TW201943738A - Photopolymerization initiator, sealant for display elements, vertical conduction material, display element, and compound - Google Patents
Photopolymerization initiator, sealant for display elements, vertical conduction material, display element, and compoundInfo
- Publication number
- TW201943738A TW201943738A TW108112686A TW108112686A TW201943738A TW 201943738 A TW201943738 A TW 201943738A TW 108112686 A TW108112686 A TW 108112686A TW 108112686 A TW108112686 A TW 108112686A TW 201943738 A TW201943738 A TW 201943738A
- Authority
- TW
- Taiwan
- Prior art keywords
- meth
- sealant
- display element
- acrylate
- liquid crystal
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 95
- 239000000565 sealant Substances 0.000 title claims abstract description 93
- 239000003999 initiator Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 12
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 82
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 238000002835 absorbance Methods 0.000 claims abstract description 12
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- -1 amine compounds Chemical class 0.000 claims description 78
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 239000010419 fine particle Substances 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 91
- 239000004593 Epoxy Substances 0.000 description 77
- 239000003795 chemical substances by application Substances 0.000 description 27
- 239000000126 substance Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 20
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 17
- 238000011109 contamination Methods 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 238000012719 thermal polymerization Methods 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group 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
- 239000011521 glass Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur 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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000002542 deteriorative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003254 radicals Chemical class 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 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
- 229930185605 Bisphenol Natural products 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Chemical group 0.000 description 2
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- 230000000903 blocking effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000005265 dialkylamine group Chemical group 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
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- 238000003756 stirring Methods 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
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- 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
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- 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
- WSOZRQWKNKJOIA-UHFFFAOYSA-N 2-ethoxyethyl dihydrogen phosphate Chemical compound CCOCCOP(O)(O)=O WSOZRQWKNKJOIA-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CITRPMHCVVMQDU-UHFFFAOYSA-N 4-(chloromethyl)-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(CCl)C=C1 CITRPMHCVVMQDU-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
- FWJOTCYZMJIOEN-UHFFFAOYSA-N C(C)OCCC1(C(=O)O)C(C(=O)O)CCCC1 Chemical compound C(C)OCCC1(C(=O)O)C(C(=O)O)CCCC1 FWJOTCYZMJIOEN-UHFFFAOYSA-N 0.000 description 1
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- 229940079865 intestinal antiinfectives imidazole derivative Drugs 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
- 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
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 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
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
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- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
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- 239000011787 zinc oxide Substances 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
-
- 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
-
- 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
Abstract
Description
本發明係關於一種對於長波長之光之反應性優異之光聚合起始劑。又，本發明係關於一種顯示元件用密封劑、以及使用該顯示元件用密封劑而成之上下導通材料及顯示元件，該顯示元件用密封劑含有該光聚合起始劑，對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。進而，本發明係關於一種構成該光聚合起始劑之化合物。The present invention relates to a photopolymerization initiator excellent in reactivity with light having a long wavelength. The present invention also relates to a sealant for a display element, and a top-to-bottom conductive material and a display element formed by using the sealant for a display element. The sealant for a display element contains the photopolymerization initiator, and is suitable for long-wavelength light. It has excellent hardenability, and also has low liquid crystal contamination when used in a liquid crystal display device. Furthermore, the present invention relates to a compound constituting the photopolymerization initiator.
近年，作為液晶顯示單元等液晶顯示元件之製造方法，就縮短生產節拍時間（takt time）、使用液晶量之最佳化等觀點而言，採用如專利文獻1、專利文獻2所揭示之使用光熱併用硬化型密封劑之被稱為滴下工法之液晶滴下方式。
於滴下工法中，首先，藉由滴塗，於2片附電極之透明基板之一者形成框狀之密封圖案。其次，於密封劑未硬化之狀態將液晶之微小滴滴下至透明基板之框內整個面，並立即貼合另一透明基板，對密封部照射紫外線等光進行預硬化。其後，於液晶退火時加熱進行正式硬化，從而製作液晶顯示元件。若於減壓進行基板之貼合，則可以極高之效率製造液晶顯示元件，現在該滴下工法成為液晶顯示元件之製造方法之主流。In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display unit, the use of light and heat as disclosed in Patent Documents 1 and 2 has been adopted from the viewpoints of shortening the production tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dripping method using a hardening type sealant together.
In the dropping method, first, a frame-shaped sealing pattern is formed on one of two transparent substrates with electrodes by drip coating. Next, in the state where the sealant is not hardened, small droplets of liquid crystal are dropped on the entire surface of the frame of the transparent substrate, and another transparent substrate is immediately bonded, and the sealed portion is irradiated with light such as ultraviolet rays to be pre-cured. Thereafter, the liquid crystal display element is produced by heating and performing main hardening during the annealing of the liquid crystal. If the substrates are bonded under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency. Now, the dripping method has become the mainstream of the manufacturing method of the liquid crystal display element.
然而，於行動電話、攜帶型遊戲機等各種附液晶面板之可攜式機器普及之現代，裝置之小型化係最為需求之課題。作為裝置之小型化之方法，可列舉液晶顯示部之窄邊緣化，例如進行有將密封部之位置配置於黑矩陣下（以下，亦稱為窄邊緣設計）。However, in modern mobile phones, portable game machines, and other portable devices with a liquid crystal panel, the miniaturization of devices is the most demanded problem in modern times. As a method of miniaturizing the device, narrow edge of the liquid crystal display portion can be cited. For example, the position of the sealing portion is arranged under a black matrix (hereinafter, also referred to as narrow edge design).
然而，於窄邊緣設計中，由於密封劑配置於黑矩陣之正下方，故而當進行滴下工法時，存在使密封劑光硬化時所照射之光被遮擋，光無法到達密封劑之內部而使硬化變得不充分之問題。當如上所述密封劑之硬化變得不充分時，存在如下問題：未硬化之密封劑成分溶出於液晶中，由於溶出之密封劑成分而發生之硬化反應於液晶中進行，由此產生液晶污染。However, in the narrow-edge design, since the sealant is disposed directly below the black matrix, when the dripping method is performed, there is a light blocking when the sealant is light-cured, and the light cannot reach the interior of the sealant to harden. The problem of becoming insufficient. When the hardening of the sealant becomes insufficient as described above, there is a problem that the unhardened sealant component dissolves in the liquid crystal, and the hardening reaction due to the dissolved sealant component proceeds in the liquid crystal, thereby causing liquid crystal contamination. .
又，通常，進行紫外線之照射作為使密封劑光硬化之方法，但尤其是於液晶滴下工法中，由於在滴下液晶後使密封劑硬化，故而存在因照射紫外線而導致液晶劣化之問題。因此，為了防止由紫外線所導致之液晶之劣化，進行有藉由介隔截止濾光器等之可見光區域之長波長之光而進行之光硬化。作為藉由長波長之光使密封劑光硬化之方法，考慮組合對於長波長之光之感度高之增感劑與光聚合起始劑而使用之方法。例如，於專利文獻3及專利文獻4中，揭示有組合光聚合起始劑與增感劑進行摻合所得之光硬化性樹脂組成物。然而，於使用該等光硬化性樹脂組成物作為液晶顯示元件用密封劑之情形時，存在如下問題：為了藉由長波長之光充分地進行光硬化，而使光聚合起始劑與增感劑之合計量變多，由此有時會產生液晶污染。
先前技術文獻
專利文獻In general, ultraviolet rays are irradiated as a method for photo-curing the sealant. However, particularly in the liquid crystal dropping method, since the sealant is cured after the liquid crystal is dropped, there is a problem that the liquid crystal is deteriorated due to ultraviolet rays. Therefore, in order to prevent deterioration of the liquid crystal caused by ultraviolet rays, light hardening is performed by blocking long-wavelength light in a visible light region such as a cut filter. As a method of photo-hardening the sealant with light of a long wavelength, a method of combining a sensitizer with a high sensitivity to light of a long wavelength and a photopolymerization initiator is considered. For example, Patent Documents 3 and 4 disclose photocurable resin compositions obtained by combining a photopolymerization initiator and a sensitizer and blending them. However, when such a photocurable resin composition is used as a sealant for a liquid crystal display element, there is a problem in that a photopolymerization initiator and a sensitizer are used to sufficiently perform photocuring by light having a long wavelength. When the total amount of the agents is increased, liquid crystal contamination may occur.
Prior art literature patent literature
專利文獻1：日本特開2001-133794號公報
專利文獻2：國際公開第02/092718號
專利文獻3：日本特開2017-125033號公報
專利文獻4：國際公開第2017/130594號Patent Literature 1: Japanese Patent Laid-Open No. 2001-133794 Patent Literature 2: International Publication No. 02/092718 Patent Literature 3: Japanese Patent Publication No. 2017-125033 Patent Literature 4: International Publication No. 2017/130594
[發明所欲解決之課題][Problems to be Solved by the Invention]
本發明之目的在於提供一種對於長波長之光之反應性優異之光聚合起始劑。又，本發明之目的在於提供一種顯示元件用密封劑、以及使用該顯示元件用密封劑而成之上下導通材料及顯示元件，該顯示元件用密封劑含有該光聚合起始劑，對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。進而，本發明之目的在於提供一種構成該光聚合起始劑之化合物。
[解決課題之技術手段]An object of the present invention is to provide a photopolymerization initiator excellent in reactivity with light having a long wavelength. Another object of the present invention is to provide a sealant for a display element, and a top-to-bottom conduction material and a display element using the sealant for a display element. The sealant for a display element contains the photopolymerization initiator, and has a long wavelength. The light has excellent curability and is also excellent in low liquid crystal contamination when used in a liquid crystal display element. Furthermore, an object of the present invention is to provide a compound constituting the photopolymerization initiator.
[Technical means to solve the problem]
本發明係一種光聚合起始劑，其係具有可經羥基取代之9-氧硫 基（thioxanthonyl）及胺基之化合物者，且以濃度成為0.1 mg/mL之方式溶解於乙腈時之在波長420 nm之吸光度為0.10以上。
以下詳細描述本發明。The present invention is a photopolymerization initiator, which has 9-oxysulfur which can be substituted by a hydroxyl group. For thioxanthonyl and amine compounds, the absorbance at a wavelength of 420 nm when dissolved in acetonitrile so that the concentration becomes 0.1 mg / mL is 0.10 or more.
The present invention is described in detail below.
本發明者發現，具有可經羥基取代之9-氧硫 基及胺基且於420 nm具有較高之吸光度的化合物對於可見光區域之長波長之光之反應性優異，且於光照射後幾乎不產生成為液晶污染之原因之殘渣。因此，本發明者發現，藉由使用該化合物作為光聚合起始劑，可獲得對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異之顯示元件用密封劑，從而完成本發明。The present inventors have discovered that the Compounds with amino and amine groups and high absorbance at 420 nm are excellent in reactivity to long-wavelength light in the visible light region, and hardly cause residues that cause liquid crystal contamination after light irradiation. Therefore, the present inventors have found that by using the compound as a photopolymerization initiator, a display element having excellent curability against long-wavelength light and excellent low liquid crystal contamination when used in a liquid crystal display element can be obtained. With a sealant, the present invention is completed.
本發明之光聚合起始劑係具有可經羥基取代之9-氧硫 基及胺基之化合物。
藉由為上述具有可經羥基取代之9-氧硫 基及胺基之化合物且顯示下述吸光度者，本發明之光聚合起始劑即便於少量摻合之情形時，硬化性樹脂組成物亦具有優異之光硬化性。因此，於使用該硬化性樹脂組成物作為液晶顯示元件用密封劑之情形時，低液晶污染性優異。
於本發明之光聚合起始劑中，上述9-氧硫 基具有藉由光照射進行脫氫或裂解等而產生自由基從而促進聚合性化合物之聚合反應之作用。又，於本發明之光聚合起始劑中，上述胺基具有藉由光照射進行能量轉移等而對上述9-氧硫 基發揮增感效果之作用。
再者，於本說明書中，上述「9-氧硫 基」意指9-側氧基-9H-硫 -基。The photopolymerization initiator of the present invention has 9-oxysulfur which can be substituted by a hydroxyl group. And amino compounds.
By having the above-mentioned 9-oxysulfur which can be substituted by a hydroxyl group In the case of a compound having an amino group and an amine group and exhibiting the following absorbance, the curable resin composition has excellent photocurability even when the photopolymerization initiator of the present invention is blended in a small amount. Therefore, when this curable resin composition is used as a sealing agent for liquid crystal display elements, it is excellent in low liquid-crystal stain | pollution property.
In the photopolymerization initiator of the present invention, the above 9-oxysulfur The radical has a function of generating radicals by dehydrogenation or cleavage by light irradiation to promote the polymerization reaction of the polymerizable compound. Further, in the photopolymerization initiator of the present invention, the amine group has a function of transferring the 9-oxysulfur to the energy by light irradiation or the like. The base plays the role of sensitization.
Furthermore, in this specification, the above-mentioned "9-oxysulfur Means `` 9- pendant oxy-9H-sulfur -base.
作為上述胺基，就成為對於長波長之光之反應性更優異者而言，較佳為一級胺基或二烷基胺基，更佳為二烷基胺基，進而更佳為二甲基胺基。
又，本發明之光聚合起始劑較佳為具有4-(N,N-二烷基胺基)苯甲醯氧基作為包含上述二烷基胺基之基，更佳為具有4-(N,N-二甲基胺基)苯甲醯氧基。The amine group is more preferably a primary amine group or a dialkyl amine group, more preferably a dialkyl amine group, and even more preferably a dimethyl group in order to be more excellent in reactivity with light having a long wavelength. Amine.
The photopolymerization initiator of the present invention preferably has 4- (N, N-dialkylamino) benzyloxy as a group containing the above-mentioned dialkylamino group, and more preferably has 4- ( N, N-dimethylamino) benzyloxy.
本發明之光聚合起始劑就低液晶污染性之觀點而言，較佳為具有羥基，更佳為1分子中具有2個以上之羥基。From the viewpoint of low liquid crystal contamination, the photopolymerization initiator of the present invention preferably has a hydroxyl group, and more preferably has two or more hydroxyl groups in one molecule.
本發明之光聚合起始劑就低液晶污染性之觀點而言，分子量較佳為200以上，更佳為400以上。
本發明之光聚合起始劑之分子量之較佳之上限並無特別，但實質之上限為3萬。
再者，於本說明書中，上述「分子量」就分子結構特定之化合物而言係由結構式求得之分子量，但就聚合度之分佈較廣之化合物及改質部位未特定之化合物而言存在使用數量平均分子量表示之情形。又，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）使用四氫呋喃作為溶劑進行測定並藉由聚苯乙烯換算所求得之值。作為藉由GPC測定由聚苯乙烯換算所獲得之數量平均分子量時所使用之管柱，例如可列舉：Shodex LF-804（昭和電工公司製造）等。From the viewpoint of low liquid crystal contamination, the photopolymerization initiator of the present invention preferably has a molecular weight of 200 or more, more preferably 400 or more.
The preferable upper limit of the molecular weight of the photopolymerization initiator of the present invention is not particularly limited, but the practical upper limit is 30,000.
In addition, in the present specification, the "molecular weight" is a molecular weight obtained from a structural formula for a compound having a specific molecular structure, but exists for a compound having a wide distribution of polymerization degree and a compound having no specific modification site. Use number average molecular weight. In addition, in this specification, the said "quantity average molecular weight" is the value calculated | required by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and calculated | required by polystyrene conversion. Examples of the column used when measuring the number average molecular weight obtained by polystyrene conversion by GPC include Shodex LF-804 (manufactured by Showa Denko Corporation).
本發明之光聚合起始劑以濃度成為0.1 mg/mL之方式溶解於乙腈時之在波長420 nm之吸光度為0.10以上。藉由使上述波長420 nm之吸光度為0.10以上，本發明之光聚合起始劑可良好地用於藉由可見光區域之長波長之光進行硬化之顯示元件用密封劑等。
上述吸光度更佳為0.15以上。
上述吸光度可使用分光光度計於光程長度1 cm之條件進行測定。作為上述分光光度計，例如可列舉：U-3900（Hitachi High-Tech Science公司製造）等。When the photopolymerization initiator of the present invention is dissolved in acetonitrile so that the concentration becomes 0.1 mg / mL, the absorbance at a wavelength of 420 nm is 0.10 or more. When the absorbance at the above-mentioned wavelength of 420 nm is 0.10 or more, the photopolymerization initiator of the present invention can be suitably used for a sealant for a display element and the like which is hardened by long-wavelength light in the visible light region.
The absorbance is more preferably 0.15 or more.
The above-mentioned absorbance can be measured using a spectrophotometer under the condition of an optical path length of 1 cm. Examples of the spectrophotometer include U-3900 (manufactured by Hitachi High-Tech Science).
本發明之光聚合起始劑具體而言較佳為下述式（1-1）或（1-2）所表示之化合物，更佳為下述式（2-1）、（2-2）或（2-3）所表示之化合物。下述式（2-1）、（2-2）或（2-3）所表示之化合物亦為本發明之一。Specifically, the photopolymerization initiator of the present invention is preferably a compound represented by the following formula (1-1) or (1-2), more preferably the following formulae (2-1), (2-2) Or the compound represented by (2-3). The compound represented by the following formula (2-1), (2-2) or (2-3) is also one aspect of the present invention.
式（1-1）及（1-2）中，R1
為可經羥基取代之碳數1~20之伸烷基、或可經羥基取代之碳數1~20之(聚)伸烷氧基，R2
分別獨立為氫原子或胺基，且至少1個R2
為胺基。
作為上述R2
所表示之胺基，較佳為一級胺基、二甲基胺基或二乙基胺基。In the formulae (1-1) and (1-2), R 1 is an alkylene group having 1 to 20 carbon atoms which may be substituted by a hydroxyl group, or a (poly) alkylene oxide group having 1 to 20 carbon atoms which may be substituted by a hydroxyl group. And R 2 are each independently a hydrogen atom or an amine group, and at least one R 2 is an amine group.
As the amine group represented by the aforementioned R 2 , a primary amine group, a dimethylamino group, or a diethylamino group is preferable.
含有硬化性樹脂與本發明之光聚合起始劑之顯示元件用密封劑亦為本發明之一。
本發明之顯示元件用密封劑由於含有本發明之光聚合起始劑，故而對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。即，本發明之顯示元件用密封劑可作為液晶顯示元件用密封劑而良好地用於液晶顯示元件。The sealant for display elements containing a curable resin and the photopolymerization initiator of the present invention is also one aspect of the present invention.
Since the sealant for display elements of the present invention contains the photopolymerization initiator of the present invention, it has excellent curability against long-wavelength light, and also has low liquid crystal contamination when used in a liquid crystal display element. That is, the sealant for display elements of this invention can be used suitably for a liquid crystal display element as a sealant for liquid crystal display elements.
作為本發明之顯示元件用密封劑中之本發明之光聚合起始劑之含量，相對於硬化性樹脂100重量份，較佳之下限為0.01重量份，較佳之上限為5重量份。藉由使本發明之光聚合起始劑之含量為該範圍，獲得之顯示元件用密封劑對於長波長之光之硬化性更加優異，且於用於液晶顯示元件之情形時使兼具對於長波長之光之硬化性及低液晶污染性之效果更加優異。本發明之光聚合起始劑之含量之更佳之下限為0.5重量份，更佳之上限為3重量份。The content of the photopolymerization initiator of the present invention in the sealant for display elements of the present invention is preferably a lower limit of 0.01 part by weight and a preferable upper limit of 5 parts by weight based on 100 parts by weight of the curable resin. By setting the content of the photopolymerization initiator of the present invention to be in this range, the obtained sealant for a display element is more excellent in curing property against light with a long wavelength, and when used in a liquid crystal display element, it has both a The effect of the light-wavelength hardening property and the low liquid crystal pollution property is more excellent. A more preferable lower limit of the content of the photopolymerization initiator of the present invention is 0.5 part by weight, and a more preferable upper limit is 3 parts by weight.
本發明之顯示元件用密封劑含有硬化性樹脂。
上述硬化性樹脂較佳為含有(甲基)丙烯酸化合物。
作為上述(甲基)丙烯酸化合物，例如可列舉：(甲基)丙烯酸酯化合物、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺酯等。其中，較佳為環氧(甲基)丙烯酸酯。又，上述(甲基)丙烯酸化合物就反應性之觀點而言，較佳為分子中具有2個以上之(甲基)丙烯醯基者。
再者，於本說明書中，上述「(甲基)丙烯酸」意指丙烯酸或甲基丙烯酸，上述「(甲基)丙烯酸化合物」意指具有(甲基)丙烯醯基之化合物，上述「(甲基)丙烯醯基」意指丙烯醯基或甲基丙烯醯基。又，上述「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯。進而，上述「環氧(甲基)丙烯酸酯」表示使環氧化合物中之所有環氧基與(甲基)丙烯酸反應所得之化合物。The sealant for display elements of this invention contains a curable resin.
The curable resin preferably contains a (meth) acrylic compound.
Examples of the (meth) acrylic compound include (meth) acrylate compounds, epoxy (meth) acrylates, and (meth) acrylates. Among these, epoxy (meth) acrylate is preferable. Moreover, it is preferable that the said (meth) acrylic compound has two (meth) acryl fluorenyl groups in a molecule | numerator from a viewpoint of reactivity.
In addition, in the present specification, the "(meth) acrylic acid" means acrylic acid or methacrylic acid, the "(meth) acrylic compound" means a compound having a (meth) acryl group, and the "(formaldehyde "Meth) acrylfluorenyl" means acrylfluorenyl or methacrylfluorenyl. The "(meth) acrylate" means an acrylate or a methacrylate. Furthermore, the "epoxy (meth) acrylate" means a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.
作為上述(甲基)丙烯酸酯化合物中之單官能者，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、醯亞胺(甲基)丙烯酸酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、鄰苯二甲酸2-(甲基)丙烯醯氧基乙基2-羥基丙酯、磷酸2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸縮水甘油酯等。Examples of the monofunctional compound in the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate. Ester, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate , Isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Isoamyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxy (meth) acrylate Ethyl ester, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylates, phenoxy diethylene glycol (Meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate, (meth) acrylate 2, 2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, fluorenimine (meth) Acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloxyethyl succinic acid, 2- (methyl) Acrylic ethoxyethyl hexahydrophthalic acid, 2- (meth) acrylic ethoxyethyl 2-hydroxypropyl phthalate, 2- (meth) acrylic ethoxyethyl phosphate, ( Glycidyl meth) acrylate and the like.
又，作為上述(甲基)丙烯酸酯化合物中之2官能者，例如可列舉：1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、二(甲基)丙烯酸二羥甲基二環戊二烯酯、環氧乙烷改質異三聚氰酸二(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、碳酸酯二醇二(甲基)丙烯酸酯、聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己內酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。Examples of the bifunctional compound in the (meth) acrylate compound include 1,3-butanediol di (meth) acrylate and 1,4-butanediol di (meth) acrylate. , 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl Alcohol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene di (meth) acrylate, ethylene oxide modified isotricyanate di (meth) acrylate, (meth) acrylic acid 2-Hydroxy-3- (meth) propylene ethoxypropyl ester, carbonate diol di (meth) propylene Ester, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) ) Acrylate, etc.
又，作為上述(甲基)丙烯酸酯化合物中之3官能以上者，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成異三聚氰酸三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、環氧丙烷加成甘油三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、磷酸三(甲基)丙烯醯氧基乙酯、二(三羥甲基丙烷)四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等。In addition, examples of the tri- or more functional group in the (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri (methyl) ) Acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, ethylene oxide addition isocyanuric acid Acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, neopentyl tetraol tri (meth) acrylate, phosphate tri (meth) acrylate Acrylic ethoxyethyl, bis (trimethylolpropane) tetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dixin Pentaerythritol hexa (meth) acrylate and the like.
作為上述環氧(甲基)丙烯酸酯，例如可列舉藉由按照慣例於鹼性觸媒之存在下使環氧化合物與(甲基)丙烯酸進行反應而獲得者等。Examples of the epoxy (meth) acrylic acid ester include those obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a basic catalyst in a conventional manner.
作為成為用於合成上述環氧(甲基)丙烯酸酯之原料之環氧化合物，例如可列舉：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚S型環氧化合物、2,2'-二烯丙基雙酚A型環氧化合物、氫化雙酚型環氧化合物、環氧丙烷加成雙酚A型環氧化合物、間苯二酚型環氧化合物、聯苯型環氧化合物、硫醚型環氧化合物、二苯醚型環氧化合物、二環戊二烯型環氧化合物、萘型環氧化合物、酚系酚醛清漆型環氧化合物、鄰甲酚酚醛清漆型環氧化合物、二環戊二烯酚醛清漆型環氧化合物、聯苯酚醛清漆型環氧化合物、萘酚系酚醛清漆型環氧化合物、縮水甘油胺型環氧化合物、烷基多元醇型環氧化合物、橡膠改質型環氧化合物、縮水甘油酯化合物等。Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate include, for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, 2 , 2'-diallyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide addition bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl ring Oxygen compounds, thioether type epoxy compounds, diphenyl ether type epoxy compounds, dicyclopentadiene type epoxy compounds, naphthalene type epoxy compounds, phenol novolac type epoxy compounds, o-cresol novolac type rings Oxygen compounds, dicyclopentadiene novolac epoxy compounds, biphenol novolac epoxy compounds, naphthol novolac epoxy compounds, glycidylamine epoxy compounds, alkyl polyol epoxy compounds , Rubber modified epoxy compounds, glycidyl ester compounds, etc.
作為上述雙酚A型環氧化合物中之市售者，例如可列舉：jER828EL、jER1004（皆為三菱化學公司製造）、Epiclon 850CRP（DIC公司製造）等。
作為上述雙酚F型環氧化合物中之市售者，例如可列舉：jER806、jER4004（皆為三菱化學公司製造）等。
作為上述雙酚S型環氧化合物中之市售者，例如可列舉：Epiclon EXA1514（DIC公司製造）等。
作為上述2,2'-二烯丙基雙酚A型環氧化合物中之市售者，例如可列舉：RE-810NM（日本化藥公司製造）等。
作為上述氫化雙酚型環氧化合物中之市售者，例如可列舉：Epiclon EXA7015（DIC公司製造）等。
作為上述環氧丙烷加成雙酚A型環氧化合物中之市售者，例如可列舉：EP-4000S（ADEKA公司製造）等。
作為上述間苯二酚型環氧化合物中之市售者，例如可列舉：EX-201（Nagase chemteX公司製造）等。
作為上述聯苯型環氧化合物中之市售者，例如可列舉：jER YX-4000H（三菱化學公司製造）等。
作為上述硫醚型環氧化合物中之市售者，例如可列舉：YSLV-50TE（NIPPON STEEL Chemical & Material公司製造）等。
作為上述二苯醚型環氧化合物中之市售者，例如可列舉：YSLV-80DE（NIPPON STEEL Chemical & Material公司製造）等。
作為上述二環戊二烯型環氧化合物中之市售者，例如可列舉：EP-4088S（ADEKA公司製造）等。
作為上述萘型環氧化合物中之市售者，例如可列舉：Epiclon HP4032、Epiclon EXA-4700（皆為DIC公司製造）等。
作為上述酚系酚醛清漆型環氧化合物中之市售者，例如可列舉：Epiclon N-770（DIC公司製造）等。
作為上述鄰甲酚酚醛清漆型環氧化合物中之市售者，例如可列舉：Epiclon N-670-EXP-S（DIC公司製造）等。
作為上述二環戊二烯酚醛清漆型環氧化合物中之市售者，例如可列舉：Epiclon HP7200（DIC公司製造）等。
作為上述聯苯酚醛清漆型環氧化合物中之市售者，例如可列舉：NC-3000P（日本化藥公司製造）等。
作為上述萘酚系酚醛清漆型環氧化合物中之市售者，例如可列舉：ESN-165S（NIPPON STEEL Chemical & Material公司製造）等。
作為上述縮水甘油胺型環氧化合物中之市售者，例如可列舉：jER630（三菱化學公司製造）、Epiclon 430（DIC公司製造）、TETRAD-X（三菱瓦斯化學公司製造）等。
作為上述烷基多元醇型環氧化合物中之市售者，例如可列舉：ZX-1542（NIPPON STEEL Chemical & Material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。
作為上述橡膠改質型環氧化合物中之市售者，例如可列舉：YR-450、YR-207（皆為NIPPON STEEL Chemical & Material公司製造）、Epolead PB（Daicel公司製造）等。
作為上述縮水甘油酯化合物中之市售者，例如可列舉：DENACOL EX-147（Nagase chemteX公司製造）等。
作為上述環氧化合物中之其他市售者，例如可列舉：YDC-1312、YSLV-80XY、YSLV-90CR（皆為NIPPON STEEL Chemical & Material公司製造）、XAC4151（旭化成公司製造）、jER1031、jER1032（皆為三菱化學公司製造）、EXA-7120（DIC公司製造）、TEPIC（日產化學公司製造）等。Examples of commercially available bisphenol A epoxy compounds include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), Epiclon 850CRP (manufactured by DIC Corporation), and the like.
Examples of a commercially available bisphenol F-type epoxy compound include jER806, jER4004 (both manufactured by Mitsubishi Chemical Corporation), and the like.
As a commercially available one among the said bisphenol S-type epoxy compounds, Epiclon EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
As a marketer among the said 2,2'- diallyl bisphenol A type epoxy compounds, RE-810NM (made by Nippon Kayakusho), etc. are mentioned, for example.
As a commercially available one of the said hydrogenated bisphenol-type epoxy compounds, Epiclon EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
As a marketer among the said propylene oxide addition bisphenol A type epoxy compounds, EP-4000S (made by ADEKA company) etc. are mentioned, for example.
As a marketer among the said resorcinol-type epoxy compounds, EX-201 (made by Nagase chemteX company) etc. are mentioned, for example.
Examples of a commercially available biphenyl type epoxy compound include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like.
Examples of a commercially available thioether-type epoxy compound include YSLV-50TE (manufactured by NIPPON STEEL Chemical & Material).
As a marketer of the said diphenyl ether type epoxy compound, YSLV-80DE (made by NIPPON STEEL Chemical & Material company) etc. are mentioned, for example.
As a marketer of the said dicyclopentadiene-type epoxy compound, EP-4088S (made by ADEKA company) etc. are mentioned, for example.
As a commercially available one among the above naphthalene-type epoxy compounds, Epiclon HP4032, Epiclon EXA-4700 (all manufactured by DIC Corporation), and the like can be cited.
As a commercially available one among the said phenolic novolak-type epoxy compounds, Epiclon N-770 (made by DIC Corporation) etc. are mentioned, for example.
As a commercially available one among the above-mentioned ortho-cresol novolak-type epoxy compounds, Epiclon N-670-EXP-S (made by DIC Corporation) etc. can be mentioned, for example.
As a marketer of the said dicyclopentadiene novolak-type epoxy compound, Epiclon HP7200 (made by DIC Corporation) etc. are mentioned, for example.
As a marketer of the said biphenol novolak-type epoxy compound, NC-3000P (made by Nippon Kayakusho), etc. are mentioned, for example.
As a marketer of the said naphthol-type novolak-type epoxy compound, ESN-165S (made by NIPPON STEEL Chemical & Material) etc. are mentioned, for example.
Examples of a commercially available glycidylamine type epoxy compound include jER630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like.
Examples of the commercially available alkyl polyol type epoxy compound include ZX-1542 (manufactured by NIPPON STEEL Chemical & Material), Epiclon 726 (manufactured by DIC), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) ), DENACOL EX-611 (manufactured by Nagase chemteX), etc.
Examples of commercially available rubber modified epoxy compounds include YR-450, YR-207 (both manufactured by NIPPON STEEL Chemical & Material), Epolead PB (made by Daicel), and the like.
Examples of a commercially available glycidyl ester compound include DENACOL EX-147 (manufactured by Nagase ChemteX) and the like.
Examples of other commercially available epoxy compounds include: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NIPPON STEEL Chemical & Material), 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), etc.
作為上述環氧(甲基)丙烯酸酯中之市售者，例如可列舉：Daicel-Allnex公司製造之環氧(甲基)丙烯酸酯、新中村化學工業公司製造之環氧(甲基)丙烯酸酯、共榮社化學公司製造之環氧(甲基)丙烯酸酯、Nagase chemteX公司製造之環氧(甲基)丙烯酸酯等。
作為上述Daicel-Allnex公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3708、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182等。
作為上述新中村化學工業公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020等。
作為上述共榮社化學公司製造之環氧(甲基)丙烯酸酯，例如可列舉：環氧酯M-600A、環氧酯40EM、環氧酯70PA、環氧酯200PA、環氧酯80MFA、環氧酯3002M、環氧酯3002A、環氧酯1600A、環氧酯3000M、環氧酯3000A、環氧酯200EA、環氧酯400EA等。
作為上述Nagase chemteX公司製造之環氧(甲基)丙烯酸酯，例如可列舉：DENACOL ACRYLATE DA-141、DENACOL ACRYLATE DA-314、DENACOL ACRYLATE DA-911等。Examples of the commercially available epoxy (meth) acrylates include epoxy (meth) acrylates manufactured by Daicel-Allnex, and epoxy (meth) acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd. , Epoxy (meth) acrylates manufactured by Kyoeisha Chemical Co., Ltd., epoxy (meth) acrylates manufactured by Nagase chemteX, etc.
Examples of the epoxy (meth) acrylate of the above-described manufacturing company Daicel-Allnex include, for example: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182 like.
Examples of the epoxy (meth) acrylate manufactured by the aforementioned Shin Nakamura Chemical Industry Company include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.
Examples of the epoxy (meth) acrylate manufactured by the aforementioned Kyoeisha Chemical Co., Ltd. include epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, ring Oxyester 3002M, epoxy ester 3002A, epoxy ester 1600A, epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA, etc.
Examples of the epoxy (meth) acrylate manufactured by the aforementioned Nagase chemteX company include DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-911, and the like.
上述(甲基)丙烯酸胺酯例如可藉由於觸媒量之錫系化合物存在下使具有羥基之(甲基)丙烯酸衍生物對異氰酸酯化合物進行反應而獲得。The (meth) acrylic acid amine ester can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalyst-based tin-based compound.
作為上述異氰酸酯化合物，例如可列舉：異佛爾酮二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯（MDI）、氫化MDI、聚合MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯（XDI）、氫化XDI、離胺酸二異氰酸酯、三苯基甲烷三異氰酸酯、硫代磷酸三(異氰酸基苯基)酯、四甲基苯二甲基二異氰酸酯、1,6,11-十一烷三異氰酸酯等。Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diisocyanate. Phenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzylamine diisocyanate, xylylene diisocyanate (XDI) , Hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanophenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecane Triisocyanate, etc.
又，作為上述異氰酸酯化合物，亦可使用藉由多元醇與過量之異氰酸酯化合物之反應所獲得之經鏈伸長之異氰酸酯化合物。
作為上述多元醇，例如可列舉：乙二醇、丙二醇、甘油、山梨醇、三羥甲基丙烷、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等。As the isocyanate compound, a chain-elongated isocyanate compound obtained by reacting a polyol with an excessive amount of an isocyanate compound can also be used.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
作為上述具有羥基之(甲基)丙烯酸衍生物，例如可列舉：單(甲基)丙烯酸羥烷基酯、二元醇之單(甲基)丙烯酸酯、三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯等。
作為上述單(甲基)丙烯酸羥烷基酯，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。
作為上述二元醇，例如可列舉：乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、聚乙二醇等。
作為上述三元醇，例如可列舉：三羥甲基乙烷、三羥甲基丙烷、甘油等。
作為上述環氧(甲基)丙烯酸酯，例如可列舉：雙酚A型環氧丙烯酸酯等。Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of a diol, and mono (meth) acrylic acid of a triol. Esters or di (meth) acrylates, epoxy (meth) acrylates, and the like.
Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like 4-hydroxybutyl (meth) acrylate and the like.
Examples of the glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
Examples of the triol include trimethylolethane, trimethylolpropane, and glycerol.
Examples of the epoxy (meth) acrylate include a bisphenol A epoxy acrylate and the like.
作為上述(甲基)丙烯酸胺酯中之市售者，例如可列舉：東亞合成公司製造之(甲基)丙烯酸胺酯、Daicel-Allnex公司製造之(甲基)丙烯酸胺酯、根上工業公司製造之(甲基)丙烯酸胺酯、新中村化學工業公司製造之(甲基)丙烯酸胺酯、共榮社化學公司製造之(甲基)丙烯酸胺酯等。
作為上述東亞合成公司製造之(甲基)丙烯酸胺酯，例如可列舉：M-1100、M-1200、M-1210、M-1600等。
作為上述Daicel-Allnex公司製造之(甲基)丙烯酸胺酯，例如可列舉：EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、EBECRYL8803、EBECRYL8804、EBECRYL8807、EBECRYL9260等。
作為上述根上工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：Artresin UN-330、Artresin SH-500B、Artresin UN-1200TPK、Artresin UN-1255、Artresin UN-3320HB、Artresin UN-7100、Artresin UN-9000A、Artresin UN-9000H等。
作為上述新中村化學工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6HA、U-6LPA、U-10H、U-15HA、U-108、U-108A、U-122A、U-122P、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4000、UA-4100、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A等。
作為上述共榮社化學公司製造之(甲基)丙烯酸胺酯，例如可列舉：AH-600、AI-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T等。As a marketer among the above (meth) acrylic acid amine esters, for example, (meth) acrylic acid esters manufactured by Toa Kosei Co., Ltd., (meth) acrylic acid amine esters manufactured by Daicel-Allnex Co., Ltd. (Meth) acrylates, amine (meth) acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd., and (meth) acrylates manufactured by Kyoeisha Chemical Co., Ltd.
Examples of the (meth) acrylic acid amine ester manufactured by the Toa Synthesis Corporation include M-1100, M-1200, M-1210, and M-1600.
Examples of the (meth) acrylic acid amine esters manufactured by the above-mentioned Daicel-Allnex company include, for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700 EBECRYL9260 and so on.
Examples of the (meth) acrylic acid amine esters manufactured by the above-mentioned Kyungsang Kogyo include Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H, etc.
Examples of the (meth) acrylic acid amine ester manufactured by the aforementioned Shin Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U -10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000 , UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc.
Examples of the (meth) acrylic acid amine manufactured by Kyoeisha Chemical Co., Ltd. include, for example, AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA -306T and so on.
上述硬化性樹脂以提高獲得之顯示元件用密封劑之接著性等為目的，較佳為含有環氧化合物。作為上述環氧化合物，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化合物、或部分(甲基)丙烯醯基改質環氧化合物等。
再者，於本說明書中，上述部分(甲基)丙烯醯基改質環氧化合物意指1分子中分別具有1個以上之環氧基與(甲基)丙烯醯基之化合物，例如可藉由使1分子中具有2個以上之環氧基的環氧化合物之一部分環氧基與(甲基)丙烯酸反應而獲得。The curable resin preferably contains an epoxy compound for the purpose of improving the adhesiveness of the obtained sealant for a display element. Examples of the epoxy compound include an epoxy compound that is a raw material for synthesizing the epoxy (meth) acrylate, or a partially (meth) acrylfluorenyl-modified epoxy compound.
In addition, in the present specification, the above-mentioned (meth) acrylfluorenyl-modified epoxy compound means a compound having one or more epoxy groups and (meth) acrylfluorene groups in one molecule, for example, it can be borrowed It is obtained by reacting a part of epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth) acrylic acid.
於含有上述(甲基)丙烯酸化合物與上述環氧化合物作為上述硬化性樹脂之情形時、或於含有上述部分(甲基)丙烯醯基改質環氧化合物作為上述硬化性樹脂之情形時，較佳為使上述硬化性樹脂中之(甲基)丙烯醯基與環氧基之合計中之(甲基)丙烯醯基之比率成為30莫耳%以上95莫耳%以下。藉由使上述(甲基)丙烯醯基之比率為該範圍，於將獲得之顯示元件用密封劑用於液晶顯示元件之情形時，抑制液晶污染之產生並且接著性更加優異。When the (meth) acrylic compound and the epoxy compound are contained as the curable resin, or when the (meth) acrylfluorenyl-modified epoxy compound is contained as the curable resin, the Preferably, the ratio of the (meth) acrylfluorenyl group in the said curable resin and the (meth) acrylfluorenyl group in the total of an epoxy group becomes 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acrylfluorenyl group is within this range, when the obtained sealant for a display element is used for a liquid crystal display element, the occurrence of liquid crystal contamination is suppressed and adhesion is more excellent.
上述硬化性樹脂就抑制液晶污染等觀點而言，較佳為具有-OH基、-NH-基、-NH2 基等氫鍵結性單元者。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, and an -NH 2 group.
上述硬化性樹脂可單獨使用，亦可組合2種以上使用。These curable resins may be used alone or in combination of two or more.
本發明之顯示元件用密封劑亦可於不妨礙本發明之目的之範圍內含有熱聚合起始劑。
作為上述熱聚合起始劑，例如可列舉：偶氮化合物、有機過氧化物等。其中，較佳為高分子偶氮化合物。
上述熱聚合起始劑可單獨使用，亦可組合2種以上使用。
再者，於本說明書中，上述「高分子偶氮化合物」意指具有偶氮基且藉由熱而生成可使(甲基)丙烯醯氧基硬化之自由基之數量平均分子量為300以上之化合物。The sealant for display elements of this invention may contain a thermal-polymerization initiator in the range which does not prevent the objective of this invention.
Examples of the thermal polymerization initiator include an azo compound and an organic peroxide. Among these, a polymer azo compound is preferable.
These thermal polymerization initiators may be used alone or in combination of two or more.
In addition, in the present specification, the above-mentioned "polymer azo compound" means that the number average molecular weight of a radical having an azo group and capable of hardening a (meth) acryloxy group by heat is 300 or more Compound.
上述高分子偶氮化合物之數量平均分子量之較佳之下限為1000，較佳之上限為30萬。藉由使上述高分子偶氮化合物之數量平均分子量為該範圍，於將獲得之顯示元件用密封劑用於液晶顯示元件之情形時，可抑制液晶污染並且容易地與硬化性樹脂混合。上述高分子偶氮化合物之數量平均分子量之更佳之下限為5000，更佳之上限為10萬，進而較佳之下限為1萬，進而較佳之上限為9萬。A preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 1,000, and a preferable upper limit is 300,000. When the number average molecular weight of the above-mentioned polymer azo compound is within this range, when the obtained sealant for a display element is used for a liquid crystal display element, liquid crystal contamination can be suppressed and easily mixed with a curable resin. A more preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 5000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a more preferable upper limit is 90,000.
作為上述高分子偶氮化合物，例如可列舉具有經由偶氮基而鍵結有多個聚環氧烷或聚二甲基矽氧烷等單元之結構者。
作為上述具有經由偶氮基而鍵結有多個聚環氧烷等單元之結構之高分子偶氮化合物，較佳為具有聚環氧乙烷結構者。
作為上述高分子偶氮化合物，具體而言，例如可列舉：4,4'-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之縮聚物、或4,4'-偶氮雙(4-氰基戊酸)與末端具有胺基之聚二甲基矽氧烷之縮聚物等。
作為上述高分子偶氮化合物中之市售者，例如可列舉：VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001（皆為FUJIFILM Wako Pure Chemical公司製造）等。
又，作為非高分子之偶氮化合物，例如可列舉：V-65、V-501（皆為FUJIFILM Wako Pure Chemical公司製造）等。Examples of the polymer azo compound include a structure having a plurality of units such as polyalkylene oxide or polydimethylsiloxane bonded via an azo group.
As the polymer azo compound having a structure in which a plurality of units such as a polyalkylene oxide are bonded via an azo group, a polymer having a polyethylene oxide structure is preferred.
Specific examples of the polymer azo compound include a polycondensate of 4,4'-azobis (4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-couple A polycondensate of azabis (4-cyanovaleric acid) and polydimethylsiloxane having an amine group at the terminal.
Examples of the commercially available polymer azo compound include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical).
Examples of the non-polymeric azo compound include V-65 and V-501 (both are manufactured by FUJIFILM Wako Pure Chemical Co., 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.
上述熱聚合起始劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為0.05重量份，較佳之上限為10重量份。藉由使上述熱聚合起始劑之含量為0.05重量份以上，本發明之顯示元件用密封劑成為熱硬化性更加優異者。藉由使上述熱聚合起始劑之含量為10重量份以下，本發明之顯示元件用密封劑成為保存穩定性更加優異者，且於用於液晶顯示元件之情形時成為低液晶污染性亦更加優異者。上述熱聚合起始劑之含量之更佳之下限為0.1重量份，更佳之上限為5重量份。Content of the said thermal-polymerization initiator with respect to 100 weight part of said curable resins, a preferable lower limit is 0.05 weight part, and a preferable upper limit is 10 weight part. When the content of the thermal polymerization initiator is 0.05 parts by weight or more, the sealant for a display element of the present invention becomes more excellent in thermosetting properties. By setting the content of the thermal polymerization initiator to 10 parts by weight or less, the sealant for a display element of the present invention becomes more excellent in storage stability, and also has a low liquid crystal contamination property when used in a liquid crystal display element. Outstanding. A more preferable lower limit of the content of the thermal polymerization initiator is 0.1 part by weight, and a more preferable upper limit is 5 parts by weight.
本發明之顯示元件用密封劑亦可含有熱硬化劑。
作為上述熱硬化劑，例如可列舉：有機酸醯肼、咪唑衍生物、胺化合物、多酚系化合物、酸酐等。其中，較佳使用有機酸醯肼。
上述熱硬化劑可單獨使用，亦可組合2種以上使用。The sealant for display elements of this invention may contain a thermosetting agent.
Examples of the thermosetting agent include organic acid hydrazine, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides. Among them, the organic acid hydrazine is preferably used.
The said thermosetting agent can be used individually or in combination of 2 or more types.
作為上述有機酸醯肼，例如可列舉：癸二醯肼、間苯二甲醯肼、己二醯肼、丙二醯肼等。
作為上述有機酸醯肼中之市售者，例如可列舉：大塚化學公司製造之有機酸醯肼、Ajinomoto Fine-Techno公司製造之有機酸醯肼等。
作為上述大塚化學公司製造之有機酸醯肼，例如可列舉：SDH、ADH等。
作為上述Ajinomoto Fine-Techno公司製造之有機酸醯肼，例如可列舉：Amicure VDH、Amicure VDH-J、Amicure UDH、Amicure UDH-J等。Examples of the organic acid hydrazine include decanediozine, m-xylylenedihydrazine, adipicium hydrazine, and malonylhydrazine.
Examples of the commercially available organic acid hydrazine include the organic acid hydrazine produced by Otsuka Chemical Co., Ltd., and the organic acid hydrazine produced by Ajinomoto Fine-Techno.
Examples of the organic acid hydrazine produced by the Otsuka Chemical Company include SDH, ADH, and the like.
Examples of the organic acid hydrazine produced by the Ajinomoto Fine-Techno company include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J, and the like.
上述熱硬化劑之含量相對於上述硬化性樹脂100重量份，較佳之下限為1重量份，較佳之上限為50重量份。藉由使上述熱硬化劑之含量為該範圍，可於不使獲得之顯示元件用密封劑之塗佈性等變差之情況下使熱硬化性更加優異。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 part with respect to the said curable resin, Preferably a minimum is 1 weight part, and a preferable upper limit is 50 weight part. By setting the content of the above-mentioned thermosetting agent within this range, the thermosetting property can be made more excellent without deteriorating the coatability and the like of the obtained sealant for a display element. 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、線膨脹率之改善等為目的，本發明之顯示元件用密封劑較佳為含有填充劑。The sealing agent for a display element of the present invention preferably contains a filler for the purpose of improving viscosity, improving adhesion caused by a stress dispersion effect, and improving linear expansion rate.
作為上述填充劑，可使用無機填充劑或有機填充劑。
作為上述無機填充劑，例如可列舉：二氧化矽、滑石、玻璃珠、石棉、石膏、矽藻土、膨潤石、膨潤土、蒙脫石、絹雲母、活性白土、氧化鋁、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、氮化鋁、氮化矽、硫酸鋇、矽酸鈣等。
作為上述有機填充劑，例如可列舉：聚酯微粒子、聚胺酯微粒子、乙烯聚合物微粒子、丙烯酸聚合物微粒子等。
上述填充劑可單獨使用，亦可組合2種以上使用。As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, and iron oxide. , Magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, ethylene polymer fine particles, and acrylic polymer fine particles.
These fillers may be used alone or in combination of two or more.
本發明之顯示元件用密封劑100重量份中之上述填充劑的含量之較佳之下限為10重量份，較佳之上限為70重量份。藉由使上述填充劑之含量為該範圍，而於不使塗佈性等變差之情況下使接著性之改善等效果更加優異。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 display element of the present invention is 10 parts by weight, and a preferable upper limit is 70 parts by weight. When the content of the filler is in this range, effects such as improvement in adhesiveness can be made more excellent without deteriorating coatability and the like. 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用以良好地接著密封劑與基板等之作為接著助劑之作用。It is preferable that the sealing agent for display elements of this invention contains a silane coupling agent. The above-mentioned silane coupling agent mainly has a function as a bonding aid for well bonding a sealant to a substrate and the like.
作為上述矽烷偶合劑，可良好地使用3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷等。該等提高與基板等之接著性之效果優異，且與硬化性樹脂進行化學鍵結，藉此於將獲得之顯示元件用密封劑用於液晶顯示元件之情形時可抑制硬化性樹脂向液晶中流出。
上述矽烷偶合劑可單獨使用，亦可組合2種以上使用。As the silane coupling agent, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanate can be favorably used. Propyltrimethoxysilane and the like. These effects of improving the adhesion to the substrate and the like are excellent, and chemical bonding with the curable resin is performed, thereby suppressing the curable resin from flowing into the liquid crystal when the obtained sealant for a display element is used for a liquid crystal display element. .
These silane coupling agents may be used alone or in combination of two or more kinds.
本發明之顯示元件用密封劑100重量份中之上述矽烷偶合劑之含量之較佳之下限為0.1重量份，較佳之上限為10重量份。藉由使上述矽烷偶合劑之含量為該範圍，於將獲得之顯示元件用密封劑用於液晶顯示元件之情形時，抑制液晶污染之產生並且提高接著性之效果更加優異。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 display element of the present invention is 0.1 part by weight, and a preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, when the obtained sealant for a display element is used for a liquid crystal display element, the effect of suppressing the occurrence of liquid crystal contamination and improving the adhesiveness is more excellent. 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，本發明之顯示元件用密封劑可良好地用作遮光密封劑。
本發明之顯示元件用密封劑由於含有對於長波長之光之反應性優異的本發明之光聚合起始劑，故而即便於含有上述遮光劑之情形時，對於長波長之光之硬化性亦優異。The sealing agent for display elements of this invention may contain a light-shielding agent. By containing the said light-shielding agent, the sealing agent for display elements of this invention can be used favorably as a light-shielding sealing agent.
Since the sealant for display elements of the present invention contains the photopolymerization initiator of the present invention which is excellent in reactivity with light having a long wavelength, even when the light-shielding agent is contained, the sealant is excellent in curing property with respect to a light having a long wavelength. .
作為上述遮光劑，例如可列舉：氧化鐵、鈦黑、苯胺黑、花青黑（cyanine black）、富勒烯、碳黑、樹脂被覆型碳黑等。其中，較佳為絕緣性較高之物質，更佳為鈦黑。Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, a substance having a high insulating property is preferable, and titanium black is more preferable.
上述鈦黑即便為未經表面處理者亦發揮充分之效果，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，經有機成分處理者就可進一步提高絕緣性之方面而言較佳。
又，使用含有上述鈦黑作為遮光劑之本發明之顯示元件用密封劑所製造之顯示元件由於具有充分之遮光性，故而可實現無光之漏出而具有較高之對比度、且具有優異之圖像顯示品質之顯示元件。The above-mentioned titanium black exhibits sufficient effects even if it is not surface-treated, and the surface may be treated with an organic component such as a coupling agent or an inorganic substance such as silicon oxide, titanium oxide, germanium oxide, alumina, zirconia, and magnesium oxide. Surface-treated titanium black, etc. Among them, those treated with an organic component are preferred in terms of further improving the insulation properties.
In addition, a display element manufactured using the sealant for a display element of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, and thus can achieve matte leakage, has a high contrast ratio, and has an excellent image. Display elements like 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（皆為Mitsubishi Materials公司製造）、Tilack D（赤穗化成公司製造）等。Examples of marketers of the titanium black include 12S, 13M, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi Materials), Tilack D (made by Akaho Kasei), and the like.
上述鈦黑之比表面積之較佳之下限為13 m2
/g，較佳之上限為30 m2
/g，更佳之下限為15 m2
/g，更佳之上限為25 m2
/g。
又，上述鈦黑之體積電阻之較佳之下限為0.5 Ω・cm，較佳之上限為3 Ω・cm，更佳之下限為1 Ω・cm，更佳之上限為2.5 Ω・cm。The preferred lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferred upper limit is 30 m 2 / g, the more preferred lower limit is 15 m 2 / g, and the more preferred upper limit is 25 m 2 / g.
In addition, a preferable lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, a preferable upper limit is 3 Ω · cm, a more preferable lower limit is 1 Ω · cm, and a more preferable upper limit is 2.5 Ω · cm.
上述遮光劑之一次粒徑只要為顯示元件之基板間之距離以下，則無特別限定，較佳之下限為1 nm，較佳之上限為5000 nm。藉由使上述遮光劑之一次粒徑為該範圍，而可於不使獲得之顯示元件用密封劑之描繪性等變差之情況下使遮光性更加優異。上述遮光劑之一次粒徑之更佳之下限為5 nm，更佳之上限為200 nm，進而較佳之下限為10 nm，進而較佳之上限為100 nm。
再者，上述遮光劑之一次粒徑可使用NICOMP 380ZLS（PARTICLE SIZING SYSTEMS公司製造）使上述遮光劑分散於溶劑（水、有機溶劑等）中而進行測定。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 display element, and the preferred lower limit is 1 nm, and the preferred upper limit is 5000 nm. By setting the primary particle diameter of the light-shielding agent to be in this range, the light-shielding property can be further improved without deteriorating the drawability and the like of the obtained sealant for a display element. The lower limit of the primary particle diameter of the above-mentioned sunscreen is more preferably 5 nm, the more preferable upper limit is 200 nm, the more preferable lower limit is 10 nm, and the more preferable upper limit is 100 nm.
The primary particle diameter of the light-shielding agent can be measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
本發明之顯示元件用密封劑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。藉由使上述遮光劑之含量為該範圍，而可於不使獲得之顯示元件用密封劑之對基板之接著性或硬化後之強度或描繪性降低之情況下發揮更加優異之遮光性。上述遮光劑之含量之更佳之下限為10重量份，更佳之上限為70重量份，進而較佳之下限為30重量份，進而較佳之上限為60重量份。A preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for a display element of the present invention is 5 parts by weight, and a preferable upper limit is 80 parts by weight. By setting the content of the light-shielding agent within this range, it is possible to exhibit more excellent light-shielding properties without reducing the adhesiveness to the substrate of the obtained sealing agent for display elements, or the strength or drawability after curing. 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.
本發明之顯示元件用密封劑亦可視需要進而含有反應性稀釋劑、觸變劑、間隔劑、硬化促進劑、消泡劑、調平劑、聚合抑制劑等添加劑。The sealant for display elements of the present invention may further contain additives such as a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor as needed.
作為製造本發明之顯示元件用密封劑之方法，例如可列舉：使用混合機將硬化性樹脂、光聚合起始劑及視需要添加之矽烷偶合劑等加以混合之方法等。
作為上述混合機，例如可列舉：勻相分散機、均質攪拌機、萬能混合機、行星式混合機、捏合機、三輥研磨機等。Examples of a method for producing the sealant for a display element of the present invention include a method of mixing a curable resin, a photopolymerization initiator, and a silane coupling agent, if necessary, using a mixer.
Examples of the mixer include a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill.
可藉由將導電性微粒子摻合於本發明之顯示元件用密封劑中而製造上下導通材料。含有本發明之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。The conductive fine particles can be mixed with the sealant for a display element of the present invention to produce a vertical conductive material. The sealant for a 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可藉由樹脂微粒子之優異之彈性而於不損傷透明基板等之情況下進行導電連接，因此較佳。As the conductive fine particles, 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 can be electrically connected without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
使用本發明之顯示元件用密封劑或本發明之上下導通材料而成之顯示元件亦為本發明之一。
作為本發明之顯示元件，較佳為液晶顯示元件，更佳為窄邊緣設計之液晶顯示元件。具體而言，較佳為液晶顯示部之周圍之框部分之寬度為2 mm以下。
又，製造窄邊緣設計之液晶顯示元件作為本發明之顯示元件時，本發明之顯示元件用密封劑之塗佈寬度較佳為1 mm以下。A display element using the sealant for a display element of the present invention or the upper-lower conductive material of the present invention is also one of the present invention.
As the display element of the present invention, a liquid crystal display element is preferred, and a liquid crystal display element with a narrow edge design is more preferred. Specifically, the width of the frame portion around the liquid crystal display portion is preferably 2 mm or less.
When a liquid crystal display element with a narrow edge design is manufactured as the display element of the present invention, the application width of the sealant for a display element of the present invention is preferably 1 mm or less.
作為製造液晶顯示元件作為本發明之顯示元件之方法，可良好地使用液晶滴下工法，具體而言，例如可列舉具有以下之各步驟之方法等。
首先，進行如下步驟：於具有ITO薄膜等電極及配向膜之2片透明基板之一者，藉由網版印刷、分注器塗佈等塗佈本發明之顯示元件用密封劑而形成框狀之密封圖案。其次，進行如下步驟：於本發明之顯示元件用密封劑未硬化之狀態下，將液晶之微小滴滴下塗佈至基板之密封圖案之框內，於真空重疊另一透明基板。其後，進行如下步驟：藉由介隔截止濾光器等對本發明之顯示元件用密封劑之密封圖案部分照射長波長之光，而使密封劑光硬化，藉由進行上述步驟之方法，可獲得液晶顯示元件。又，除了上述使密封劑光硬化之步驟以外，亦可進行加熱密封劑使之熱硬化之步驟。
[發明之效果]As a method for manufacturing a liquid crystal display element as the display element of the present invention, a liquid crystal dropping method can be favorably used. Specifically, for example, a method having the following steps can be cited.
First, the following steps are performed: one of two transparent substrates having an electrode such as an ITO film and an alignment film is coated with the sealant for a display element of the present invention by screen printing, dispenser coating, or the like to form a frame shape Its seal pattern. Next, the following steps are performed: in a state where the sealant for a display element of the present invention is not hardened, minute droplets of liquid crystal are drip-coated onto a frame of a sealing pattern of a substrate, and another transparent substrate is overlapped in a vacuum. Thereafter, the following steps are performed: the sealing pattern portion of the sealant for a display element of the present invention is irradiated with light of a long wavelength by a cut-off filter or the like, and the sealant is light-cured. Liquid crystal display element. Furthermore, in addition to the above-mentioned step of photo-curing the sealant, a step of heating the sealant to thermally harden it may be performed.
[Effect of the invention]
根據本發明，可提供一種對於長波長之光之反應性優異之光聚合起始劑。又，根據本發明，可提供一種顯示元件用密封劑、以及使用該顯示元件用密封劑而成之上下導通材料及顯示元件，該顯示元件用密封劑含有該光聚合起始劑，對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。進而，根據本發明，可提供一種構成該光聚合起始劑之化合物。According to the present invention, it is possible to provide a photopolymerization initiator excellent in reactivity with light having a long wavelength. Furthermore, according to the present invention, it is possible to provide a sealant for a display element, and a top-to-bottom conductive material and a display element using the sealant for a display element. The sealant for a display element contains the photopolymerization initiator, and has a long wavelength. The light has excellent curability and is also excellent in low liquid crystal contamination when used in a liquid crystal display element. Furthermore, according to the present invention, a compound constituting the photopolymerization initiator can be provided.
以下揭示實施例進一步詳細地說明本發明，但本發明不僅限定於該等實施例。The following disclosed examples will further explain the present invention, but the present invention is not limited to these examples.
（合成例1）
（式（2-1）所表示之化合物之製作）
於二氯甲烷100重量份中加入4-(二甲基胺基)苯甲醯氯10重量份、及作為觸媒之吡啶0.5重量份，於0℃之環境滴下去水甘油1重量份，放冷後，於室溫整夜攪拌。自獲得之反應液去除二氯甲烷，藉此獲得反應產物。於N,N-二甲基甲醯胺100重量份中添加獲得之反應產物10重量份、及2-羥基-9H-硫 -9-酮5重量份，於作為鹼性觸媒之碳酸鉀存在下，一面於120℃攪拌48小時一面進行反應。自獲得之反應液去除N,N-二甲基甲醯胺，藉由管柱層析法進行精製，藉此獲得上述式（2-1）所表示之化合物。
再者，獲得之上述式（2-1）所表示之化合物之結構藉由1
H-NMR、13
C-NMR及FT-IR進行確認。將獲得之式（2-1）所表示之化合物之1
H-NMR光譜示於圖1。
又，使獲得之式（2-1）所表示之化合物以濃度成為0.1 mg/mL之方式溶解於乙腈。對於獲得之乙腈溶液，使用分光光度計（Hitachi High-Tech Science公司製造，「U-3900」），於光程長度1 cm之條件測定300n m以上800 nm以下之範圍之吸收光譜。其結果為，確認到式（2-1）所表示之化合物於420 nm之吸光度為0.10以上。將獲得之式（2-1）所表示之化合物之吸收光譜示於圖2。(Synthesis example 1)
(Production of compound represented by formula (2-1))
To 100 parts by weight of dichloromethane, 10 parts by weight of 4- (dimethylamino) benzamidine chloride and 0.5 parts by weight of pyridine as a catalyst were added, and 1 part by weight of glycerol was dropped in an environment at 0 ° C. After cooling, stir at room temperature overnight. Dichloromethane was removed from the obtained reaction solution, thereby obtaining a reaction product. 10 parts by weight of the obtained reaction product and 2-hydroxy-9H-sulfur were added to 100 parts by weight of N, N-dimethylformamide. 5 parts by weight of -9-one was reacted in the presence of potassium carbonate as an alkaline catalyst while stirring at 120 ° C for 48 hours. N, N-dimethylformamide was removed from the obtained reaction solution, and purification was performed by column chromatography, thereby obtaining a compound represented by the above formula (2-1).
The structure of the obtained compound represented by the formula (2-1) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR. The 1 H-NMR spectrum of the obtained compound represented by the formula (2-1) is shown in FIG. 1.
The obtained compound represented by the formula (2-1) was dissolved in acetonitrile so that the concentration became 0.1 mg / mL. With respect to the obtained acetonitrile solution, an absorption spectrum in a range of 300 nm to 800 nm was measured using a spectrophotometer ("U-3900" manufactured by Hitachi High-Tech Science Co., Ltd.) under the condition of an optical path length of 1 cm. As a result, the absorbance of the compound represented by Formula (2-1) at 420 nm was confirmed to be 0.10 or more. The absorption spectrum of the obtained compound represented by the formula (2-1) is shown in FIG. 2.
（合成例2）
（式（2-2）所表示之化合物之製作）
將2-羥基-9H-硫 -9-酮變更為2,7-二羥基-9H-硫 -9-酮，除此以外，以與合成例1相同之方式獲得上述式（2-2）所表示之化合物。
再者，獲得之上述式（2-2）所表示之化合物之結構藉由1
H-NMR、13
C-NMR及FT-IR進行確認。
又，使獲得之式（2-2）所表示之化合物以濃度成為0.1 mg/mL之方式溶解於乙腈。對於獲得之乙腈溶液，使用分光光度計（Hitachi High-Tech Science公司製造，「U-3900」），於光程長度1 cm之條件測定300 nm以上800 nm以下之範圍之吸收光譜。其結果為，確認到式（2-2）所表示之化合物於420 nm之吸光度為0.10以上。(Synthesis example 2)
(Production of compound represented by formula (2-2))
Add 2-hydroxy-9H-sulfur -9-one changed to 2,7-dihydroxy-9H-sulfur A compound represented by the above formula (2-2) was obtained in the same manner as in Synthesis Example 1 except for -9-one.
The structure of the obtained compound represented by the formula (2-2) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
The obtained compound represented by the formula (2-2) was dissolved in acetonitrile so that the concentration became 0.1 mg / mL. With respect to the obtained acetonitrile solution, an absorption spectrum in a range of 300 nm to 800 nm was measured using a spectrophotometer ("U-3900" manufactured by Hitachi High-Tech Science Co., Ltd.) under a condition of an optical path length of 1 cm. As a result, it was confirmed that the absorbance of the compound represented by Formula (2-2) at 420 nm was 0.10 or more.
（合成例3）
（式（2-3）所表示之化合物之製作）
將4-(二甲基胺基)苯甲醯氯變更為3,5-雙-(二甲基胺基)苯甲醯氯，除此以外，以與合成例1相同之方式獲得上述式（2-3）所表示之化合物。
再者，獲得之上述式（2-3）所表示之化合物之結構藉由1
H-NMR、13
C-NMR及FT-IR進行確認。
又，使獲得之式（2-3）所表示之化合物以濃度成為0.1 mg/mL之方式溶解於乙腈。對於獲得之乙腈溶液，使用分光光度計（Hitachi High-Tech Science公司製造，「U-3900」），於光程長度1 cm之條件測定300 nm以上800 nm以下之範圍之吸收光譜。其結果為，確認到式（2-3）所表示之化合物於420 nm之吸光度為0.10以上。(Synthesis example 3)
(Production of compound represented by formula (2-3))
The above formula was obtained in the same manner as in Synthesis Example 1 except that 4- (dimethylamino) benzyl chloride was changed to 3,5-bis- (dimethylamino) benzyl chloride. 2-3).
The structure of the obtained compound represented by the formula (2-3) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
The obtained compound represented by the formula (2-3) was dissolved in acetonitrile so that the concentration became 0.1 mg / mL. With respect to the obtained acetonitrile solution, an absorption spectrum in a range of 300 nm to 800 nm was measured using a spectrophotometer ("U-3900" manufactured by Hitachi High-Tech Science Co., Ltd.) under a condition of an optical path length of 1 cm. As a result, the absorbance of the compound represented by Formula (2-3) at 420 nm was confirmed to be 0.10 or more.
（實施例1~7及比較例1~4）
依照表1所記載之摻合比，使用行星式攪拌機（Thinky公司製造，「Awatori Rentaro」）將各材料進行混合後，進而使用三輥研磨機進行混合，藉此製備實施例1~7及比較例1~4之顯示元件用密封劑。(Examples 1 to 7 and Comparative Examples 1 to 4)
In accordance with the blending ratios described in Table 1, the materials were mixed using a planetary mixer ("Awatori Rentaro" manufactured by Thinky, Inc.), and then mixed using a three-roll mill, thereby preparing Examples 1 to 7 and comparison. Sealants for display elements of Examples 1 to 4.
＜評價＞
針對實施例及比較例中所獲得之各顯示元件用密封劑，進行以下之評價。將結果示於表1。＜ Evaluation ＞
The following evaluations were performed about each sealant for display elements obtained in an Example and a comparative example. The results are shown in Table 1.
（光硬化性）
使間隔劑微粒子（積水化學工業公司製造，「Micropearl SI-H050」）1重量份分散於實施例及比較例中所獲得之各顯示元件用密封劑100重量份。其次，將密封劑填充於滴塗用注射器（Musashi Engineering公司製造，「PSY-10E」），進行脫泡處理後，藉由分注器（Musashi Engineering公司製造，「SHOTMASTER300」）塗佈於玻璃基板上。藉由真空貼合裝置於5 Pa之減壓對該基板貼合同尺寸之玻璃基板。使用金屬鹵化物燈對貼合之玻璃基板之密封劑部分照射100 mW/cm2
之光10秒。光照射係介隔截止波長400 nm以下之光之截止濾光器（400 nm截止濾光器）而進行。
使用紅外分光裝置（BIORAD公司製造，「FTS3000」）進行密封劑之FT-IR測定，測定源自(甲基)丙烯醯基之峰值之光照射前後之變化量。於光照射後，將源自(甲基)丙烯醯基之峰值減少85%以上之情形設為「◎」，將減少70%以上且未達85%之情形設為「○」，將減少60%以上且未達70%之情形設為「Δ」，將光照射後之源自(甲基)丙烯醯基之峰值之減少未達60%之情形設為「×」，從而評價光硬化性。(Light hardening)
One part by weight of spacer particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each of the sealants for display elements obtained in the examples and comparative examples. Next, the sealant was filled in a drip coating syringe (Musashi Engineering Co., Ltd., "PSY-10E"), and after performing defoaming treatment, it was applied to a glass substrate with a dispenser (Musashi Engineering Co., Ltd., "SHOTMASTER300") on. A vacuum-bonding device was used to affix a contract-sized glass substrate to the substrate at a reduced pressure of 5 Pa. The sealant portion of the bonded glass substrate was irradiated with light of 100 mW / cm 2 for 10 seconds using a metal halide lamp. The light irradiation is performed through a cut-off filter (400 nm cut-off filter) for light having a cut-off wavelength of 400 nm or less.
FT-IR measurement of the sealant was performed using an infrared spectroscopic device ("FTS3000" manufactured by Biorad Corporation), and the amount of change before and after light irradiation from the peak of the (meth) acrylfluorenyl group was measured. After light irradiation, the case where the peak derived from (meth) acrylfluorenyl group is reduced by 85% or more is set to "◎", and the case that is reduced by 70% or more and less than 85% is set to "○", which is reduced by 60 A case where the percentage is more than 70% and less than 70% is set to "Δ", and a case where the peak value of the peak derived from (meth) acrylfluorenyl group after light irradiation is reduced to less than 60% is set to "x" to evaluate the photohardenability .
（低液晶污染性）
使間隔劑微粒子（積水化學工業公司製造，「Micropearl SI-H050」）1重量份分散於實施例及比較例中所獲得之各顯示元件用密封劑100重量份。其次，藉由分注器以線寬成為1 mm之方式將分散有間隔劑微粒子之密封劑塗佈於經摩擦過之配向膜及附透明電極之基板。
繼而，將液晶（Chisso公司製造，「JC-5004LA」）之微小滴滴下塗佈至附透明電極之基板之密封劑之框內整個面，且立即貼合附透明電極之彩色濾光片基板。其後，使用金屬鹵化物燈對密封劑部分照射100 mW/cm2
之光30秒使之硬化，進而，於120℃加熱1小時，從而獲得液晶顯示元件。光照射係介隔截止波長400 nm以下之光之截止濾光器（400 nm截止濾光器）而進行。
液晶顯示元件係藉由分注器控制密封劑之塗佈位置，製作光完全照射至密封劑之液晶顯示元件（無遮光部）、及將密封劑以覆及線寬之50%之方式塗佈於彩色濾光片基板之黑矩陣所得之液晶顯示元件（有遮光部）之2種。圖3係示意性地表示使用實施例及比較例中所獲得之各顯示元件用密封劑以無遮光部之狀態製作之液晶顯示元件之剖視圖，圖4係示意性地表示使用實施例及比較例中所獲得之各顯示元件用密封劑以有遮光部之狀態製作之液晶顯示元件之剖視圖。如圖3所示，密封劑1上無遮光部之狀態者係光完全照射至密封劑1之狀態，另一方面，密封劑1上有遮光部之狀態者如圖4所示，光被黑矩陣2遮蔽而幾乎不會到達與液晶3接觸之部分之密封劑1。
對於獲得之液晶顯示元件，進行100小時動作試驗後，藉由目視確認到於80℃設為1000小時電壓施加狀態後之液晶配向混亂（顯示不均）。
將於液晶顯示元件完全未看到顯示不均之情形設為「◎」，將於液晶顯示元件之密封劑附近（周邊部）看到少量較淡之顯示不均之情形設為「○」，將於周邊部存在明顯較厚之顯示不均之情形設為「Δ」，將明顯較厚之顯示不均不僅存在於周邊部且亦擴散至中央部之情形設為「×」，從而評價低液晶污染性。
再者，評價為「◎」、「○」之液晶顯示元件係實際應用中完全無問題之等級，評價為「Δ」之液晶顯示元件係視顯示設計而可能成為問題之等級，評價為「×」之液晶顯示元件係不耐於實際應用之等級。(Low liquid crystal pollution)
One part by weight of spacer particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of each of the sealants for display elements obtained in the examples and comparative examples. Next, the sealant in which the spacer particles are dispersed is applied to the rubbed alignment film and the substrate with a transparent electrode by a dispenser so that the line width becomes 1 mm.
Then, a small drop of liquid crystal (manufactured by Chisso Corporation, "JC-5004LA") was applied dropwise to the entire surface inside the frame of the sealant of the substrate with transparent electrodes, and the color filter substrate with transparent electrodes was immediately bonded. Thereafter, the sealant portion was irradiated with light of 100 mW / cm 2 for 30 seconds using a metal halide lamp, and then cured at 120 ° C. for 1 hour to obtain a liquid crystal display element. The light irradiation is performed through a cut-off filter (400 nm cut-off filter) for light having a cut-off wavelength of 400 nm or less.
The liquid crystal display element uses a dispenser to control the application position of the sealant, to produce a liquid crystal display element (without a light-shielding portion) that completely irradiates light to the sealant, and to apply the sealant to cover 50% of the line width There are two types of liquid crystal display elements (with light-shielding portions) obtained on the black matrix of the color filter substrate. FIG. 3 is a cross-sectional view schematically showing a liquid crystal display element manufactured using a sealant for each display element obtained in Examples and Comparative Examples without a light-shielding portion, and FIG. 4 is a schematic view showing a usage example and a comparative example. A cross-sectional view of a liquid crystal display element produced by the sealant for each display element obtained in the state with a light-shielding portion. As shown in FIG. 3, the state where no light-shielding portion is on the sealant 1 is a state in which light is completely irradiated to the sealant 1. On the other hand, the state where the light-shielding portion on the sealant 1 is shown in FIG. 4, the light is black The matrix 2 shields the sealant 1 which hardly reaches the portion in contact with the liquid crystal 3.
The obtained liquid crystal display device was subjected to a 100-hour operation test, and it was visually confirmed that the liquid crystal alignment was disordered (display unevenness) after the voltage application state was set to 1000 hours at 80 ° C.
Set "◎" when the liquid crystal display element does not see display unevenness at all, and set "○" when a small amount of light display unevenness is seen near the sealant (peripheral portion) of the liquid crystal display element. The case where a noticeably thicker display unevenness exists in the peripheral part is set to "Δ", and the case where the noticeably thicker display unevenness exists not only in the peripheral part but also spreads to the center part is set to "×", so that the evaluation is low Liquid crystal contamination.
In addition, the liquid crystal display elements evaluated as "◎" and "○" are grades without any problems in practical applications, and the liquid crystal display elements evaluated as "Δ" are grades that may become a problem depending on the display design, and evaluated as "× "The liquid crystal display element is a grade that is not resistant to practical applications.
[表1]
[產業上之可利用性][Table 1]
[Industrial availability]
根據本發明，可提供一種對於長波長之光之反應性優異之光聚合起始劑。又，根據本發明，可提供一種顯示元件用密封劑、以及使用該顯示元件用密封劑而成之上下導通材料及顯示元件，該顯示元件用密封劑對於長波長之光之硬化性優異，且於用於液晶顯示元件之情形時低液晶污染性亦優異。進而，根據本發明，可提供一種構成該光聚合起始劑之化合物。According to the present invention, it is possible to provide a photopolymerization initiator excellent in reactivity with light having a long wavelength. Furthermore, according to the present invention, it is possible to provide a sealant for a display element, and a top-to-bottom conductive material and a display element using the sealant for a display element. The sealant for a display element is excellent in hardenability against long-wavelength light, and When it is used for a liquid crystal display element, it is also excellent in low liquid-crystal contamination. Furthermore, according to the present invention, a compound constituting the photopolymerization initiator can be provided.
1‧‧‧密封劑1‧‧‧ Sealant
2‧‧‧黑矩陣 2‧‧‧ Black Matrix
3‧‧‧液晶 3‧‧‧ LCD
圖1係合成例1中所獲得之式（2-1）所表示之化合物之1 H-NMR光譜。FIG. 1 is a 1 H-NMR spectrum of a compound represented by the formula (2-1) obtained in Synthesis Example 1. FIG.
圖2係合成例1中所獲得之式（2-1）所表示之化合物之吸收光譜。 FIG. 2 is an absorption spectrum of a compound represented by the formula (2-1) obtained in Synthesis Example 1. FIG.
圖3係示意性地表示使用實施例及比較例中所獲得之各顯示元件用密封劑以無遮光部之狀態製作之液晶顯示元件之剖視圖。 FIG. 3 is a cross-sectional view schematically showing a liquid crystal display element manufactured using a sealant for each display element obtained in Examples and Comparative Examples in a state without a light-shielding portion.
圖4係示意性地表示使用實施例及比較例中所獲得之各顯示元件用密封劑以有遮光部之狀態製作之液晶顯示元件之剖視圖。 FIG. 4 is a cross-sectional view schematically showing a liquid crystal display element manufactured using a sealant for each display element obtained in Examples and Comparative Examples in a state having a light-shielding portion.
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| CN112079813B (en) * | 2020-08-18 | 2021-05-25 | 新丰博兴聚合材料有限公司 | UV LED photoinitiator and preparation method thereof |
| KR20230078950A (en) * | 2020-09-30 | 2023-06-05 | 세키스이가가쿠 고교가부시키가이샤 | Thioxanthone compound, photopolymerization initiator, curable resin composition, display element composition, liquid crystal display element sealant, upper and lower conduction material, and liquid crystal display element |
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| KR101788399B1 (en) * | 2015-09-23 | 2017-10-19 | (주)경인양행 | Oxime ester compound having improved heat stability, photopolymerization initiator and photoresist composition comprising the same |
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