TWI643941B - Sealant for liquid crystal display element, vertical conductive material, and liquid crystal display element - Google Patents
Sealant for liquid crystal display element, vertical conductive material, and liquid crystal display element Download PDFInfo
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- TWI643941B TWI643941B TW103139152A TW103139152A TWI643941B TW I643941 B TWI643941 B TW I643941B TW 103139152 A TW103139152 A TW 103139152A TW 103139152 A TW103139152 A TW 103139152A TW I643941 B TWI643941 B TW I643941B
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- Taiwan
- Prior art keywords
- liquid crystal
- crystal display
- display element
- sealant
- meth
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 132
- 239000000565 sealant Substances 0.000 title claims abstract description 65
- 239000004020 conductor Substances 0.000 title claims abstract description 10
- -1 caprolactone polyols Chemical class 0.000 claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 238000007789 sealing Methods 0.000 claims abstract description 31
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011187 glycerol Nutrition 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- 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 claims abstract description 7
- 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 claims abstract description 6
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000010419 fine particle Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 1
- 229920001748 polybutylene Polymers 0.000 claims 1
- 238000011109 contamination Methods 0.000 abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 85
- 239000003822 epoxy resin Substances 0.000 description 43
- 229920000647 polyepoxide Polymers 0.000 description 43
- 239000004593 Epoxy Substances 0.000 description 21
- 239000000758 substrate Substances 0.000 description 20
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 15
- 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 14
- 238000000034 method Methods 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- 239000003999 initiator Substances 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
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- 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
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- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007870 radical polymerization initiator Substances 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 239000002994 raw material Substances 0.000 description 5
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- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- 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
- 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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004841 bisphenol A epoxy resin 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
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 2
- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 238000001723 curing Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
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- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
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- 239000004632 polycaprolactone Substances 0.000 description 2
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- 235000013824 polyphenols Nutrition 0.000 description 2
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- 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
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
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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
- SCWNYUDYCSFNTK-UHFFFAOYSA-N 1-(9h-fluoren-1-yl)prop-2-en-1-one Chemical group C1C2=CC=CC=C2C2=C1C(C(=O)C=C)=CC=C2 SCWNYUDYCSFNTK-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
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- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- RUVNKAUVVBCURD-UHFFFAOYSA-N 2-[[4-[2-[4-(oxiran-2-ylmethoxy)-3-prop-2-enylphenyl]propan-2-yl]-2-prop-2-enylphenoxy]methyl]oxirane Chemical compound C=1C=C(OCC2OC2)C(CC=C)=CC=1C(C)(C)C(C=C1CC=C)=CC=C1OCC1CO1 RUVNKAUVVBCURD-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
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- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- MIUFWHOMWWNKFK-UHFFFAOYSA-N 4-(dimethylamino)benzenecarboximidamide;hydrochloride Chemical compound [Cl-].CN(C)C1=CC=C(C(N)=[NH2+])C=C1 MIUFWHOMWWNKFK-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
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- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 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 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 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 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- G02F2202/28—Adhesive materials or arrangements
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Sealing Material Composition (AREA)
- Liquid Crystal (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Conductive Materials (AREA)
Abstract
本發明之目的在於提供一種光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 An object of the present invention is to provide a sealant for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination. Another object of the present invention is to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
本發明係含有硬化性樹脂、9-氧硫系聚合起始劑、及下述式(1)所表示之胺系增感劑之液晶顯示元件用密封劑。 The present invention contains a curable resin and 9-oxysulfur A sealing agent for a liquid crystal display element based on a polymerization initiator and an amine-based sensitizer represented by the following formula (1).
式(1)中，z表示1以上之整數，P為(聚)乙二醇、(聚)丙二醇、(聚)丁二醇、甘油、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇、或己內酯多元醇之殘基。 In formula (1), z represents an integer of 1 or more, and P is (poly) ethylene glycol, (poly) propylene glycol, (poly) butanediol, glycerin, trimethylolpropane, di-trimethylolpropane, Residues of neopentaerythritol, dipentaerythritol, or caprolactone polyols.
Description
本發明係關於一種光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑。又，本發明係關於一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 The present invention relates to a sealant for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination. The present invention also relates to a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
近年來，作為液晶顯示單元等液晶顯示元件之製造方法，就產距時間(tact time)縮短、使用液晶量之最佳化等觀點而言，可使用如專利文獻1、專利文獻2中所揭示之使用含有硬化性樹脂、光聚合起始劑及熱硬化劑之光熱併用硬化型之密封劑的稱為滴下方法的液晶滴下方式。 In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display unit, from the viewpoints of shortening the tact time and optimizing the amount of liquid crystal used, as disclosed in Patent Documents 1 and 2 A liquid crystal dropping method called a dropping method using a photo-thermal method containing a curable resin, a photopolymerization initiator, and a thermosetting agent and a hardening type sealant is used.
於滴下方法中，首先，於2片附有電極之基板之一片藉由滴塗(dispense)而形成長方形狀之密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微滴滴至基板之密封框內，於真空下重疊另一片基板，並對密封部照射紫外線等光而進行暫時硬化。其後，實施加熱而進行正式硬化，製作液晶顯示元件。目前該滴下方法正成為液晶顯示元件之製造方法之主流。 In the dropping method, first, a rectangular sealing pattern is formed by dispensing on one of the two substrates with electrodes. Then, in a state where the sealant is not hardened, liquid crystal droplets are dropped into the sealing frame of the substrate, another substrate is stacked under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to be temporarily hardened. After that, it is heated to perform main hardening to produce a liquid crystal display element. At present, the dripping method is becoming the mainstream of the manufacturing method of the liquid crystal display element.
且說，於行動電話、攜帶型遊戲機等各種附有液晶面板之移動機器正在普及之現代，機器之小型化為最被要求之課題。作為機器之小型化之方法，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)。 In addition, modern mobile phones with liquid crystal panels, such as mobile phones and portable game consoles, are becoming popular. The miniaturization of devices is the most demanded issue. As a method for miniaturizing the device, narrow edge of the liquid crystal display portion can be cited, for example, the position of the sealing portion is arranged at Under the black matrix (hereinafter, also referred to as narrow edge design).
然而，於窄邊緣設計中，由於將密封劑配置於黑矩陣之正下方，故而有如下問題：若實施滴下方法，則於使密封劑光硬化時照射之光被遮蔽，光難以到達至密封劑之內部，硬化變得不充分。若如此密封劑之硬化變得不充分，則有未硬化之密封劑成分溶出至液晶中而容易產生液晶污染之問題。 However, in the narrow-edge design, since the sealant is arranged directly below the black matrix, there is a problem that if the dropping method is implemented, the light irradiated when the sealant is light-cured is blocked, and the light is difficult to reach the sealant. Inside, hardening becomes insufficient. If the hardening of the sealant becomes insufficient in this way, there is a problem that the uncured sealant component is dissolved into the liquid crystal and liquid crystal contamination is liable to occur.
於專利文獻3中，揭示將高感度之光聚合起始劑調配於密封劑中。然而，若僅調配高感度之光聚合起始劑，則無法使密封劑充分地光硬化。又，於專利文獻4中，揭示將高感度之光聚合起始劑與增感劑組合而調配於密封劑中。然而，由於使用增感劑，故而有容易產生液晶污染之問題。 Patent Document 3 discloses that a high-sensitivity photopolymerization initiator is formulated in a sealant. However, if only a high-sensitivity photopolymerization initiator is blended, the sealant cannot be sufficiently photocured. In addition, Patent Document 4 discloses that a high-sensitivity photopolymerization initiator and a sensitizer are combined and formulated in a sealant. However, since a sensitizer is used, there is a problem that liquid crystal contamination is liable to occur.
專利文獻1：日本特開2001-133794號公報 Patent Document 1: Japanese Patent Laid-Open No. 2001-133794
專利文獻2：國際公開第02/092718號 Patent Document 2: International Publication No. 02/092718
專利文獻3：國際公開第2011/002028號 Patent Document 3: International Publication No. 2011/002028
專利文獻4：日本特開2010-286640號公報 Patent Document 4: Japanese Patent Application Laid-Open No. 2010-286640
本發明之目的在於提供一種光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 An object of the present invention is to provide a sealant for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination. Another object of the present invention is to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
本發明係含有硬化性樹脂、9-氧硫系聚合起始劑、及 下述式(1)所表示之胺系增感劑之液晶顯示元件用密封劑。 The present invention contains a curable resin and 9-oxysulfur A sealing agent for a liquid crystal display element based on a polymerization initiator and an amine-based sensitizer represented by the following formula (1).
式(1)中，z表示1以上之整數，P為(聚)乙二醇、(聚)丙二醇、(聚)丁二醇、甘油、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇、或己內酯多元醇之殘基。 In formula (1), z represents an integer of 1 or more, and P is (poly) ethylene glycol, (poly) propylene glycol, (poly) butanediol, glycerin, trimethylolpropane, di-trimethylolpropane, Residues of neopentaerythritol, dipentaerythritol, or caprolactone polyols.
以下詳細地說明本發明。 The present invention will be described in detail below.
本發明人等發現，令人驚訝的是，具有特定之結構之化合物對液晶之污染性較低，且增感作用優異。因此，本發明者等人發現：藉由調配該化合物作為增感劑，可獲得光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑，從而完成本發明。 The present inventors have found that, surprisingly, a compound having a specific structure has a low contamination property to liquid crystals and has an excellent sensitizing effect. Therefore, the present inventors have found that by formulating the compound as a sensitizer, a sealant for a liquid crystal display element that is excellent in photocurability and can suppress liquid crystal contamination can be obtained, and completed the present invention.
本發明之液晶顯示元件用密封劑含有上述式(1)所表示之胺系增感劑。藉由將上述式(1)所表示之胺系增感劑與9-氧硫系聚合起始劑組合而含有，本發明之液晶顯示元件用密封劑成為高感度而光硬化性優異、且可抑制液晶污染者。 The sealing agent for liquid crystal display elements of this invention contains the amine-type sensitizer represented by said Formula (1). By combining the amine sensitizer represented by the above formula (1) with 9-oxysulfur It is contained as a combination of a polymerization initiator, and the sealing agent for liquid crystal display elements of this invention has high sensitivity, is excellent in photocurability, and can suppress liquid crystal contamination.
上述式(1)中，z表示1以上之整數，較佳之下限為2，較佳之上限為6。若上述z未達2，則存在引起液晶污染之情形。若上述z超過6，則存在黏度增高而難以使用之情形。 In the above formula (1), z represents an integer of 1 or more, a preferred lower limit is 2, and a preferred upper limit is 6. If z is less than 2, the liquid crystal may be contaminated. When the above-mentioned z exceeds 6, the viscosity may increase and it may be difficult to use.
上述式(1)中，P為(聚)乙二醇、(聚)丙二醇、(聚)丁二醇、甘油、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇、或己內酯多元醇之殘基。 In the above formula (1), P is (poly) ethylene glycol, (poly) propylene glycol, (poly) butanediol, glycerol, trimethylolpropane, di-trimethylolpropane, neopentyl alcohol, diethylene glycol Residues of neopentyl alcohol, or caprolactone polyols.
上述式(1)中之P之分子量的較佳下限為100，較佳上限為2000。若P之分子量未達100，則存在引起液晶污染之情形。若P之分子量超過2000，則存在黏度變得過高而難以使用之情形。 The preferable lower limit of the molecular weight of P in the formula (1) is 100, and the preferable upper limit is 2000. If the molecular weight of P is less than 100, liquid crystal contamination may occur. When the molecular weight of P exceeds 2,000, the viscosity may become too high, making it difficult to use.
上述式(1)所表示之胺系增感劑中，較佳為式(1)中之z為2，P為聚乙二醇之殘基。 Among the amine-based sensitizers represented by the formula (1), it is preferable that z in the formula (1) is 2 and P is a residue of polyethylene glycol.
作為製造上述式(1)所表示之胺系增感劑之方法，具體而言，例如可列舉使4-(二甲胺基)苯甲醯氯與聚環氧乙烷反應之方法等。 Specific examples of a method for producing the amine-based sensitizer represented by the formula (1) include a method of reacting 4- (dimethylamino) benzamidine chloride with polyethylene oxide.
本發明之液晶顯示元件用密封劑100重量份中之上述式(1)所表示之胺系增感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。若上述式(1)所表示之胺系增感劑之含量未達0.1重量份，則存在所獲得之液晶顯示元件用密封劑成為光硬化性較差者而產生液晶污染之情形。若上述式(1)所表示之胺系增感劑之含量超過10重量份，則存在產生因上述式(1)所表示之胺系增感劑所導致之液晶污染之情形。上述式(1)所表示之胺系增感劑之含量的更佳之下限為0.3重量份，更佳之上限為7重量份。 The lower limit of the content of the amine sensitizer represented by the formula (1) in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 0.1 parts by weight, and the preferable upper limit is 10 parts by weight. If the content of the amine-based sensitizer represented by the formula (1) is less than 0.1 part by weight, the obtained sealant for a liquid crystal display element may be poor in photocurability and cause liquid crystal contamination. When the content of the amine-based sensitizer represented by the formula (1) exceeds 10 parts by weight, liquid crystal contamination due to the amine-based sensitizer represented by the formula (1) may occur. A more preferable lower limit of the content of the amine-based sensitizer represented by the formula (1) is 0.3 part by weight, and a more preferable upper limit is 7 parts by weight.
本發明之液晶顯示元件用密封劑含有9-氧硫系聚合起始劑。 The sealing agent for liquid crystal display elements of the present invention contains 9-oxysulfur System polymerization initiator.
作為上述9-氧硫系聚合起始劑，例如可列舉：下述式(2)所表示之化合物、2,4-二乙基9-氧硫、2-異丙基9-氧硫、4-異 丙基9-氧硫、2-氯9-氧硫、1-氯-4-丙氧基9-氧硫等。其中，就所獲得之液晶顯示元件用密封劑成為硬化性優異者而言，較佳為下述式(2)所表示之化合物(以下，亦稱為「式(2)所表示之9-氧硫系聚合起始劑」)。 As the above 9-oxysulfur Examples of the polymerization initiator include a compound represented by the following formula (2), 2,4-diethyl 9-oxosulfur , 2-isopropyl 9-oxysulfur , 4-isopropyl 9-oxysulfur , 2-chloro9-oxysulfur , 1-chloro-4-propoxy9-oxysulfur Wait. Among them, a compound represented by the following formula (2) (hereinafter, also referred to as "9-oxygen represented by the formula (2)" is preferred because the obtained sealant for a liquid crystal display element has excellent curability. sulfur System polymerization initiator ").
式(2)中，n為1~6，R3為氫原子、甲基、或乙基，於n大於1之情形時，R3所表示之基或原子可相同亦可不同。A表示式-O-、-[O(CHR2CHR1)a]y-、-[O(CH2)bCO]y-、或-[O(CH2)bCO](y-1)-[O(CHR2CHR1)a]-之基，R1與R2之一者表示氫原子，另一者表示氫原子、甲基、或乙基，a為1~2，b為4~5，Q為(聚)乙二醇、(聚)丙二醇、(聚)丁二醇、甘油、三羥甲基丙烷、二-三羥甲基丙烷、新戊四醇、二新戊四醇、或己內酯多元醇之殘基，Q內之游離羥基亦可經酯化，x為大於1且不超過Q之羥基數的數目，於x大於1且不超過2之情形時，y為1~10，於x超過2之情形時，y為3~10。 In formula (2), n is 1 to 6, and R 3 is a hydrogen atom, a methyl group, or an ethyl group. When n is greater than 1, the groups or atoms represented by R 3 may be the same or different. A represents the formula -O-,-[O (CHR 2 CHR 1 ) a ] y -,-[O (CH 2 ) b CO] y- , or-[O (CH 2 ) b CO] (y-1) -[O (CHR 2 CHR 1 ) a ]-, one of R 1 and R 2 represents a hydrogen atom, the other represents a hydrogen atom, a methyl group, or an ethyl group, a is 1 to 2, and b is 4 ~ 5, Q is (poly) ethylene glycol, (poly) propylene glycol, (poly) butanediol, glycerol, trimethylolpropane, di-trimethylolpropane, neopentyl tetraol, dipentaerythritol , Or the residue of a caprolactone polyol, the free hydroxyl groups in Q can also be esterified, and x is the number of hydroxyl groups greater than 1 and not more than Q. When x is greater than 1 and not more than 2, y is 1 to 10, when x exceeds 2, y is 3 to 10.
上述式(2)中，x為大於1且不超過Q之羥基數之數，較佳之下限為2，較佳之上限為6。若上述x未達2，則存在引起液晶污染之情形。若上述x超過6，則存在黏度增高而難以使用之情形。 In the above formula (2), x is a number greater than 1 and not more than the number of hydroxyl groups of Q, with a preferred lower limit of 2 and a preferred upper limit of 6. If x is less than 2, the liquid crystal may be contaminated. When the above-mentioned x exceeds 6, the viscosity may increase and it may be difficult to use.
上述式(2)所表示之9-氧硫系聚合起始劑中，較佳 為上述式(2)中之n為1，R3為氫原子，A為式-O-之基。 9-oxysulfur represented by the above formula (2) In the system polymerization initiator, it is preferable that n in the formula (2) is 1, R 3 is a hydrogen atom, and A is a group of the formula -O-.
上述式(2)中之Q較佳為聚丁二醇之殘基。 Q in the above formula (2) is preferably a residue of polybutanediol.
又，於Q內之游離羥基經酯化之情形時，上述式(2)所表示之9-氧硫系聚合起始劑較佳為低級脂肪酸酯。 In the case where the free hydroxyl group in Q is esterified, the 9-oxysulfur represented by the above formula (2) The polymerization initiator is preferably a lower fatty acid ester.
上述式(2)中，A-Q之分子量之較佳下限為100，較佳上限為2000。若A-Q之分子量未達100，則存在引起液晶污染之情形。若A-Q之分子量超過2000，則存在黏度變得過高而難以使用之情形。 In the above formula (2), the preferable lower limit of the molecular weight of A-Q is 100, and the preferable upper limit is 2000. If the molecular weight of A-Q is less than 100, liquid crystal contamination may occur. When the molecular weight of A-Q exceeds 2,000, the viscosity may become too high, making it difficult to use.
作為製造上述式(2)所表示之9-氧硫系聚合起始劑之方法，具體而言，例如可列舉使羧基甲氧基9-氧硫與聚乙二醇反應之方法等。 Production of 9-oxysulfur represented by the above formula (2) As a method of the polymerization initiator, specifically, for example, carboxymethoxy 9-oxysulfur Methods of reaction with polyethylene glycol.
本發明之液晶顯示元件用密封劑100重量份中之上述9-氧硫系聚合起始劑的含量之較佳之下限為0.1重量份，較佳之上限為10重量份。若上述9-氧硫系聚合起始劑之含量未達0.1重量份，則存在未充分地進行所獲得之液晶顯示元件用密封劑之光聚合之情形。若上述9-氧硫系聚合起始劑之含量超過10重量份，則存在未反應之9-氧硫系聚合起始劑大量殘留，所獲得之液晶顯示元件用密封劑成為耐候性或保存穩定性差者，或產生液晶污染之情形。上述9-氧硫系聚合起始劑之含量之更佳之下限為0.3重量份，更佳之上限為7重量份。 The above 9-oxysulfur in 100 parts by weight of the sealant for a liquid crystal display element of the present invention The preferable lower limit of the content of the polymerization initiator is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. If the above 9-oxysulfur If the content of the polymerization initiator is less than 0.1 part by weight, the photopolymerization of the obtained sealing agent for a liquid crystal display element may not be sufficiently performed. If the above 9-oxysulfur If the content of the polymerization initiator exceeds 10 parts by weight, unreacted 9-oxysulfur is present A large amount of the polymerization initiator remains, and the obtained sealing agent for a liquid crystal display element may have poor weather resistance or poor storage stability, or may cause liquid crystal contamination. 9-oxysulfur The more preferable lower limit of the content of the polymerization initiator is 0.3 part by weight, and the more preferable upper limit is 7 parts by weight.
關於上述9-氧硫系聚合起始劑與上述式(1)所表示之胺系增感劑之含有比例，以重量比計，較佳為9-氧硫系聚合起始劑：式(1)所表示之胺系增感劑=1：0.05~1：5。藉由使上述9-氧硫 系聚合起始劑與上述式(1)所表示之胺系增感劑之含有比例在該範圍 內，本發明之液晶顯示元件用密封劑成為抑制液晶污染之效果、及光硬化性尤其優異者。上述9-氧硫系聚合起始劑與上述式(1)所表示之胺系增感劑之含有比例更佳為9-氧硫系聚合起始劑：式(1)所表示之胺系增感劑=1：0.1~1：2。 About the above 9-oxysulfur The content ratio of the polymerization initiator and the amine sensitizer represented by the above formula (1) is preferably 9-oxysulfur in terms of weight ratio. Polymerization initiator: amine sensitizer represented by formula (1) = 1: 0.05 ~ 1: 5. By making the above 9-oxysulfur The content ratio of the system-based polymerization initiator and the amine-based sensitizer represented by the above formula (1) is within this range, and the sealant for a liquid crystal display element of the present invention has an effect of suppressing liquid crystal contamination and is particularly excellent in photocurability . 9-oxysulfur The content ratio of the polymerization initiator and the amine sensitizer represented by the formula (1) is more preferably 9-oxysulfur Polymerization initiator: Amine sensitizer represented by formula (1) = 1: 0.1 ~ 1: 2.
本發明之液晶顯示元件用密封劑含有硬化性樹脂。 The sealing agent for liquid crystal display elements of this invention contains a curable resin.
上述硬化性樹脂較佳為含有(甲基)丙烯酸樹脂。 The curable resin is preferably a (meth) acrylic resin.
作為上述(甲基)丙烯酸樹脂，例如可列舉：藉由使具有羥基之化合物與(甲基)丙烯酸反應而獲得之酯化合物、藉由使(甲基)丙烯酸與環氧化合物反應而獲得之環氧(甲基)丙烯酸酯、藉由使具有羥基之(甲基)丙烯酸衍生物與異氰酸酯化合物反應而獲得之(甲基)丙烯酸胺酯(urethane(meth)acrylate)等。其中，較佳為環氧(甲基)丙烯酸酯。再者，於本說明書中，上述所謂「(甲基)丙烯酸」，係指丙烯酸或甲基丙烯酸，上述所謂「(甲基)丙烯酸樹脂」，係指具有丙烯醯基或甲基丙烯醯基(以下，亦合併稱為「(甲基)丙烯醯基」)之樹脂。又，上述所謂「(甲基)丙烯酸酯」，係指丙烯酸酯或甲基丙烯酸酯。進而，上述所謂「環氧(甲基)丙烯酸酯」，表示使環氧樹脂中之所有環氧基與(甲基)丙烯酸反應而成之化合物。 Examples of the (meth) acrylic resin include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and a ring obtained by reacting a (meth) acrylic acid with an epoxy compound. Oxy (meth) acrylate, urethane (meth) acrylate, etc. obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound. Among these, epoxy (meth) acrylate is preferable. In addition, in the present specification, the above-mentioned "(meth) acrylic acid" refers to acrylic acid or methacrylic acid, and the above-mentioned "(meth) acrylic resin" refers to those having an acrylyl group or a methacrylmethyl group ( Hereinafter, resins called "(meth) acrylfluorenyl") are also combined. The "(meth) acrylate" refers to an acrylate or a methacrylate. Furthermore, the above-mentioned "epoxy (meth) acrylate" means a compound obtained by reacting all epoxy groups in an epoxy resin with (meth) acrylic acid.
作為上述酯化合物中之單官能者，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4-羥基丁酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸四氫糠 酯、(甲基)丙烯酸苄酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、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、甲氧基聚乙二醇(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)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸二甲胺基乙酯、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、(甲基)丙烯酸縮水甘油酯、磷酸2-(甲基)丙烯醯氧基乙酯等。 Examples of the monofunctional compound in the ester compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (methyl) ) 2-hydroxybutyl acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, (hard) (meth) acrylate Fatty ester, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, (methyl ) 2-ethoxyethyl acrylate, tetrahydrofurfuryl (meth) acrylate Ester, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy Polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2 (meth) acrylate, 3,3-tetrafluoropropyl ester, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, ammonium (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate , N-butyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, (formyl) (Isopropyl) myristyl acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, dicyclopentene (meth) acrylate, (meth) acrylic acid Isodecyl ester, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloxyethyl succinate, hexahydrophthalic acid 2 -(Meth) acryloxyethyl, 2- (meth) acryloxyethyl 2-hydroxypropyl phthalate, ( Yl) acrylate phosphate, 2- (meth) acrylate and the like Bing Xixi group.
又，作為上述酯化合物中之二官能者，例如可列舉：1,4-丁二醇二(甲基)丙烯酸酯、1,3-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、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(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、環氧丙烷加成雙酚A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、1,3-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷改質異氰尿酸二(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。 Examples of the difunctional group in the ester compound include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,6- Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol 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 (meth) acrylate, ethylene glycol di (methyl) Acrylate), diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene oxide addition bisphenol A di (Meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, di (meth) acrylate dihydroxymethyl Dicyclopentadiene ester, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylic acid ester, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol Di (meth) acrylate, polycaprolactone glycol di (meth) acrylate, polybutadiene glycol di (meth) acrylate, and the like.
又，作為上述酯化合物中之三官能以上者，例如可列舉：新戊四醇三(甲基)丙烯酸酯、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、環氧乙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、環氧乙烷加成異氰尿酸三(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、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、三(甲基)丙烯酸甘油酯、環氧丙烷加成三(甲基)丙烯酸甘油酯、磷酸三(甲基)丙烯醯氧基乙酯等。 In addition, examples of the tri- or more functional group among the ester compounds include neopentyl tetraol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and propylene oxide addition trimethylol. Propane tri (meth) acrylate, ethylene oxide addition trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, ethylene oxide Alkane addition isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di-trimethylolpropane tetra (methyl) Acrylate), neopentaerythritol tetra (meth) acrylate, glyceryl tri (meth) acrylate, glyceryl tri (meth) acrylate addition, tris (meth) acrylic acid phosphate Ethyl esters, etc.
作為上述環氧(甲基)丙烯酸酯，例如可列舉藉由使環氧樹脂與(甲基)丙烯酸依據常法於鹼性觸媒之存在下進行反應而獲得者等。 Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy resin with (meth) acrylic acid in the presence of a basic catalyst in accordance with a conventional method.
作為成為用於合成上述環氧(甲基)丙烯酸酯之原料之環氧樹脂，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、2,2'-二烯丙基雙酚A型環氧樹脂、氫化雙酚型環氧樹脂、環氧丙烷加成雙酚A型環氧樹脂、間苯二酚型環氧樹脂、聯苯型環氧樹脂、硫化物型環氧樹脂、二苯醚型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、二環戊二烯酚醛清漆型環氧樹脂、聯苯酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、縮水甘油胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧樹脂、縮水甘油酯化合物等。 Examples of the epoxy resin used as a raw material for synthesizing the above-mentioned epoxy (meth) acrylate include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, 2 , 2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl ring Oxygen resin, sulfide epoxy resin, diphenyl ether epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin Resin, dicyclopentadiene novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol epoxy resin, rubber Modified epoxy resin, glycidyl ester compound, etc.
作為上述雙酚A型環氧樹脂中之市售者，例如可列舉：jER828EL、jER1004(均為三菱化學公司製造)、Epiclon 850CRP(DIC公司製造)等。 Examples of commercially available bisphenol A epoxy resins include jER828EL, jER1004 (both manufactured by Mitsubishi Chemical Corporation), Epiclon 850CRP (manufactured by DIC Corporation), and the like.
作為上述雙酚F型環氧樹脂中之市售者，例如可列舉jER806、jER4004(均為三菱化學公司製造)等。 Examples of a commercially available bisphenol F-type epoxy resin include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
作為上述雙酚S型環氧樹脂中之市售者，例如可列舉Epiclon EXA1514(DIC公司製造)等。 Examples of a commercially available bisphenol S-type epoxy resin include Epiclon EXA1514 (manufactured by DIC Corporation).
作為上述2,2'-二烯丙基雙酚A型環氧樹脂中之市售者，例如可列舉RE-810NM(日本化藥公司製造)等。 Examples of the commercially available 2,2'-diallyl bisphenol A type epoxy resin include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
作為上述氫化雙酚型環氧樹脂中之市售者，例如可列舉Epiclon EXA7015(DIC公司製造)等。 As a commercial one among the said hydrogenated bisphenol-type epoxy resins, Epiclon EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
作為上述環氧丙烷加成雙酚A型環氧樹脂中之市售者，例如可列舉：EP-4000S(ADEKA公司製造)等。 Examples of a commercially available propylene oxide-added bisphenol A type epoxy resin include EP-4000S (manufactured by ADEKA).
作為上述間苯二酚型環氧樹脂中之市售者，例如可列舉EX-201(Nagase chemteX公司製造)等。 As a marketer among the said resorcinol-type epoxy resins, EX-201 (made by Nagase chemteX company) etc. are mentioned, for example.
作為上述聯苯型環氧樹脂中之市售者，例如可列舉jERYX-4000H(三菱化學公司製造)等。 Examples of a commercially available biphenyl type epoxy resin include jERYX-4000H (manufactured by Mitsubishi Chemical Corporation).
作為上述硫化物型環氧樹脂中之市售者，例如可列舉YSLV-50TE(新日鐵住金化學公司製造)等。 As a commercially available one among the said sulfide-type epoxy resins, YSLV-50TE (made by Nippon Steel & Sumitomo Chemical Co., Ltd.) etc. are mentioned, for example.
作為上述二苯醚型環氧樹脂中之市售者，例如可列舉YSLV-80DE(新日鐵住金化學公司製造)等。 Examples of a commercially available diphenyl ether type epoxy resin include YSLV-80DE (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).
作為上述二環戊二烯型環氧樹脂中之市售者，例如可列舉EP-4088S (ADEKA公司製造)等。 As a marketer of the above-mentioned dicyclopentadiene-type epoxy resins, for example, EP-4088S can be cited. (Manufactured by ADEKA).
作為上述萘型環氧樹脂中之市售者，例如可列舉Epiclon HP4032、Epiclon EXA-4700(均為DIC公司製造)等。 Examples of the commercially available naphthalene-type epoxy resin include Epiclon HP4032 and Epiclon EXA-4700 (both manufactured by DIC Corporation).
作為上述苯酚酚醛清漆型環氧樹脂中之市售者，例如可列舉Epiclon N-770(DIC公司製造)等。 As a marketer among the said phenol novolak-type epoxy resins, Epiclon N-770 (made by DIC Corporation) etc. are mentioned, for example.
作為上述鄰甲酚酚醛清漆型環氧樹脂中之市售者，例如可列舉Epiclon N-670-EXP-S(DIC公司製造)等。 As a commercially available one among the above-mentioned ortho-cresol novolac-type epoxy resins, Epiclon N-670-EXP-S (made by DIC Corporation) etc. can be mentioned, for example.
作為上述二環戊二烯酚醛清漆型環氧樹脂中之市售者，例如可列舉Epiclon HP7200(DIC公司製造)等。 Examples of a commercially available dicyclopentadiene novolac-type epoxy resin include Epiclon HP7200 (manufactured by DIC Corporation).
作為上述聯苯酚醛清漆型環氧樹脂中之市售者，例如可列舉NC-3000P(日本化藥公司製造)等。 As a commercially available one among the above-mentioned biphenol novolak-type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) is mentioned, for example.
作為上述萘酚酚醛清漆型環氧樹脂中之市售者，例如可列舉ESN-165S(新日鐵住金化學公司製造)等。 As a marketer of the said naphthol novolak-type epoxy resin, ESN-165S (made by Nippon Steel & Sumitomo Chemical Co., Ltd.) etc. are mentioned, for example.
作為上述縮水甘油胺型環氧樹脂中之市售者，例如可列舉：jER630(三菱化學公司製造)、Epiclon 430(DIC公司製造)、TETRAD-X(三菱瓦斯化學公司製造)等。 Examples of a commercially available glycidylamine type epoxy resin include jER630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like.
作為上述烷基多元醇型環氧樹脂中之市售者，例如可列舉：ZX-1542(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(Nagase chemteX公司製造)等。 As a marketer of the above-mentioned alkyl polyol type epoxy resin, for example, 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 (manufactured by Nagase chemteX) and the like.
作為上述橡膠改質型環氧樹脂中之市售者，例如可列舉：YR-450、YR-207(均為新日鐵住金化學公司製造)、Epolead PB(Daicel公司製造)等。 Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and Epolead PB (manufactured by Daicel).
作為上述縮水甘油酯化合物中之市售者，例如可列舉Denacol EX-147(Nagase chemteX公司製造)等。 Examples of a commercially available glycidyl ester compound include Denacol EX-147 (manufactured by Nagase ChemteX).
作為上述環氧樹脂中之其他市售者，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 other commercially available epoxy resins include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), XAC4151 (made by Asahi Kasei Corporation), jER1031, jER1032 ( All are manufactured by Mitsubishi Chemical Corporation), EXA-7120 (made by DIC Corporation), TEPIC (made by Nissan Chemical Corporation), and the like.
作為製造上述環氧(甲基)丙烯酸酯之方法，具體而言，例如可藉由一面對間苯二酚型環氧樹脂(EX-201，Nagase chemteX公司製造)360重量份、作為聚合抑制劑之對甲氧基苯酚2重量份、作為反應觸媒之三乙胺2重量份、及丙烯酸210重量份吹送空氣而進行回流攪拌，一面於90℃使之反應5小時，而獲得間苯二酚型環氧丙烯酸酯。 As a method for producing the above-mentioned epoxy (meth) acrylate, specifically, for example, 360 parts by weight of a resorcinol-type epoxy resin (EX-201, manufactured by Nagase chemteX) can be used as polymerization inhibition. 2 parts by weight of p-methoxyphenol, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid were blown under air and stirred under reflux, and reacted at 90 ° C for 5 hours to obtain m-benzenediene A phenolic epoxy acrylate.
作為上述環氧(甲基)丙烯酸酯中之市售者，例如可列舉：EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182(均為Daicel-Allnex公司製造)、EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020(均為新中村化學工業公司製造)、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(均為共榮社化學公司製造)、Denacol Acrylate DA-141、Denacol Acrylate DA-314、Denacol Acrylate DA-911(均為Nagase chemteX公司製造)等。 As the marketers of the aforementioned epoxy (meth) acrylates, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, and EBECRYD Rcel63182 (Manufactured by the company), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 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 (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 (all manufactured by Nagase chemteX), and the like.
作為上述藉由使具有羥基之(甲基)丙烯酸衍生物與異氰酸酯化合物反應而獲得之(甲基)丙烯酸胺酯，例如可藉由相對於具有2個異氰酸酯基之異氰酸酯化合物1當量，使具有羥基之(甲基)丙烯酸衍生物2當量於觸媒量之錫系化合物存在下反應而獲得。 As the above-mentioned (meth) acrylic acid amine ester obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound, for example, it is possible to make a hydroxyl group having 1 equivalent to an isocyanate compound having two isocyanate groups. 2 equivalents of the (meth) acrylic acid derivative are obtained by reacting in the presence of a catalyst-based tin-based compound.
作為成為上述(甲基)丙烯酸胺酯之原料之異氰酸酯化合物，例如可列舉：異佛酮二異氰酸酯、2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯(MDI)、氫化MDI、聚合MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯(XDI)、氫化XDI、離胺酸二異氰酸酯(lysine diisocyanate)、三苯基甲烷三異氰酸酯、硫代磷酸三(異氰酸酯基苯基)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 isocyanate compound used as a raw material of the (meth) acrylic acid amine ester include isophorone diisocyanate, 2,4-methylenephenyl diisocyanate, 2,6-methylenephenyl diisocyanate, and hexamethylene. Methyl diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate , Ditoluidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, four Methyl xylene diisocyanate, 1,6,11-undecane triisocyanate and the like.
又，作為成為上述(甲基)丙烯酸胺酯之原料之異氰酸酯化合物，例如亦可使用藉由使乙二醇、甘油、山梨糖醇、三羥甲基丙烷、(聚)丙二醇、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等多元醇與過量之異氰酸酯化合物之反應而獲得的經鏈延長之異氰酸酯化合物。 Moreover, as an isocyanate compound used as a raw material of the said (meth) acrylic acid amine ester, ethylene glycol, glycerol, sorbitol, trimethylolpropane, (poly) propylene glycol, and carbonate diol can be used, for example. A chain-extended isocyanate compound obtained by reacting a polyhydric alcohol such as polyether diol, polyester diol, and polycaprolactone diol with an excessive amount of an isocyanate compound.
作為成為上述(甲基)丙烯酸胺酯之原料之具有羥基之(甲基)丙烯酸衍生物，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4-羥基丁酯、(甲基)丙烯酸2-羥基丁酯等之市售品，或乙二醇、丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、聚乙二醇等二元醇之單(甲基)丙烯酸酯，或三羥甲基乙烷、三羥甲基丙烷、甘油等三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯，或雙酚A型環氧丙烯酸 酯等環氧(甲基)丙烯酸酯等。 Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material of the (meth) acrylic acid amine ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Commercially available products such as 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1, Mono (meth) acrylates of diols such as 4-butanediol and polyethylene glycol, or mono (meth) acrylates of diols such as trimethylolethane, trimethylolpropane, and glycerol Or di (meth) acrylate, or bisphenol A epoxy acrylic Epoxy (meth) acrylate, etc.
具體而言，上述(甲基)丙烯酸胺酯例如可藉由如下方式而獲得：添加三羥甲基丙烷134重量份、作為聚合抑制劑之BHT 0.2重量份、作為反應觸媒之二月桂酸二丁基錫0.01重量份、及異佛酮二異氰酸酯666重量份，一面於60℃進行回流攪拌，一面使之反應2小時，繼而，添加丙烯酸2-羥基乙酯51重量份，一面吹送空氣而進行回流攪拌，一面於90℃使之反應2小時。 Specifically, the above-mentioned (meth) acrylic acid amine ester can be obtained, for example, by adding 134 parts by weight of trimethylolpropane, 0.2 parts by weight of BHT as a polymerization inhibitor, and dilauric acid diacetate as a reaction catalyst. 0.01 parts by weight of butyltin and 666 parts by weight of isophorone diisocyanate were refluxed and stirred at 60 ° C for 2 hours. Then, 51 parts by weight of 2-hydroxyethyl acrylate was added, and the mixture was stirred under reflux while blowing air. While reacting at 90 ° C for 2 hours.
作為上述(甲基)丙烯酸胺酯中之市售者，例如可列舉：M-1100、M-1200、M-1210、M-1600(均為東亞合成公司製造)、EBECRYL230、EBECRYL270、EBECRYL4858、EBECRYL8402、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL1290、EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、EBECRYL2220(均為Daicel-Allnex公司製造)、Artresin UN-9000H、Artresin UN-9000A、Artresin UN-7100、Artresin UN-1255、Artresin UN-330、Artresin UN-3320HB、Artresin UN-1200TPK、Artresin SH-500B(均為根上工業公司製造)、U-122P、U-108A、U-340P、U-4HA、U-6HA、U-324A、U-15HA、UA-5201P、UA-W2A、U-1084A、U-6LPA、U-2HA、U-2PHA、UA-4100、UA-7100、UA-4200、UA-4400、UA-340P、U-3HA、UA-7200、U-2061BA、U-10H、U-122A、U-340A、U-108、U-6H、UA-4000(均為新中村化學工業公司製造)、AH-600、AT-600、UA-306H、AI-600、UA-101T、UA-101I、UA-306T、UA-306I(均為共榮社化學公司製 造)等。 Examples of commercially available amine (meth) acrylates include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toa Synthesis), EBCRYL230, EBCRYL270, EBCRYL4858, and EBCRYL8402. , EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (All are manufactured by Daicel-Allnex UN-Reinin, Artinin9000, Artinin9000, Artresin9000, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all manufactured by Genjo Industrial Co., Ltd.), U-122P, U-108A, U-340P, U-4HA, U- 6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd. Made) and so on.
為了提高所獲得之液晶顯示元件用密封劑之接著性，上述硬化性樹脂較佳為進而含有環氧樹脂。作為上述環氧樹脂，例如可列舉成為用於合成上述環氧(甲基)丙烯酸酯之原料之環氧樹脂、或部分(甲基)丙烯醯基改質環氧樹脂等。 In order to improve the adhesiveness of the obtained sealant for liquid crystal display elements, it is preferred that the curable resin further contains an epoxy resin. As said epoxy resin, the epoxy resin used as a raw material for synthesizing the said epoxy (meth) acrylate, or a partial (meth) acryl fluorenyl modified epoxy resin etc. are mentioned, for example.
再者，於本說明書中，上述所謂部分(甲基)丙烯醯基改質環氧樹脂，係指1分子中具有各1個以上之環氧基與(甲基)丙烯醯氧基之樹脂，例如可藉由使2個以上之環氧樹脂之一部分之環氧基與(甲基)丙烯酸反應而獲得。 In addition, in the present specification, the so-called partially (meth) acrylfluorene-modified epoxy resin refers to a resin having one or more epoxy groups and (meth) acrylfluorene groups in one molecule, For example, it can be obtained by reacting an epoxy group of a part of two or more epoxy resins with (meth) acrylic acid.
於本發明之液晶顯示元件用密封劑含有上述環氧樹脂之情形時，較佳為以使(甲基)丙烯醯氧基與環氧基之比成為30：70~95：5之方式調配上述(甲基)丙烯酸樹脂與上述環氧樹脂。若(甲基)丙烯醯氧基之比率未達30%，則存在如下情形：由於即便(甲基)丙烯醯氧基之聚合結束亦大量存在未硬化之環氧樹脂成分，故而產生液晶污染。若(甲基)丙烯醯氧基之比率超過95%，則存在所獲得之液晶顯示元件用密封劑成為接著性差者之情形。 When the sealing agent for liquid crystal display elements of this invention contains the said epoxy resin, it is preferable to mix | blend the said so that the ratio of a (meth) acryl fluorenyl group and an epoxy group may become 30: 70-95: 5 (Meth) acrylic resin and the above-mentioned epoxy resin. If the ratio of the (meth) acrylic fluorenyloxy group is less than 30%, there is a case where a large amount of uncured epoxy resin components are present even if the polymerization of the (meth) acryl fluorenyloxy group is completed, so that liquid crystal pollution occurs. When the ratio of the (meth) acrylic fluorenyloxy group exceeds 95%, the obtained sealing agent for liquid crystal display elements may become inferior in adhesiveness.
就抑制液晶污染之觀點而言，上述硬化性樹脂較佳為-OH基、-NH-基、-NH2基等具有氫鍵性之單元者。 From the viewpoint of suppressing liquid crystal contamination, the curable resin is preferably one having a hydrogen bonding unit such as an -OH group, an -NH- group, or an -NH 2 group.
又，就反應性之程度而言，上述(甲基)丙烯酸樹脂較佳為分子中具有2~3個(甲基)丙烯醯氧基者。 Moreover, it is preferable that the said (meth) acrylic resin has 2 to 3 (meth) acrylic fluorenyloxy groups in a molecule | numerator in terms of reactivity.
本發明之液晶顯示元件用密封劑亦可含有熱自由基聚合起始劑。 The sealing agent for liquid crystal display elements of this invention may contain a thermal radical polymerization initiator.
作為上述熱自由基聚合起始劑，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起始劑(以下，亦稱為「高分子偶氮起始劑」)。 Examples of the thermal radical polymerization initiator include azo compounds and organic peroxygen. Chemical compounds. Among them, a starter composed of a polymer azo compound (hereinafter, also referred to as a “polymer azo starter”) is preferred.
再者，於本說明書中，所謂高分子偶氮起始劑，係指具有偶氮基、且藉由熱而產生可使(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。 In addition, in this specification, the term "polymer azo initiator" means that the number average molecular weight of radicals which have an azo group and which can harden a (meth) acryloxy group by heat is 300. The above compounds.
上述高分子偶氮起始劑之數量平均分子量之較佳之下限為1000，較佳之上限為30萬。若上述高分子偶氮起始劑之數量平均分子量未達1000，則存在高分子偶氮起始劑對液晶造成不良影響之情形。若上述高分子偶氮起始劑之數量平均分子量超過30萬，則存在難以混合至硬化性樹脂中之情形。上述高分子偶氮起始劑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。 A preferable lower limit of the number average molecular weight of the polymer azo initiator is 1,000, and a preferable upper limit is 300,000. If the number average molecular weight of the polymer azo initiator is less than 1,000, there may be a case where the polymer azo initiator has an adverse effect on the liquid crystal. When the number average molecular weight of the above-mentioned high molecular azo initiator is more than 300,000, it may be difficult to mix into the curable resin. A more preferable lower limit of the number average molecular weight of the above-mentioned polymer azo initiator is 5000, a more preferable upper limit is 100,000, a more preferable lower limit is 10,000, and a more preferable upper limit is 90,000.
再者，於本說明書中，上述數量平均分子量係藉由凝膠滲透層析法(GPC)進行測定，並藉由聚苯乙烯換算而求出之值。作為藉由GPC測定由聚苯乙烯換算而得之數量平均分子量時之管柱，例如可列舉Shodex LF-804(昭和電工公司製造)等。 In addition, in this specification, the said number average molecular weight is a value measured by gel permeation chromatography (GPC), and calculated | required by polystyrene conversion. Examples of the column used when measuring the number average molecular weight obtained by conversion of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
作為上述高分子偶氮起始劑，例如可列舉具有經由偶氮基而鍵結有複數個聚環氧烷或聚二甲基矽氧烷等單元之結構者。 Examples of the polymer azo initiator include a structure having a plurality of units such as polyalkylene oxide or polydimethylsiloxane bonded via an azo group.
作為上述具有經由偶氮基而鍵結有複數個聚環氧烷等單元之結構之高分子偶氮起始劑，較佳為具有聚環氧乙烷結構者。作為此種高分子偶氮起始劑，例如可列舉：4,4'-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之聚縮合物、或4,4'-偶氮雙(4-氰基戊酸)與具有末端胺基之聚二甲基矽氧烷之聚縮 合物等，具體而言，例如可列舉：VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001(均為和光純藥工業公司製造)等。 As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group, those having a polyethylene oxide structure are preferred. Examples of such a polymer azo initiator include a polycondensate of 4,4'-azobis (4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-couple Polycondensation of azabis (4-cyanovaleric acid) and polydimethylsiloxane with terminal amine groups Specific examples include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.).
又，作為非高分子之偶氮化合物之例，可列舉：V-65、V-501(均為和光純藥工業公司製造)等。 Examples of non-polymeric azo compounds include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
作為上述有機過氧化物，例如可列舉：過氧化酮、過氧縮酮、過氧化氫、過氧化二烷基、過氧酯、過氧化二醯基、過氧化二碳酸酯等。 Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, difluorenyl peroxide, and peroxydicarbonate.
關於上述熱自由基聚合起始劑之含量，相對於硬化性樹脂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。若上述熱自由基聚合起始劑之含量未達0.05重量份，則存在未充分地進行所獲得之液晶顯示元件用密封劑之熱聚合之情形。若上述熱自由基聚合起始劑之含量超過10重量份，則存在因未反應之熱自由基聚合起始劑而產生液晶污染之情形。上述熱自由基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。 Regarding the content of the thermal radical polymerization initiator, the lower limit is preferably 0.05 parts by weight, and the upper limit is preferably 10 parts by weight based on 100 parts by weight of the curable resin. If the content of the thermal radical polymerization initiator is less than 0.05 parts by weight, the thermal polymerization of the obtained sealing agent for a liquid crystal display element may not be sufficiently performed. If the content of the above-mentioned thermal radical polymerization initiator exceeds 10 parts by weight, the liquid crystal may be contaminated by the unreacted thermal radical polymerization initiator. A more preferable lower limit of the content of the thermal radical polymerization initiator is 0.1 part by weight, and a more preferable upper limit is 5 parts by weight.
本發明之液晶顯示元件用密封劑亦可含有熱硬化劑。 The sealing agent for liquid crystal display elements of this invention may contain a thermosetting agent.
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。 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.
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。 Examples of the organic acid hydrazine include dihydrazine sebacate, dihydrazine isophthalate, dihydrazine adipate, and dihydrazine malonate.
作為上述有機酸醯肼中之市售者，例如可列舉：SDH、ADH(均為大塚化學公司製造)、Amicure VDH、Amicure VDN-J、Amicure UDH、Amicure UDH-J(均為Ajinomoto Fine-Techno公司製造)等。 Examples of the commercially available organic acid hydrazine include SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDN-J, Amicure UDH, and Amicure UDH-J (both Ajinomoto Fine-Techno Company)).
關於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。若上述熱硬化劑之含量未達1重量份，則存在無法使所獲得之液晶顯示元件用密封劑充分地熱硬化之情形。若上述熱硬化劑之含量超過50重量份，則存在所獲得之液晶顯示元件用密封劑之黏度增高而塗佈性變差之情形。上述熱硬化劑之含量之更佳之上限為30重量份。 Content of the said thermosetting agent is 100 weight with respect to the said curable resin The preferred lower limit is 1 part by weight, and the preferred upper limit is 50 parts by weight. If the content of the above-mentioned thermosetting agent is less than 1 part by weight, the obtained sealing agent for a liquid crystal display element may not be sufficiently thermo-hardened. When the content of the above-mentioned thermosetting agent exceeds 50 parts by weight, the viscosity of the obtained sealant for a liquid crystal display element may increase and the applicability may deteriorate. A more preferable upper limit of the content of the heat curing agent is 30 parts by weight.
以黏度之提高、由應力分散效果所引起之接著性之改善、線膨脹率之改善、硬化物之耐濕性之進一步之提高等為目的，本發明之液晶顯示元件用密封劑較佳為含有填充劑。 The sealing agent for a liquid crystal display element of the present invention preferably contains an improvement in viscosity, an improvement in adhesion caused by a stress dispersing effect, an improvement in linear expansion ratio, and a further improvement in moisture resistance of a cured product, and the like. Filler.
作為上述填充劑，例如可列舉：滑石、石棉、二氧化矽、矽藻土、膨潤石(smectite)、膨土(bentonite)、碳酸鈣、碳酸鎂、氧化鋁、蒙脫石、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、氫氧化鎂、氫氧化鋁、玻璃珠、氮化矽、硫酸鋇、石膏、矽酸鈣、絹雲母、活性白土、氮化鋁等無機填充劑，或聚酯微粒子、聚胺酯微粒子、乙烯基聚合物微粒子、丙烯酸系聚合物微粒子等有機填充劑。該等填充劑可單獨使用，亦可併用兩種以上。 Examples of the filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, and oxidation. Inorganic fillers such as iron, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated white clay, aluminum nitride, or Organic fillers such as polyester particles, polyurethane particles, vinyl polymer particles, and acrylic polymer particles. These fillers may be used alone or in combination of two or more.
本發明之液晶顯示元件用密封劑100重量份中之上述填充劑之含量的較佳之下限為10重量份，較佳之上限為70重量份。若上述填充劑之含量未達10重量份，則存在未充分地發揮接著性之改善等效果之情形。若上述填充劑之含量超過70重量份，則存在所獲得之液晶顯示元件用密封劑之黏度增高而塗佈性變差之情形。上述填充劑之含量之更佳之下限為20重量份，更佳之上限為60重量份。 A preferable lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 10 parts by weight, and a preferable upper limit is 70 parts by weight. If the content of the filler is less than 10 parts by weight, effects such as improvement in adhesion may not be sufficiently exhibited. When content of the said filler exceeds 70 weight part, the viscosity of the sealing compound for liquid crystal display elements obtained may become high, and a coating property may worsen. A more preferable lower limit of the content of the filler is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.
本發明之液晶顯示元件用密封劑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良好地接著密封劑與基板等之接著助劑之作用。 It is preferable that the sealing agent for liquid crystal display elements of this invention contains a silane coupling agent. on The silane coupling agent mainly functions as a bonding aid for adhering a sealant to a substrate and the like well.
作為上述矽烷偶合劑，就提高與基板等之接著性之效果優異，且可藉由與硬化性樹脂進行化學鍵結而抑制硬化性樹脂向液晶中之流出而言，例如可較佳地使用3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷等。該等矽烷偶合劑可單獨使用，亦可併用兩種以上。 As the above-mentioned silane coupling agent, it is excellent in the effect of improving the adhesion to a substrate and the like, and can suppress the outflow of the hardening resin into the liquid crystal by chemical bonding with the hardening resin. For example, 3- Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and the like. These silane coupling agents may be used alone or in combination of two or more.
本發明之液晶顯示元件用密封劑100重量份中之上述矽烷偶合劑之含量的較佳之下限為0.1重量份，較佳之上限為10重量份。若上述矽烷偶合劑之含量未達0.1重量份，則存在未充分地發揮由調配矽烷偶合劑所產生之效果之情形。若上述矽烷偶合劑之含量超過10重量份，則存在所獲得之液晶顯示元件用密封劑引起液晶污染之情形。上述矽烷偶合劑之含量之更佳之下限為0.3重量份，更佳之上限為5重量份。 A preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 0.1 part by weight, and a preferable upper limit is 10 parts by weight. If the content of the silane coupling agent is less than 0.1 part by weight, the effect produced by the preparation of the silane coupling agent may not be sufficiently exhibited. When the content of the silane coupling agent exceeds 10 parts by weight, the obtained sealing agent for a liquid crystal display element may cause liquid crystal contamination. A more preferable lower limit of the content of the silane coupling agent is 0.3 part by weight, and a more preferable upper limit is 5 parts by weight.
本發明之液晶顯示元件用密封劑亦可含有遮光劑。藉由含有上述遮光劑，本發明之液晶顯示元件用密封劑可較佳地用作遮光密封劑。 The sealing agent for liquid crystal display elements of this invention may contain a light-shielding agent. By containing the said light-shielding agent, the sealing agent for liquid crystal display elements of this invention can be used suitably as a light-shielding sealing agent.
作為上述遮光劑，例如可列舉：氧化鐵、鈦黑、苯胺黑、花青黑、富勒烯、碳黑、樹脂被覆型碳黑等。其中，較佳為鈦黑。 Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among these, titanium black is preferred.
上述鈦黑係與對波長300~800nm之光之平均透過率相比，對紫外線區域附近、尤其是波長370~450nm之光之透過率增高之物質。即，上述鈦黑係具有如下性質之遮光劑：藉由充分地遮蔽可見光區域之波長之光，而對本發明之液晶顯示元件用密封劑賦予遮光性，另一方面，使紫外線區域附近之波長之光透過。作為本發明之液晶顯示元件用密封劑中所含 之遮光劑，較佳為絕緣性較高之物質，作為絕緣性較高之遮光劑，亦較佳為鈦黑。 The titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, especially in the light having a wavelength of 370 to 450 nm, as compared with the average transmittance to light having a wavelength of 300 to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent that sufficiently shields light having a wavelength in a visible light region, thereby imparting light-shielding properties to the sealant for a liquid crystal display element of the present invention, and that Light is transmitted. Contained in the sealant for a liquid crystal display element of the present invention The light-shielding agent is preferably a substance with high insulation, and as the light-shielding agent with high insulation, titanium black is also preferable.
上述鈦黑即便為未經表面處理者亦發揮充分之效果，但亦可使用表面經偶合劑等有機成分處理者，或經氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等經表面處理之鈦黑。其中，就可進一步提高絕緣性之觀點而言，較佳為經有機成分處理者。 The above titanium black exhibits sufficient effects even if it is not surface-treated, but it can also be treated with organic components such as coupling agents on its surface, or silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Surface-treated titanium black, such as those coated with inorganic components. Among them, from the viewpoint of further improving the insulation properties, those treated with an organic component are preferred.
又，使用含有上述鈦黑作為遮光劑之本發明之液晶顯示元件用密封劑而製造的液晶顯示元件由於具有充分之遮光性，故而可實現無光之漏出，具有較高之對比度，而具有優異之圖像顯示品質之液晶顯示元件。 In addition, the liquid crystal display element manufactured by using the sealant for liquid crystal display elements of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, so that it can realize no light leakage, has high contrast, and is excellent Liquid crystal display element with image display quality.
作為上述鈦黑中之市售者，例如可列舉：12S、13M、13M-C、13R-N、14M-C(均為Mitsubishi Materials公司製造)、Tilack D(赤穗化成公司製造)等。 As a marketer in the said titanium black, 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials), Tilack D (made by Ako Chemical Co., Ltd.), etc. are mentioned, for example.
上述鈦黑之比表面積之較佳下限為13m2/g，較佳上限為30m2/g，更佳下限為15m2/g，更佳之上限為25m2/g。 The preferred lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferred upper limit is 30 m 2 / g, the more preferred lower limit is 15 m 2 / g, and the more preferred upper limit is 25 m 2 / g.
又，上述鈦黑之體積電阻之較佳下限為0.5Ω‧cm，較佳上限為3Ω‧cm，更佳下限為1Ω‧cm，更佳上限為2.5Ω‧cm。 In addition, the preferred lower limit of the volume resistance of the titanium black is 0.5Ω‧cm, the preferred upper limit is 3Ω‧cm, the more preferred lower limit is 1Ω‧cm, and the more preferred upper limit is 2.5Ω‧cm.
上述遮光劑之一次粒徑只要為液晶顯示元件之基板間之距離以下，則並無特別限定，較佳之下限為1nm，較佳之上限為5μm。若上述遮光劑之一次粒徑未達1nm，則存在所獲得之液晶顯示元件用密封劑之黏度或搖變性大幅增大，作業性變差之情形。若上述遮光劑之一次粒徑超過5μm，則存在所獲得之液晶顯示元件用密封劑向基板之塗佈性變差之情形。上述遮光劑之一次粒徑之更佳之下限為5nm，更佳之上限為200nm，進 而較佳之下限為10nm，進而較佳之上限為100nm。 The primary particle diameter of the above-mentioned light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element. The preferred lower limit is 1 nm, and the preferred upper limit is 5 μm. If the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity or shake of the obtained sealant for a liquid crystal display element may be significantly increased, and the workability may be deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the applicability of the obtained sealant for a liquid crystal display element to a substrate may be deteriorated. The lower limit of the primary particle size of the above-mentioned light-shielding agent is preferably 5 nm, and the upper limit is more preferably 200 nm. The preferred lower limit is 10 nm, and the preferred upper limit is 100 nm.
本發明之液晶顯示元件用密封劑100重量份中之上述遮光劑之含量的較佳之下限為5重量份，較佳之上限為80重量份。若上述遮光劑之含量未達5重量份，則存在無法獲得充分之遮光性之情形。若上述遮光劑之含量超過80重量份，則存在所獲得之液晶顯示元件用密封劑對基板之密接性或硬化後之強度降低、或描繪性降低之情形。上述遮光劑之含量之更佳之下限為10重量份，更佳之上限為70重量份，進而較佳之下限為30重量份，進而較佳之上限為60重量份。 A preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and a preferable upper limit is 80 parts by weight. If the content of the light-shielding agent is less than 5 parts by weight, sufficient light-shielding properties may not be obtained. When the content of the above-mentioned light-shielding agent exceeds 80 parts by weight, the adhesiveness of the obtained sealing agent for a liquid crystal display element to a substrate, the strength after curing, or the drawability may be reduced. A more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.
作為製造本發明之液晶顯示元件用密封劑之方法，例如可列舉如下方法等：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、3輥混練機等混合機而混合硬化性樹脂、9-氧硫系聚合起始劑、胺系增感劑、及視需要添加之矽烷偶合劑等添加劑。 As a method for producing the sealant for a liquid crystal display element of the present invention, for example, the following methods can be mentioned: mixing and curing using a mixer such as a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a 3-roll kneader Resin, 9-oxysulfur Additives such as polymerization initiators, amine-based sensitizers, and silane coupling agents, if necessary.
藉由在本發明之液晶顯示元件用密封劑中調配導電性微粒子，可製造上下導通材料。此種含有本發明之液晶顯示元件用密封劑與導電性微粒子之上下導通材料亦為本發明之一。 By disposing conductive fine particles in the sealant for a liquid crystal display element of the present invention, a vertical conductive material can be manufactured. Such a sealant for a liquid crystal display element of the present invention and a conductive material for upper and lower conductive particles are also one aspect of the present invention.
作為上述導電性微粒子，可使用金屬球、於樹脂微粒子之表面形成有導電金屬層者等。其中，於樹脂微粒子之表面形成有導電金屬層者因樹脂微粒子之優異之彈性，可不損傷透明基板等而進行導電連接，故而較佳。 As the conductive fine particles, metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are preferable because of the excellent elasticity of the resin fine particles and the conductive connection can be performed without damaging the transparent substrate or the like.
使用本發明之液晶顯示元件用密封劑、或本發明之上下導通材料而製造之液晶顯示元件亦為本發明之一。 A liquid crystal display element manufactured by using the sealant for liquid crystal display elements of the present invention or the upper-lower conductive material of the present invention is also one aspect of the present invention.
作為製造本發明之液晶顯示元件之方法，例如可列舉具有如 下步驟之方法等：於附有ITO薄膜等電極之玻璃基板或聚對苯二甲酸乙二酯基板等2片基板之一片藉由網版印刷、分注器塗佈等使本發明之液晶顯示元件用密封劑等形成長方形狀之密封圖案；於本發明之液晶顯示元件用密封劑等未硬化之狀態下將液晶之微滴滴下塗佈至基板之密封框內，於真空下重疊另一基板；及對本發明之液晶顯示元件用密封劑等之密封圖案部分照射紫外線等光而使密封劑暫時硬化；及加熱暫時硬化之密封劑而使之正式硬化。 As a method for manufacturing the liquid crystal display element of the present invention, for example, The method of the next step, etc .: The liquid crystal display of the present invention is printed on a glass substrate with electrodes such as an ITO film or one of two substrates such as a polyethylene terephthalate substrate by screen printing, dispenser coating, etc. A sealant for the element is used to form a rectangular seal pattern. In the uncured state of the sealant for the liquid crystal display element of the present invention, droplets of liquid crystal are dripped and applied to a sealing frame of a substrate, and another substrate is overlapped under vacuum ; And irradiating light such as ultraviolet rays to the sealing pattern portion of the sealant for a liquid crystal display element of the present invention to temporarily harden the sealant; and heating the temporarily hardened sealant to formally harden the sealant.
根據本發明，可提供一種光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 According to the present invention, it is possible to provide a sealant for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination. Furthermore, according to the present invention, it is possible to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
以下揭示實施例更詳細地說明本發明，但本發明並不僅限定於該等實施例。 The following disclosed examples explain the present invention in more detail, but the present invention is not limited to these examples.
(實施例1~13、比較例1~5) (Examples 1 to 13, Comparative Examples 1 to 5)
依據表1、2中所記載之調配比，使用行星式攪拌機(Thinky公司製造之「脫泡練太郎」)而混合各材料後，進而使用3輥混練機進行混合，藉此製備實施例1~13、比較例1~5之各液晶顯示元件用密封劑。 According to the blending ratios described in Tables 1 and 2, the materials were mixed using a planetary mixer ("Defoaming Rentaro" manufactured by Thinky), and then mixed using a 3-roll kneader to prepare Examples 1 to 1 13. Sealants for liquid crystal display elements of Comparative Examples 1 to 5.
<評價> <Evaluation>
對實施例及比較例中獲得之各液晶顯示元件用密封劑進行以下之評價。將結果示於表1、2。 The sealing agents for liquid crystal display elements obtained in the examples and comparative examples were evaluated as follows. The results are shown in Tables 1 and 2.
(光硬化性) (Light hardening)
將於實施例及比較例中獲得之各液晶顯示元件用密封劑100重量份中分散有間隔物微粒子(積水化學工業公司製造之「Micropearl SI-H050」)1重量份者塗佈於玻璃基板上，使同尺寸之玻璃基板重疊於該基板，繼而，使用金屬鹵化物燈照射100mW/cm2之光10秒，而製作光硬化性試片。光照射係進行無截止濾光片(cut filter)之情形與有400nm截止濾光片之情形之2種模式，並對各情形製作3片試片。使用紅外分光裝置(BIORAD公司製造之「FTS3000」)，測定源自(甲基)丙烯醯基之峰值之光照射前後之變化量，藉此進行光硬化性之評價。將於光照射後源自(甲基)丙烯醯基之峰值減少90%以上之情形評價為「◎」，將於光照射後源自(甲基)丙烯醯基之峰值減少80%以上且未達90%之情形評價為「○」，將於光照射後源自(甲基)丙烯醯基之峰值減少70%以上且未達80%之情形評價為「△」，將於光照射後源自(甲基)丙烯醯基之峰值之減少未達70%之情形評價為「×」而評價光硬化性。 One part by weight of spacer particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Industry Co., Ltd.) were dispersed in 100 parts by weight of each of the sealants for liquid crystal display elements obtained in the examples and comparative examples, and coated on a glass substrate. A glass substrate of the same size was superimposed on the substrate, and then a light of 100 mW / cm 2 was irradiated with a metal halide lamp for 10 seconds to produce a photohardenable test piece. The light irradiation was performed in two modes: a case of a cut filter and a case of a 400 nm cut filter, and three test pieces were prepared for each case. An infrared spectrometer ("FTS3000" manufactured by Biorad Corporation) was used to measure the amount of change before and after light irradiation from a peak derived from a (meth) acrylfluorenyl group, thereby evaluating the photohardenability. The case where the peak derived from (meth) acrylfluorenyl group was reduced by more than 90% after light irradiation was evaluated as "◎", and the peak derived from (meth) acrylfluorenyl group after light irradiation was reduced by more than 80% without The case where it reaches 90% is evaluated as "○", and the case where the peak derived from (meth) acrylfluorenyl group is reduced by more than 70% and less than 80% after light irradiation is evaluated as "△". When the decrease from the peak of the (meth) acrylfluorenyl group was less than 70%, it was evaluated as “×” and the photohardenability was evaluated.
再者，源自(甲基)丙烯醯基之峰值之光照射前後的變化量係取由3片試片獲得之平均值。 In addition, the amount of change before and after light irradiation from a peak derived from a (meth) acrylfluorenyl group is an average value obtained from three test pieces.
(液晶污染性) (Liquid crystal contamination)
使間隔物微粒子(積水化學工業公司製造之「Micropearl SI-H050」)1重量份分散於實施例及比較例中獲得之各液晶顯示元件用密封劑100重量 份，以作為液晶顯示元件用密封劑，於2片已摩擦之配向膜及附有透明電極之基板之一片上以使密封劑之線寬成為1mm的方式利用分注器進行塗佈。 1 part by weight of spacer fine particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Industry Co., Ltd.) was dispersed in 100 parts of each sealing agent for liquid crystal display elements obtained in the examples and comparative examples. As a sealant for a liquid crystal display element, the coating was applied with a dispenser on one of two rubbed alignment films and one of the substrates with a transparent electrode so that the line width of the sealant became 1 mm.
繼而將液晶(Chisso公司製造之「JC-5004LA」)之微滴滴下塗佈於附有透明電極之基板的密封劑之框內整個面上，並立即貼合另一片附有透明電極之彩色濾光片基板，對密封劑部分使用金屬鹵化物燈照射100mW/cm2之紫外線30秒而使之硬化，進而以120℃加熱1小時而獲得液晶顯示元件。光照射係進行無截止濾光片之情形與有400nm截止濾光片之情形之2種模式，並對各情形製作3片液晶顯示元件。 Then, droplets of liquid crystal ("JC-5004LA" manufactured by Chisso Corporation) were drip-coated on the entire surface of the sealant frame of the substrate with a transparent electrode, and another color filter with a transparent electrode attached immediately The light sheet substrate was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds to a sealant portion using a metal halide lamp for 30 seconds to be cured, and further heated at 120 ° C. for 1 hour to obtain a liquid crystal display element. The light irradiation was performed in two modes, a case without a cut filter and a case with a 400 nm cut filter, and three liquid crystal display elements were produced for each case.
對所獲得之液晶顯示元件藉由目測確認設為於60℃施加電壓1000小時之狀態後之密封劑附近之液晶污染。 The obtained liquid crystal display element was visually confirmed to be contaminated with a liquid crystal near the sealant after a voltage was applied at 60 ° C. for 1000 hours.
液晶污染係藉由3片液晶顯示元件之色不均進行判斷，根據色不均之程度，將所有液晶顯示元件完全無色不均之情形評價為「◎」，將至少1片液晶顯示元件略微有色不均之情形評價為「○」，將至少1片液晶顯示元件有稍許色不均之情形評價為「△」，將至少1片液晶顯示元件有相當多色不均之情形評價為「×」而評價液晶污染性。 Liquid crystal pollution is judged by the color unevenness of three liquid crystal display elements. According to the degree of color unevenness, all liquid crystal display elements are evaluated as "◎", and at least one liquid crystal display element is slightly colored. The case of unevenness was evaluated as "○", the case of at least one liquid crystal display element having a slight color unevenness was evaluated as "△", and the case of at least one liquid crystal display element having a considerable amount of color unevenness was evaluated as "×" The liquid crystal contamination was evaluated.
再者，評價為「◎」、「○」之液晶顯示元件係於實用方面完全無問題之等級。 In addition, the liquid crystal display elements evaluated as "◎" and "○" are grades which have no practical problems at all.
[產業上之可利用性] [Industrial availability]
根據本發明，可提供一種光硬化性優異、且可抑制液晶污染之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 According to the present invention, it is possible to provide a sealant for a liquid crystal display element which is excellent in photocurability and can suppress liquid crystal contamination. Furthermore, according to the present invention, it is possible to provide a top-to-bottom conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
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