物中之市售者，例如可列舉：YR-450、YR-207（均為新日鐵住金化學公司製造）、Epolead PB（Daicel公司製造）等。 作為上述縮水甘油酯化合物中之市售者，例如可列舉：DENACOL EX-147（長瀨化成公司製造）等。 作為上述環氧化合物中之其他市售者，例如可列舉：YDC-1312、YSLV-80XY、YSLV-90CR（均為新日鐵住金化學公司製造）、XAC4151（旭化成公司製造）、jER1031、jER1032（均為三菱化學公司製造）、EXA-7120（DIC公司製造）、TEPIC（日產化學公司製造）等。Examples of commercially available bisphenol A epoxy compounds include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), and EPICLON EXA-850CRP (manufactured by DIC Corporation). Examples of commercially available bisphenol F-type epoxy compounds include jER806 and jER4004 (all manufactured by Mitsubishi Chemical Corporation). Examples of the commercially available bisphenol S-type epoxy compound include EPICLON EXA1514 (manufactured by DIC). As a commercial item among the said 2,2'- diallyl bisphenol A type epoxy compound, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example. Examples of the commercially available hydrogenated bisphenol-type epoxy compounds include EPICLON EXA7015 (manufactured by DIC). Examples of the commercially available propylene oxide-added bisphenol A-type epoxy compound include EP-4000S (manufactured by ADEKA). Examples of commercially available resorcinol-type epoxy compounds include EX-201 (manufactured by Nagase Chemicals) and the like. Examples of the commercially available ones of the biphenyl-type epoxy compounds include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation). Examples of commercially available thioether-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like. Examples of the commercially available diphenyl ether-type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and the like. Examples of the commercially available dicyclopentadiene-type epoxy compounds include EP-4088S (made by ADEKA). Examples of the commercially available naphthalene-type epoxy compounds include EPICLON HP4032 and EPICLON EXA-4700 (all manufactured by DIC Corporation). Examples of the commercially available phenol novolac-type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation) and the like. As a commercially available one of the above-mentioned o-cresol novolak type epoxy compounds, for example, EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like can be cited. Examples of the commercially available dicyclopentadiene novolac-type epoxy compounds include EPICLON HP7200 (manufactured by DIC Corporation) and the like. Examples of the commercially available ones of the biphenol novolac-type epoxy compounds include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like. Examples of the commercially available naphthol novolak-type epoxy compounds include ESN-165S (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.). Examples of commercially available glycidylamine-type epoxy compounds include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like. Examples of the commercially available among the alkyl polyol-type epoxy compounds include ZX-1542 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) ), DENACOL EX-611 (made by Nagase Chemical Co., Ltd.), etc. Examples of commercially available rubber modified epoxy compounds include YR-450, YR-207 (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epolead PB (manufactured by Daicel), and the like. Examples of commercially available glycidyl ester compounds include DENACOL EX-147 (manufactured by Nagase Kasei Corporation) and the like. Examples of other commercially available epoxy compounds include YDC-1312, YSLV-80XY, and YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, and jER1032 ( All are made by Mitsubishi Chemical Corporation), EXA-7120 (made by DIC Corporation), TEPIC (made by Nissan Chemical Corporation), etc.
作為上述環氧(甲基)丙烯酸酯中之市售者，例如可列舉：DAICEL-ALLNEX公司製造之環氧(甲基)丙烯酸酯、新中村化學工業公司製造之環氧(甲基)丙烯酸酯、共榮社化學公司製造之環氧(甲基)丙烯酸酯、長瀨化成公司製造之環氧(甲基)丙烯酸酯等。 作為上述DAICEL-ALLNEX公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3708、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182等。 作為上述新中村化學工業公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020等。 作為上述共榮社化學公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EPOXY ESTER M-600A、EPOXY ESTER 40EM、EPOXY ESTER 70PA、EPOXY ESTER 200PA、EPOXY ESTER 80MFA、EPOXY ESTER 3002M、EPOXY ESTER 3002A、EPOXY ESTER 1600A、EPOXY ESTER 3000M、EPOXY ESTER 3000A、EPOXY ESTER 200EA、EPOXY ESTER 400EA等。 作為上述長瀨化成公司製造之環氧(甲基)丙烯酸酯，例如可列舉：DENACOL ACRYLATE DA-141、DENACOL ACRYLATE DA-314、DENACOL ACRYLATE DA-911等。Examples of the commercially available epoxy (meth)acrylates include epoxy (meth)acrylates manufactured by DAICEL-ALLNEX Corporation and epoxy (meth)acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd. , Epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase Chemicals, etc. Examples of the epoxy (meth)acrylates manufactured by DAICEL-ALLNEX include: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL60800EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYLL3800, EBECRYL3800, EBECRYL3800, EBECRYLL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL60800 Examples of the epoxy (meth)acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020. Examples of the epoxy (meth)acrylate produced by the Kyoeisha Chemical Company include: EPOXY ESTER M-600A, EPOXY ESTER 40EM, EPOXY ESTER 70PA, EPOXY ESTER 200PA, EPOXY ESTER 80MFA, EPOXY ESTER 3002M, EPOXY ESTER 3002A, EPOXY ESTER 1600A, EPOXY ESTER 3000M, EPOXY ESTER 3000A, EPOXY ESTER 200EA, EPOXY ESTER 400EA, etc. Examples of the epoxy (meth)acrylate produced by the Nagase Chemical Company include DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-911, and the like.
上述(甲基)丙烯酸胺酯例如可藉由使具有羥基之(甲基)丙烯酸衍生物於觸媒量之錫系化合物存在下與多官能異氰酸酯化合物反應而獲得。The above-mentioned (meth)acrylic acid amine ester can be obtained, for example, by reacting a (meth)acrylic acid derivative having a hydroxyl group with a polyfunctional isocyanate compound in the presence of a tin amount of a catalyst.
作為上述多官能異氰酸酯化合物，例如可列舉：異佛爾酮二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯（MDI）、氫化MDI、聚合MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、二甲苯二異氰酸酯（XDI）、氫化XDI、離胺酸二異氰酸酯、三苯甲烷三異氰酸酯、三(異氰酸基苯基)硫代磷酸酯、四甲基二甲苯二異氰酸酯、1,6,11-十一烷三異氰酸酯等。Examples of the polyfunctional isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. , Diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzidine diisocyanate, xylene diisocyanate (XDI) , Hydrogenated XDI, ionic acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethylxylene diisocyanate, 1,6,11-undecane triisocyanate, etc. .
又，作為上述多官能異氰酸酯化合物，亦可使用藉由多元醇與過量之多官能異氰酸酯化合物反應而獲得之經擴鏈之多官能異氰酸酯化合物。 作為上述多元醇，例如可列舉：乙二醇、丙二醇、甘油、山梨醇、三羥甲基丙烷、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等。In addition, as the above-mentioned polyfunctional isocyanate compound, a chain-extended polyfunctional isocyanate compound obtained by reacting a polyol with an excess of the polyfunctional isocyanate compound can also be used. Examples of the above-mentioned polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
作為上述具有羥基之(甲基)丙烯酸衍生物，例如可列舉：單(甲基)丙烯酸羥基烷基酯、二元醇之單(甲基)丙烯酸酯、三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等。 作為上述單(甲基)丙烯酸羥基烷基酯，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。 作為上述二元醇，例如可列舉：乙二醇、丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、聚乙二醇等。 作為上述三元醇，例如可列舉：三羥甲基乙烷、三羥甲基丙烷、甘油等。 作為上述環氧(甲基)丙烯酸酯，例如可列舉：雙酚A型環氧丙烯酸酯等。Examples of the (meth)acrylic acid derivatives having hydroxyl groups include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of glycols, and mono(meth)acrylic acid of triols. Ester or di(meth)acrylate, epoxy (meth)acrylate, etc. Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate and the like. Examples of the above-mentioned glycols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Examples of the triols include trimethylolethane, trimethylolpropane, and glycerin. Examples of the epoxy (meth)acrylate include bisphenol A epoxy acrylate.
作為上述(甲基)丙烯酸胺酯中之市售者，例如可列舉：東亞合成公司製造之(甲基)丙烯酸胺酯、DAICEL-ALLNEX公司製造之(甲基)丙烯酸胺酯、根上工業公司製造之(甲基)丙烯酸胺酯、新中村化學工業公司製造之(甲基)丙烯酸胺酯、共榮社化學公司製造之(甲基)丙烯酸胺酯等。 作為上述東亞合成公司製造之(甲基)丙烯酸胺酯，例如可列舉：M-1100、M-1200、M-1210、M-1600等。 作為上述DAICEL-ALLNEX公司製造之(甲基)丙烯酸胺酯，例如可列舉：EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、EBECRYL8803、EBECRYL8804、EBECRYL8807、EBECRYL9260等。 作為上述根上工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：Artresin UN-330、Artresin SH-500B、Artresin UN-1200TPK、Artresin UN-1255、Artresin UN-3320HB、Artresin UN-7100、Artresin UN-9000A、Artresin UN-9000H等。 作為上述新中村化學工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6HA、U-6LPA、U-10H、U-15HA、U-108、U-108A、U-122A、U-122P、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4000、UA-4100、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A等。 作為上述共榮社化學公司製造之(甲基)丙烯酸胺酯，例如可列舉：AH-600、AI-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T等。Examples of the commercially available among the above-mentioned (meth)acrylate amine esters include: (meth)acrylic acid amine esters manufactured by Toya Synthetic Corporation, DAICEL-ALLNEX (meth)acrylic acid amine esters, manufactured by Negami Industrial Co., Ltd. Amine (meth)acrylate, amine (meth)acrylate manufactured by Shin Nakamura Chemical Industry Co., Ltd., amine (meth)acrylate manufactured by Kyoeisha Chemical Company, etc. Examples of the amine (meth)acrylate manufactured by the above-mentioned East Asia Synthesizer include M-1100, M-1200, M-1210, and M-1600. Examples of the amine (meth)acrylates manufactured by the DAICEL-ALLNEX company include: EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL8401, EBECRYL8401, EBECRYL6700, EBECRYL67003 EBECRYL9260 and so on. Examples of the amine (meth)acrylates produced by the above-mentioned Kinsung Industries Co., Ltd. include: Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H, etc. Examples of the amine (meth)acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U -10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000 , UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc. Examples of the amine (meth)acrylate manufactured by the Kyoeisha Chemical Company include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA -306T etc.
為了提高所獲得之液晶元件用密封劑之接著性等，上述硬化性樹脂可含有環氧化合物。作為上述環氧化合物，例如可列舉上述作為用於合成環氧(甲基)丙烯酸酯之原料之環氧化合物、部分(甲基)丙烯酸改質環氧化合物等。 再者，於本說明書中，上述部分(甲基)丙烯酸改質環氧化合物意指例如可藉由使於1分子中具有2個以上之環氧基之環氧化合物之一部分環氧基與(甲基)丙烯酸反應而獲得之於1分子中具有分別1個以上之環氧基及(甲基)丙烯醯基之化合物。In order to improve the adhesiveness of the obtained sealing compound for liquid crystal elements, etc., the said curable resin may contain an epoxy compound. Examples of the above-mentioned epoxy compound include the above-mentioned epoxy compounds as raw materials for synthesizing epoxy (meth)acrylates, partially (meth)acrylic modified epoxy compounds, and the like. In addition, in this specification, the partial (meth)acrylic modified epoxy compound means that, for example, a part of the epoxy group of the epoxy compound having two or more epoxy groups in one molecule and ( A compound obtained by reacting meth)acrylic acid with at least one epoxy group and (meth)acryloyl group in one molecule.
於上述硬化性樹脂含有上述(甲基)丙烯酸化合物及上述環氧化合物之情形時、或含有上述部分(甲基)丙烯酸改質環氧化合物之情形時，較佳為將上述硬化性樹脂中之(甲基)丙烯醯基與環氧基之合計中的(甲基)丙烯醯基之比率設為30莫耳%以上且95莫耳%以下。藉由上述(甲基)丙烯醯基之比率於該範圍內，所獲得之液晶元件用密封劑成為抑制發生液晶污染、並且接著性更優異者。In the case where the curable resin contains the (meth)acrylic compound and the epoxy compound, or when the partially (meth)acrylic modified epoxy compound is contained, it is preferred that The ratio of the (meth)acryloyl group in the total of (meth)acryloyl group and epoxy group is 30 mol% or more and 95 mol% or less. When the ratio of the (meth)acryl acetyl group is within this range, the obtained sealant for liquid crystal elements becomes more excellent in suppressing occurrence of liquid crystal contamination and having better adhesion.
自使所獲得之液晶元件用密封劑之低液晶污染性更優異之觀點而言，上述硬化性樹脂較佳具有-OH基、-NH-基、-NH2 基等氫鍵性單元。From the viewpoint of making the obtained liquid crystal element sealant more excellent in low liquid crystal contamination, the curable resin preferably has hydrogen bonding units such as —OH groups, —NH— groups, and —NH 2 groups.
上述硬化性樹脂可單獨使用，亦可2種以上組合使用。The above curable resins may be used alone or in combination of two or more.
本發明之液晶元件用密封劑可於無損本發明之目的之範圍內含有熱聚合起始劑。 作為上述熱聚合起始劑，例如可列舉由偶氮化合物、有機過氧化物等所構成者。其中，較佳為由高分子偶氮化合物所構成之高分子偶氮起始劑。 上述熱聚合起始劑可單獨使用，亦可2種以上組合使用。 再者，於本說明書中，上述「高分子偶氮化合物」意指具有偶氮基，藉由熱而生成可使(甲基)丙烯醯氧基硬化之自由基之數量平均分子量為300以上之化合物。The sealant for liquid crystal elements of the present invention may contain a thermal polymerization initiator within a range that does not impair the object of the present invention. Examples of the thermal polymerization initiator include those composed of an azo compound, an organic peroxide, and the like. Among them, a polymer azo initiator composed of a polymer azo compound is preferred. The above thermal polymerization initiator may be used alone or in combination of two or more. In addition, in the present specification, the above-mentioned "polymer azo compound" means an azo group, and the number average molecular weight of the radicals that can harden the (meth)acryloyloxy group by heat is 300 or more Compound.
上述高分子偶氮化合物之數量平均分子量之較佳之下限為1000，較佳之上限為30萬。藉由上述高分子偶氮化合物之數量平均分子量於該範圍內，可抑制液晶污染，且可容易地與硬化性樹脂混合。上述高分子偶氮化合物之數量平均分子量之更佳之下限為5000，更佳之上限為10萬，進而較佳之下限為1萬，進而較佳之上限為9萬。The preferable lower limit of the number average molecular weight of the above polymer azo compound is 1,000, and the preferable upper limit is 300,000. When the number average molecular weight of the above-mentioned polymer azo compound is within this range, liquid crystal contamination can be suppressed, and it can be easily mixed with the curable resin. The more preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 5000, the more preferable upper limit is 100,000, the more preferable lower limit is 10,000, and the more preferable upper limit is 90,000.
作為上述高分子偶氮化合物，例如可列舉具有下述結構者，該結構由多個聚環氧烷或聚二甲基矽氧烷等單元經由偶氮基鍵結而成。 作為具有多個聚環氧烷等單元經由上述偶氮基鍵結而成之結構之高分子偶氮化合物，較佳為具有聚環氧乙烷結構者。 作為上述高分子偶氮化合物，具體而言，例如可列舉：4,4'-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之縮聚物、4,4'-偶氮雙(4-氰基戊酸)與具有末端胺基之聚二甲基矽氧烷之縮聚物等。 作為上述高分子偶氮化合物中之市售者，例如可列舉：VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001（均為FUJIFILM Wako Pure Chemical Industries公司製造）等。 又，作為非高分子之偶氮化合物，例如可列舉：V-65、V-501（均為FUJIFILM Wako Pure Chemical Industries公司製造）等。Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group. The polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide is bonded via the azo group is preferably a polyethylene oxide structure. Specific examples of the polymer azo compound include, for example, polycondensates of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycols, and 4,4'-azo Condensation polymers of bis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amine groups. Examples of the commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical Industries). In addition, examples of non-polymer azo compounds include V-65 and V-501 (all manufactured by FUJIFILM Wako Pure Chemical Industries).
作為上述有機過氧化物，例如可列舉：酮過氧化物、過氧縮酮、氫過氧化物、二烷基過氧化物、過氧酯、二醯基過氧化物、過氧化二碳酸酯等。Examples of the organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, and peroxydicarbonates. .
上述熱聚合起始劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為0.05重量份，較佳之上限為10重量份。藉由上述熱聚合起始劑之含量為0.05重量份以上，本發明之液晶元件用密封劑成為熱硬化性更優異者。藉由上述熱聚合起始劑之含量為10重量份以下，本發明之液晶元件用密封劑成為低液晶污染性或保存穩定性更優異者。上述熱聚合起始劑之含量之更佳之下限為0.1重量份，更佳之上限為5重量份。The content of the thermal polymerization initiator relative to 100 parts by weight of the curable resin is preferably a lower limit of 0.05 parts by weight and a preferred upper limit of 10 parts by weight. When the content of the thermal polymerization initiator is 0.05 parts by weight or more, the sealing agent for liquid crystal elements of the present invention is more excellent in thermosetting property. When the content of the thermal polymerization initiator is 10 parts by weight or less, the sealing agent for liquid crystal elements of the present invention has low liquid crystal contamination and more excellent storage stability. The lower limit of the content of the thermal polymerization initiator is more preferably 0.1 part by weight, and the upper limit is more preferably 5 parts by weight.
本發明之液晶元件用密封劑可含有熱硬化劑。 作為上述熱硬化劑，例如可列舉：有機酸醯肼、咪唑衍生物、胺化合物、多酚系化合物、酸酐等。其中，可較佳地使用有機酸醯肼。 上述熱硬化劑可單獨使用，亦可2種以上組合使用。The sealing compound for liquid crystal elements of this invention may contain a thermosetting agent. Examples of the thermosetting agent include organic acid hydrazine, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides. Among them, the organic acid hydrazine can be preferably used. The above-mentioned thermosetting agents may be used alone or in combination of two or more.
作為上述有機酸醯肼，例如可列舉：癸二酸二醯肼、間苯二甲酸二醯肼、己二酸二醯肼、丙二酸二醯肼等。 作為上述有機酸醯肼中之市售者，例如可列舉：Otsuka Chemical公司製造之有機酸醯肼、Ajinomoto Fine-Techno公司製造之有機酸醯肼等。 作為上述Otsuka Chemical公司製造之有機酸醯肼，例如可列舉：SDH、ADH等。 作為上述Ajinomoto Fine-Techno公司製造之有機酸醯肼，例如可列舉：Amicure VDH、Amicure VDH-J、Amicure UDH、Amicure UDH-J等。Examples of the organic acid hydrazide include, for example, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide. Examples of the commercially available organic acid hydrazide include organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd., and organic acid hydrazide manufactured by Ajinomoto Fine-Techno Corporation. Examples of the organic acid hydrazide manufactured by the above-mentioned Otsuka Chemical Company include SDH and ADH. Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Techno include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J, and the like.
上述熱硬化劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為1重量份，較佳之上限為50重量份。藉由上述熱硬化劑之含量於該範圍內，可於不使所獲得之液晶元件用密封劑之塗佈性等變差之情況下使熱硬化性更優異。上述熱硬化劑之含量之更佳之上限為30重量份。The content of the above-mentioned thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the above-mentioned curable resin, and the preferred upper limit is 50 parts by weight. When the content of the above-mentioned thermosetting agent is within this range, the thermosetting property can be made more excellent without deteriorating the coating properties and the like of the obtained sealing compound for liquid crystal elements. The more preferable upper limit of the content of the above-mentioned thermosetting agent is 30 parts by weight.
為了提高黏度、改善應力分散效果所致之接著性、改善線膨脹率等，本發明之液晶元件用密封劑較佳為含有填充劑。又，藉由含有上述填充劑，易於將觸變指數設為後述範圍。In order to increase the viscosity, improve the adhesion due to the stress dispersion effect, improve the linear expansion rate, etc., the sealing compound for liquid crystal devices of the present invention preferably contains a filler. In addition, by containing the filler, it is easy to set the thixotropic index to the range described below.
作為上述填充劑，可使用無機填充劑或有機填充劑。 作為上述無機填充劑，例如可列舉：矽石、滑石、玻璃珠、石棉、石膏、矽藻土、膨潤石、膨潤土、蒙脫石、絹雲母、活性白土、氧化鋁、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、氮化鋁、氮化矽、硫酸鋇、矽酸鈣等。 作為上述有機填充劑，例如可列舉：聚酯微粒子、聚胺酯微粒子、乙烯基聚合物微粒子、丙烯酸聚合物微粒子等。 上述填充劑可單獨使用，亦可2種以上組合使用。As the above-mentioned filler, an inorganic filler or an organic filler can be used. Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, Magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc. Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like. These fillers may be used alone or in combination of two or more.
上述填充劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為30重量份，較佳之上限為100重量份。藉由上述填充劑之含量於該範圍內，可於不使塗佈性等變差之情況下使接著性之改善等效果更優異。上述填充劑之含量之更佳之下限為45重量份，更佳之上限為80重量份。The content of the filler is preferably 100 parts by weight relative to 100 parts by weight of the curable resin, and the upper limit is preferably 100 parts by weight. When the content of the filler is within this range, the effect of improving the adhesiveness and the like can be made more excellent without deteriorating the coatability and the like. The lower limit of the content of the filler is more preferably 45 parts by weight, and the upper limit is more preferably 80 parts by weight.
本發明之液晶元件用密封劑較佳為含有矽烷偶合劑。上述矽烷偶合劑主要具有作為用於將密封劑與基板等良好地接著之接著助劑之作用。The sealing agent for liquid crystal elements of the present invention preferably contains a silane coupling agent. The above-mentioned silane coupling agent mainly has a role as an adhesion aid for good adhesion of the sealant to the substrate and the like.
作為上述矽烷偶合劑，例如可較佳地使用：3-胺基丙基三甲氧基矽烷、3-巰丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷等。該等之提高與基板等之接著性之效果優異，藉由與硬化性樹脂化學鍵結而可抑制硬化性樹脂向液晶中流出。 上述矽烷偶合劑可單獨使用，亦可2種以上組合使用。As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-iso Cyanopropyl trimethoxysilane etc. These effects of improving the adhesion to the substrate and the like are excellent, and chemical bonding with the curable resin can suppress the outflow of the curable resin into the liquid crystal. The above-mentioned silane coupling agent may be used alone or in combination of two or more.
本發明之液晶元件用密封劑100重量份中之上述矽烷偶合劑之含量的較佳之下限為0.1重量份，較佳之上限為10重量份。藉由上述矽烷偶合劑之含量於該範圍內，而成為抑制發生液晶污染、並且提高接著性之效果更優異者。上述矽烷偶合劑之含量的更佳之下限為0.3重量份，更佳之上限為5重量份。The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealing compound for liquid crystal elements of the present invention is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the effect of suppressing the occurrence of liquid crystal contamination and improving the adhesion is more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.3 part by weight, and the upper limit is more preferably 5 parts by weight.
本發明之液晶元件用密封劑進而可根據需要含有反應性稀釋劑、觸變劑、間隔劑、硬化促進劑、消泡劑、調平劑、聚合抑制劑等添加劑。The sealing agent for liquid crystal elements of the present invention may further contain additives such as a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, a defoamer, a leveling agent, and a polymerization inhibitor, if necessary.
作為製造本發明之液晶元件用密封劑之方法，例如可列舉使用勻相分散機、均質攪拌機、萬能攪拌機、行星式攪拌機、捏合機、三輥研磨機等混合機將硬化性樹脂、光聚合起始劑及根據需要添加之矽烷偶合劑等進行混合之方法等。As a method of manufacturing the sealing agent for liquid crystal elements of the present invention, for example, a blender such as a homogenizer, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill can be used to polymerize the curable resin and photopolymerization. The method of mixing the starting agent and the silane coupling agent added as needed.
本發明之液晶元件用密封劑之觸變指數之較佳之下限為1.2，較佳之上限為3.0。藉由上述觸變指數於該範圍內，所獲得之液晶元件用密封劑成為液晶之插入防止性更優異者。上述觸變指數之更佳之下限為1.3，更佳之上限為2.0。 再者，於本說明書中，上述觸變指數意指使用E型黏度計於25℃、0.5 rpm之條件下測得之黏度除以於25℃、5.0 rpm之條件下測得之黏度而得出之值。The preferable lower limit of the thixotropic index of the sealing compound for liquid crystal elements of the present invention is 1.2, and the preferable upper limit is 3.0. When the thixotropic index is within this range, the obtained sealing compound for liquid crystal elements becomes more excellent in the prevention of insertion of liquid crystal. The better lower limit of the above thixotropic index is 1.3, and the better upper limit is 2.0. Furthermore, in this specification, the above thixotropic index means the viscosity measured using the E-type viscometer at 25°C and 0.5 rpm divided by the viscosity measured at 25°C and 5.0 rpm Value.
藉由在本發明之液晶元件用密封劑中摻合導電性微粒子，可製造上下導通材料。含有本發明之液晶元件用密封劑及導電性微粒子之上下導通材料亦為本發明之一。By blending conductive fine particles in the sealant for liquid crystal elements of the present invention, a vertical conduction material can be manufactured. The upper and lower conductive materials containing the sealing compound for liquid crystal elements of the present invention and conductive fine particles are also one of the present invention.
作為上述導電性微粒子，可使用於金屬球、樹脂微粒子之表面形成導電金屬層而成者等。其中，於樹脂微粒子之表面形成導電金屬層而成者藉由樹脂微粒子之優異彈性，能夠於不損傷透明基板等之情況下進行導電連接，因此較佳。As the conductive fine particles, those formed by forming a conductive metal layer on the surface of metal balls or resin fine particles can be used. Among them, it is preferable to form a conductive metal layer on the surface of the resin microparticles because of the excellent elasticity of the resin microparticles, which can perform conductive connection without damaging the transparent substrate or the like.
使用本發明之液晶元件用密封劑或本發明之上下導通材料而成之液晶元件亦為本發明之一。 作為本發明之液晶元件，較佳為窄邊緣設計之液晶元件。具體而言，較佳為液晶顯示部之周圍的框部分之寬度為2 mm以下。 又，製造本發明之液晶元件時之本發明的液晶元件用密封劑之塗佈寬度較佳為1 mm以下。The liquid crystal element formed by using the sealing compound for liquid crystal elements of the present invention or the upper and lower conduction materials of the present invention is also one of the present invention. As the liquid crystal element of the present invention, a liquid crystal element with a narrow edge design is preferred. Specifically, it is preferable that the width of the frame portion around the liquid crystal display portion is 2 mm or less. Moreover, the coating width of the sealing compound for liquid crystal elements of this invention when manufacturing the liquid crystal element of this invention is preferably 1 mm or less.
作為製造本發明之液晶元件之方法，可較佳地使用液晶滴下法，具體而言，例如可列舉具有以下之各步驟之方法等。 首先，進行如下步驟：於具有ITO薄膜等電極及配向膜之2塊透明基板之一者上藉由網版印刷、分注器塗佈等塗佈本發明之液晶元件用密封劑，從而形成框狀之密封圖案。繼而，進行如下步驟：於本發明之液晶元件用密封劑未硬化之狀態下將液晶之微滴滴下塗佈於基板的密封圖案之框內，於真空下與另一透明基板重合。其後，進行如下步驟：藉由對本發明之液晶元件用密封劑之密封圖案部分照射紫外線、或介隔截止濾光鏡等照射長波長之光，而使密封劑光硬化，藉由進行以上各步驟之方法可獲得液晶元件。又，除使上述密封劑光硬化之步驟以外，亦可進行對密封劑加熱而使之熱硬化之步驟。 [發明之效果]As a method of manufacturing the liquid crystal element of the present invention, a liquid crystal dropping method can be preferably used. Specifically, for example, a method having the following steps can be cited. First, perform the following steps: apply the sealant for a liquid crystal element of the present invention by screen printing, dispenser coating, etc. on one of the two transparent substrates having electrodes and alignment films such as ITO thin film to form a frame Seal pattern. Then, the following steps are carried out: droplets of liquid crystal are applied to the frame of the sealing pattern of the substrate in a state where the sealing agent for liquid crystal elements of the present invention is not cured, and overlap with another transparent substrate under vacuum. Thereafter, the following steps are carried out: by irradiating ultraviolet light to the sealing pattern portion of the sealant for liquid crystal elements of the present invention, or irradiating long-wavelength light with a cut-off filter, etc., the photo-hardening of the sealant is performed by performing the above The method of steps can obtain a liquid crystal element. In addition to the step of photo-curing the sealant, a step of heat-curing the sealant may be performed. [Effect of invention]
根據本發明，可提供一種對長波長之光的深部硬化性優異、可抑制液晶向密封劑插入或由密封劑所導致之液晶污染的液晶元件用密封劑。又，根據本發明，可提供一種使用該液晶元件用密封劑而成之上下導通材料及液晶元件。According to the present invention, it is possible to provide a sealant for a liquid crystal element which is excellent in deep curing of long-wavelength light and can suppress insertion of liquid crystal into the sealant or contamination of liquid crystal caused by the sealant. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal element using the sealant for a liquid crystal element.
以下，列舉實施例對本發明更詳細地進行說明，然而，本發明並未僅限定於該等實施例。Hereinafter, the present invention will be described in more detail with examples. However, the present invention is not limited to these examples.
（式（1-1）所表示之化合物之製作） 向稀釋於甲苯300 g中之2-(2-羥基乙基硫代)-9,10-蒽醌19.5 g中，歷時1小時滴加稀釋於甲苯300 g中之六亞甲基二異氰酸酯縮二脲變異體（三井化學公司製造，「Takenate D-165N」）14 g，獲得上述式（1-1）所表示之化合物。作為反應觸媒，使用二丁基二月桂酸錫（東京化成工業公司製造）0.01 g。為了提昇所獲得之化合物之純度，反覆進行3次利用甲苯與異丙醇之再結晶作業。再者，所獲得之上述式（1-1）所表示之化合物之結構藉由1 H-NMR、13 C-NMR及FT-IR進行確認。(Preparation of the compound represented by formula (1-1)) To 19.5 g of 2-(2-hydroxyethylthio)-9,10-anthraquinone diluted in 300 g of toluene, the dilution is added dropwise over 1 hour A hexamethylene diisocyanate biuret variant (made by Mitsui Chemicals, "Takenate D-165N") 14 g in 300 g of toluene obtained the compound represented by the above formula (1-1). As a reaction catalyst, 0.01 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. In order to improve the purity of the obtained compound, recrystallization operations using toluene and isopropanol were repeated three times. Furthermore, the structure of the obtained compound represented by the above formula (1-1) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
（式（2）所表示之化合物之製作） （1）化合物A之合成 於二氯甲烷50 mL中添加氯化鋁7.36 g，進而於0℃分數次添加二苯硫醚9.31 g。繼而，於0℃添加氯乙醯氯5.56 g，於室溫攪拌2小時後，於0℃添加氯化鋁7.33 g及4-甲基戊醯氯7.06 g，攪拌一晩。於將所獲得之反應混合物注入至冰水中後，藉由二氯甲烷對有機層進行萃取。利用MgSO4 對所萃取之溶液進行乾燥並濃縮，藉由管柱層析法對殘留物進行純化，藉此，獲得作為白色粉末之下述式（4）所表示之化合物A。(Preparation of compound represented by formula (2)) (1) Synthesis of compound A 7.36 g of aluminum chloride was added to 50 mL of dichloromethane, and 9.31 g of diphenyl sulfide was added in portions at 0°C. Then, 5.56 g of chloroacetamide chloride was added at 0°C, and after stirring at room temperature for 2 hours, 7.33 g of aluminum chloride and 7.06 g of 4-methylpentylchloride were added at 0°C, and the mixture was stirred overnight. After the obtained reaction mixture was poured into ice water, the organic layer was extracted with dichloromethane. The extracted solution was dried with MgSO 4 and concentrated, and the residue was purified by column chromatography, thereby obtaining Compound A represented by the following formula (4) as a white powder.
（2）化合物B之合成 於丙酮30 mL中添加1.0 g所獲得之化合物A後，進而添加碳酸鉀1.11 g及柳醛0.73 g，於回流下攪拌3小時。在室溫於所獲得之反應混合物中添加水後，添加鹽酸使其酸性化，獲得沈澱物。藉由過濾回收所獲得之沈澱物，並對其進行乾燥，藉此，獲得下述式（5）所表示之化合物B。(2) Synthesis of Compound B After adding 1.0 g of the obtained compound A to 30 mL of acetone, 1.11 g of potassium carbonate and 0.73 g of salicylaldehyde were further added, and the mixture was stirred under reflux for 3 hours. After adding water to the obtained reaction mixture at room temperature, hydrochloric acid was added to make it acidic to obtain a precipitate. The obtained precipitate is recovered by filtration and dried, thereby obtaining Compound B represented by the following formula (5).
（3）化合物C之合成 於乙酸乙酯10 mL中添加1.0 g所獲得之化合物B後，進而添加氯化羥銨0.35 g及吡啶5 mL，於回流下攪拌3小時。於室溫將所獲得之反應混合物注入水中後，藉由乙酸乙酯對有機層進行萃取。利用MgSO4 對所萃取之溶液進行乾燥並濃縮，藉由管柱層析法對粗產物進行純化，藉此，獲得作為淡黃色固體之下述式（6）所表示之化合物C。(3) Synthesis of compound C After adding 1.0 g of the obtained compound B to 10 mL of ethyl acetate, 0.35 g of hydroxylammonium chloride and 5 mL of pyridine were further added, and stirred under reflux for 3 hours. After the obtained reaction mixture was poured into water at room temperature, the organic layer was extracted with ethyl acetate. The extracted solution was dried with MgSO 4 and concentrated, and the crude product was purified by column chromatography, whereby compound C represented by the following formula (6) was obtained as a pale yellow solid.
（4）式（2）所表示之化合物之合成 於乙酸乙酯14 mL中添加300 mg所獲得之化合物C後，進而添加乙醯氯78.5 mg及三乙胺111 mg，於室溫攪拌3小時。於將所獲得之反應混合物注入水中後，藉由乙酸乙酯對有機層進行萃取。對所萃取之溶液進行濃縮，藉由管柱層析法對粗產物進行純化，藉此，獲得上述式（2）所表示之化合物。再者，所獲得之式（2）所表示之化合物之結構藉由1 H-NMR、13 C-NMR及FT-IR進行確認。(4) Synthesis of the compound represented by formula (2) After adding 300 mg of the obtained compound C to 14 mL of ethyl acetate, further adding 78.5 mg of acetyl chloride and 111 mg of triethylamine, stirring at room temperature for 3 hours . After the obtained reaction mixture was poured into water, the organic layer was extracted with ethyl acetate. The extracted solution was concentrated, and the crude product was purified by column chromatography, thereby obtaining the compound represented by the above formula (2). In addition, the structure of the obtained compound represented by the formula (2) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.
（式（3）所表示之化合物之製作） 於上述「（1）化合物A之合成」中，使用正辛醯氯8.53 g代替4-甲基戊醯氯7.06 g，除此以外，與上述「（式（2）所表示之化合物之製作）」相同地操作，從而獲得上述式（3）所表示之化合物。再者，所獲得之式（3）所表示之化合物之結構藉由1 H-NMR、13 C-NMR及FT-IR進行確認。(Preparation of the compound represented by formula (3)) In the above "(1) Synthesis of Compound A", n-octyl chloride 8.53 g is used instead of 4-methylpentyl chloride 7.06 g. (Preparation of the compound represented by the formula (2))" In the same manner, the compound represented by the above formula (3) is obtained. In addition, the structure of the obtained compound represented by the formula (3) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.
（實施例1~9及比較例1~5） 按照表1、2所記載之摻合比，使用行星式攪拌機（Thinky公司製造，「去泡攪拌太郎」）將各材料進行混合後，進而使用三輥研磨機進行混合，藉此，製備實施例1~9及比較例1~5之液晶元件用密封劑。(Examples 1 to 9 and Comparative Examples 1 to 5) According to the blending ratios described in Tables 1 and 2, the materials were mixed using a planetary mixer (Thinky Corporation, "defoaming and stirring Taro"), and then further mixed using a three-roll mill to prepare examples. Sealants for liquid crystal elements 1 to 9 and Comparative Examples 1 to 5.
＜評價＞ 對於實施例及比較例中所獲得之各液晶元件用密封劑，進行以下之評價。將結果表示於表1、2中。<Evaluation> The following evaluation was performed about each sealing compound for liquid crystal elements obtained in the Example and the comparative example. The results are shown in Tables 1 and 2.
（觸變指數） 對於實施例及比較例中所獲得之各液晶元件用密封劑，使用E型黏度計（東機產業公司製造，「VISCOMETER TV-22」）於25℃、0.5 rpm之條件及25℃、5.0 rpm之條件下對黏度進行測定。 藉由將於25℃、0.5 rpm之條件下測得之黏度除以於25℃、5 rpm之條件下測得之黏度，從而算出觸變指數。(Thixotropic index) For each sealant for liquid crystal elements obtained in Examples and Comparative Examples, an E-type viscometer (manufactured by Toki Industries, Inc., "VISCOMETER TV-22") was used at 25°C and 0.5 rpm and 25°C and 5.0 rpm Measure the viscosity under the conditions. The thixotropic index is calculated by dividing the viscosity measured at 25°C and 0.5 rpm by the viscosity measured at 25°C and 5 rpm.
（深部硬化性） 將間隔劑微粒子（積水化學工業公司製造，「Micropearl GS-L300」）1重量份分散於實施例及比較例中所獲得之各液晶元件用密封劑100重量份中。繼而，將密封劑填充於滴塗用之注射器（武藏高科技公司製造，「PSY-10E」）中，進行脫泡處理後，藉由分注器（武藏高科技公司製造，「SHOTMASTER300」）塗佈於玻璃基板上。藉由真空貼合裝置於5 Pa之減壓下於該基板貼合同尺寸之玻璃基板，從而獲得單元間隙為300 μm之單元。使用金屬鹵化物燈對所獲得之單元之密封劑部分照射100 mW/cm2 之光30秒。光照射係介隔對波長420 nm以下之光進行截止之截止濾光鏡（420 nm截止濾光鏡）進行。 使用紅外分光裝置（BIORAD公司製造，「FTS3000」）進行密封劑之FT-IR測定，測定源自(甲基)丙烯醯基之峰於光照射前後之變化量。將光照射後源自(甲基)丙烯醯基之峰減少90%以上之情形設為「◎」，將減少80%以上且未達90%之情形設為「○」，將減少70%以上且未達80%之情形設為「Δ」，將光照射後之源自(甲基)丙烯醯基之峰之減少未達70%之情形設為「×」，而對深部硬化性進行評價。(Deep Curability) 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., "Micropearl GS-L300") was dispersed in 100 parts by weight of each sealant for liquid crystal elements obtained in Examples and Comparative Examples. Then, the sealant was filled in a syringe for dispensing (Musashi Hi-Tech Co., Ltd., "PSY-10E"), defoamed, and then applied by a dispenser (Musashi Hi-Tech Co., Ltd., "SHOTMASTER300") It is placed on the glass substrate. A glass substrate with a contract size was attached to the substrate by a vacuum bonding apparatus under a reduced pressure of 5 Pa to obtain a cell with a cell gap of 300 μm. The sealant portion of the obtained unit was irradiated with light of 100 mW/cm 2 for 30 seconds using a metal halide lamp. Light irradiation is performed through a cut-off filter (420 nm cut-off filter) that cuts off light below a wavelength of 420 nm. FT-IR measurement of the sealant was performed using an infrared spectrometer (manufactured by Biorad, "FTS3000"), and the amount of change of the peak derived from (meth)acryloyl group before and after light irradiation was measured. The case where the peak derived from (meth)acryloyl group is reduced by more than 90% after light irradiation is set to "◎", and the case where it is reduced by more than 80% and less than 90% is set to "○", which is reduced by more than 70% The case where it is less than 80% is set to “Δ”, and the case where the decrease of the peak derived from (meth)acryloyl group after light irradiation is less than 70% is set to “×”, and the deep sclerosis is evaluated.
（插入防止性） 將間隔劑微粒子（積水化學工業公司製造，「Micropearl SP-250」）1重量份分散於實施例及比較例中所獲得之各液晶元件用密封劑100重量份中。繼而，將密封劑填充於滴塗用之注射器（武藏高科技公司製造，「PSY-10E」）中，進行脫泡處理。藉由分注器（武藏高科技公司製造，「SHOTMASTER300」）將脫泡處理後之密封劑以成為線寬1 mm之框狀之方式塗佈於2塊附經摩擦之配向膜及透明電極之基板之一者。 繼而，將液晶（Chisso公司製造，「JC-5004LA」）之微滴滴下塗佈於附透明電極之基板之密封劑之框內整個面，立刻將另一基板貼合。其後，使用金屬鹵化物燈對密封劑部分照射100 mW/cm2 之光30秒，進而於120℃加熱1小時，從而獲得液晶元件（單元間隙為50 μm）。光照射係介隔對波長420 nm以下之光進行截止之截止濾光鏡（420 nm截止濾光鏡）進行。 對於所獲得之液晶元件，進行密封圖案之形狀觀察。其結果，將密封圖案之形狀未被內部之液晶打亂者設為「◎」，將密封圖案之形狀稍微混亂者設為「○」，將密封圖案之形狀大幅混亂者設為「Δ」，將液晶突破密封圖案而露出至外部者設為「×」，而對插入防止性進行評價。(Insertion prevention property) 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SP-250") was dispersed in 100 parts by weight of each sealant for liquid crystal elements obtained in Examples and Comparative Examples. Then, the sealant was filled in a syringe for dispensing (manufactured by Musashi Hi-Tech, "PSY-10E"), and defoamed. The defoamed sealant was applied to two rubbed alignment films and transparent electrodes with a dispenser (made by Musashi Hi-Tech Co., Ltd., "SHOTMASTER300") in a frame shape with a line width of 1 mm. One of the substrates. Subsequently, droplets of liquid crystal (manufactured by Chisso Corporation, "JC-5004LA") were dropped onto the entire surface of the frame of the sealant applied to the substrate with transparent electrodes, and the other substrate was immediately attached. Thereafter, a metal halide lamp was used to irradiate the sealant portion with light of 100 mW/cm 2 for 30 seconds, and then heated at 120° C. for 1 hour to obtain a liquid crystal element (cell gap of 50 μm). Light irradiation is performed through a cut-off filter (420 nm cut-off filter) that cuts off light below a wavelength of 420 nm. With respect to the obtained liquid crystal element, the shape of the sealing pattern was observed. As a result, the shape of the seal pattern that is not disturbed by the internal liquid crystal is set to "◎", the shape of the seal pattern that is slightly disturbed is set to "○", and the shape of the seal pattern is greatly disturbed to "Δ", The liquid crystal that broke through the seal pattern and exposed to the outside was set to “×”, and the insertion prevention property was evaluated.
（低液晶污染性） 對於與上述「（插入防止性）」相同地操作而獲得之液晶元件，藉由目視對於25℃、50%RH之環境下施加1小時電壓之狀態後之液晶配向混亂度（顯示不均）進行確認。 將完全未觀察到液晶元件顯示不均之情形設為「◎」，將於液晶元件之密封劑附近（周邊部）觀察到少量輕微之顯示不均之情形設為「○」，將周邊部存在明顯之較深之顯示不均之情形設為「Δ」，將明顯之較深之顯示不均不僅存在於周邊部、且擴散至中央部之情形設為「×」，而對低液晶污染性進行評價。 再者，評價為「◎」、「○」之液晶元件係實際使用完全不存在問題之水準，「Δ」之液晶元件係根據設計而可能存在問題之水準，「×」之液晶元件係經不起實際使用之水準。(Low liquid crystal pollution) For the liquid crystal device obtained by the same operation as the above "(insertion prevention)", the liquid crystal alignment disorder (uneven display) after applying a voltage for 1 hour in an environment of 25°C and 50%RH was visually observed confirm. The case where the display unevenness of the liquid crystal element is not observed at all is set to "◎", and the case where a slight slight display unevenness is observed near the sealant (peripheral part) of the liquid crystal element is set to "○", and the peripheral part exists The apparently deeper display unevenness is set to "Δ", and the apparently deeper display unevenness is not only present in the peripheral part and diffuses to the central part is set to "×", which has low liquid crystal pollution. Make an evaluation. In addition, the liquid crystal elements evaluated as "◎" and "○" are at a level where there is no problem at all in actual use, the liquid crystal elements of "Δ" are at a level that may have problems according to the design, and the liquid crystal elements of "×" are not From actual use.
[表1]
[表2]
根據本發明，可提供一種對長波長之光的深部硬化性優異、可抑制液晶向密封劑插入或由密封劑所導致之液晶污染的液晶元件用密封劑。又，根據本發明，可提供一種使用該液晶元件用密封劑而成之上下導通材料及液晶元件。According to the present invention, it is possible to provide a sealant for a liquid crystal element which is excellent in deep curing of long-wavelength light and can suppress insertion of liquid crystal into the sealant or contamination of liquid crystal caused by the sealant. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal element using the sealant for a liquid crystal element.
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Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP2018-130748 | 2018-07-10 | ||
| JP2018130748 | 2018-07-10 |
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| TW202005990A true TW202005990A (en) | 2020-02-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW108124247A TW202005990A (en) | 2018-07-10 | 2019-07-10 | Sealant for liquid crystal element, vertical conduction material, and liquid crystal element |
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|---|---|
| JP (1) | JP6703650B1 (en) |
| KR (1) | KR20210030248A (en) |
| CN (1) | CN111771160A (en) |
| TW (1) | TW202005990A (en) |
| WO (1) | WO2020013128A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200012739A (en) * | 2018-07-27 | 2020-02-05 | 닛뽄 가야쿠 가부시키가이샤 | Sealant for electronic component, electronic component and liquid crystal display cell |
| JP7144627B2 (en) * | 2020-09-30 | 2022-09-29 | 積水化学工業株式会社 | Thioxanthone compound, photopolymerization initiator, curable resin composition, composition for display element, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3583326B2 (en) | 1999-11-01 | 2004-11-04 | 協立化学産業株式会社 | Sealant for dripping method of LCD panel |
| EP1405888A1 (en) | 2001-05-16 | 2004-04-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| JP2003315761A (en) * | 2002-04-26 | 2003-11-06 | Dainippon Ink & Chem Inc | Light controlling layer forming material and liquid crystal device |
| 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 |
| KR101569333B1 (en) * | 2013-03-06 | 2015-11-13 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
| JP6491490B2 (en) * | 2015-02-06 | 2019-03-27 | 株式会社Adeka | Sealant for liquid crystal dropping method |
| JP2016184072A (en) * | 2015-03-26 | 2016-10-20 | 東レ株式会社 | Photosensitive resin composition, method for producing photospacer, color filter and liquid crystal display device |
| KR101981422B1 (en) * | 2015-06-30 | 2019-05-22 | 미쓰이 가가쿠 가부시키가이샤 | Photo-curing resin composition, display element sealing agent, liquid crystal sealing agent, liquid crystal display panel and manufacturing method of liquid crystal display panel |
| TW201704437A (en) * | 2015-07-21 | 2017-02-01 | 日本化藥股份有限公司 | Sealing agent for liquid crystal and liquid displaying cell using the sealing agent for liquid crystal |
| JP2017149794A (en) * | 2016-02-22 | 2017-08-31 | 三井化学株式会社 | Photocurable resin composition, display element sealant, liquid crystal sealant and liquid crystal display panel |
| CN108139637A (en) * | 2016-05-13 | 2018-06-08 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
| JP2018104662A (en) * | 2016-12-22 | 2018-07-05 | 日本化薬株式会社 | Photocurable resin composition and electronic component sealant |
-
2019
- 2019-07-08 KR KR1020207022617A patent/KR20210030248A/en not_active Application Discontinuation
- 2019-07-08 WO PCT/JP2019/026986 patent/WO2020013128A1/en active Application Filing
- 2019-07-08 JP JP2019545817A patent/JP6703650B1/en active Active
- 2019-07-08 CN CN201980014405.1A patent/CN111771160A/en active Pending
- 2019-07-10 TW TW108124247A patent/TW202005990A/en unknown
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| Publication number | Publication date |
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| JP6703650B1 (en) | 2020-06-03 |
| JPWO2020013128A1 (en) | 2020-07-16 |
| CN111771160A (en) | 2020-10-13 |
| WO2020013128A1 (en) | 2020-01-16 |
| KR20210030248A (en) | 2021-03-17 |
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