WO2019013194A1 - Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element - Google Patents
Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element Download PDFInfo
- Publication number
- WO2019013194A1 WO2019013194A1 PCT/JP2018/025999 JP2018025999W WO2019013194A1 WO 2019013194 A1 WO2019013194 A1 WO 2019013194A1 JP 2018025999 W JP2018025999 W JP 2018025999W WO 2019013194 A1 WO2019013194 A1 WO 2019013194A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid crystal
- meth
- compound
- crystal display
- acrylate
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 91
- 238000007789 sealing Methods 0.000 title claims abstract description 75
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 74
- 239000004020 conductor Substances 0.000 title claims abstract 3
- -1 maleimide compound Chemical class 0.000 claims abstract description 91
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 238000010521 absorption reaction Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 123
- 239000004593 Epoxy Substances 0.000 claims description 104
- 239000010419 fine particle Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000000565 sealant Substances 0.000 claims description 4
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 14
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 111
- 239000000758 substrate Substances 0.000 description 21
- 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
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 238000001723 curing 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
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- 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
- 230000000052 comparative effect Effects 0.000 description 6
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- 125000003118 aryl group Chemical group 0.000 description 5
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
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- 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 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 235000010290 biphenyl Nutrition 0.000 description 4
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
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- 229940105570 ornex Drugs 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
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- 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
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 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
- 238000005227 gel permeation chromatography Methods 0.000 description 3
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- 125000006850 spacer group Chemical group 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 2
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
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- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
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- MBAQOFIMVJQPOE-UHFFFAOYSA-N butane;pyrrole-2,5-dione Chemical compound CCCC.O=C1NC(=O)C=C1 MBAQOFIMVJQPOE-UHFFFAOYSA-N 0.000 description 1
- IADGHSROEWQWLL-UHFFFAOYSA-M butyl(trimethyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](C)(C)C IADGHSROEWQWLL-UHFFFAOYSA-M 0.000 description 1
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- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 150000003949 imides Chemical class 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 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
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
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- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
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- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
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- 230000008569 process Effects 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
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910021647 smectite Inorganic materials 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
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 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
- 239000010409 thin film Substances 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 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
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- AMJYHMCHKZQLAY-UHFFFAOYSA-N tris(2-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound O=C=NC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)N=C=O)OC1=CC=CC=C1N=C=O AMJYHMCHKZQLAY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- 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
Definitions
- the present invention relates to a sealing agent for a liquid crystal display element which is excellent in curability to long wavelength light and can suppress the generation of foreign matter. Further, the present invention relates to a vertical conduction material and a liquid crystal display element formed by using the sealing agent for the liquid crystal display element.
- a photo-thermal combination curing seal as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used.
- a liquid crystal dropping method called a dropping method using an agent is used.
- the dropping method first, a frame-like seal pattern is formed on one of the two transparent substrates with electrodes by dispensing. Next, while the sealing agent is in an uncured state, minute droplets of liquid crystal are dropped over the entire surface of the frame of the transparent substrate, the other transparent substrate is immediately bonded, and light such as ultraviolet light is irradiated on the sealing portion to perform temporary curing. .
- liquid crystal display element is manufactured. If bonding of the substrates is performed under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency, and the dropping method is currently the mainstream of the manufacturing method of the liquid crystal display element.
- narrowing the frame of the liquid crystal display portion is mentioned, and for example, the position of the seal portion is disposed under the black matrix (hereinafter, also referred to as narrow frame design).
- the sealing agent is disposed immediately below the black matrix in the narrow frame design, when the dropping method is performed, the light irradiated when the sealing agent is photocured is blocked, and the light does not reach the inside of the sealing agent. There is a problem that curing becomes insufficient. As described above, when the curing of the sealing agent is insufficient, the uncured sealing agent component is eluted into the liquid crystal, and the curing reaction by the eluted sealing agent component proceeds in the liquid crystal, thereby causing liquid crystal contamination. there were.
- irradiation of ultraviolet light is performed as a method of photocuring the sealing agent, but in the liquid crystal dropping method, since the sealing agent is hardened after dropping the liquid crystal, the liquid crystal is deteriorated by irradiating the ultraviolet light.
- a photopolymerization initiator which is excellent in the reactivity to the long wavelength light and to photocure it with the long wavelength light through a cut filter or the like.
- a photopolymerization initiator when such a photopolymerization initiator is used, there is a problem that the sealing agent is partially cured by a slight light before the photocuring step, and foreign matter is generated.
- the present invention contains a curable resin, a photopolymerization initiator and a maleimide compound, and the photopolymerization initiator has a light absorption coefficient at a wavelength of 430 nm of 0.8 ⁇ 10 2 mL / g ⁇ cm or more. It is a sealing agent.
- the present invention will be described in detail below.
- the present inventors have surprisingly found that, even if a photopolymerization initiator excellent in reactivity with long wavelength light is used by blending a maleimide compound in the sealing agent, the sealing agent is partially formed before the light curing step. It has been found that it is possible to obtain a sealing agent for a liquid crystal display element capable of suppressing the generation of foreign matter due to curing to complete the present invention.
- the sealing agent for a liquid crystal display element of the present invention contains a photopolymerization initiator.
- the photopolymerization initiator has an absorption coefficient of at least 0.8 ⁇ 10 2 mL / g ⁇ cm at a wavelength of 430 nm.
- the photopolymerization initiator having an absorption coefficient of 0.8 ⁇ 10 2 mL / g ⁇ cm or more at a wavelength of 430 nm is also referred to as “the photopolymerization initiator according to the present invention”.
- the photopolymerization initiator according to the present invention has a light absorption coefficient at a wavelength of 430 nm of 0.8 ⁇ 10 2 mL / g ⁇ cm or more, so that the sealing agent for a liquid crystal display element of the present invention is curable to long wavelength light. Excellent.
- the preferable lower limit of the absorption coefficient at a wavelength of 430 nm of the photopolymerization initiator according to the present invention is 1.0 ⁇ 10 2 mL / g ⁇ cm.
- the preferable upper limit of the light absorption coefficient in wavelength 430nm of the photoinitiator concerning this invention is 1.0 * 10 ⁇ 4 > mL / g * cm.
- the said absorption coefficient can be measured using a spectrophotometer, after melt
- the solvent is not particularly limited as long as it can dissolve the compound to be measured and does not absorb light at the absorption wavelength to be measured, and examples thereof include acetonitrile and methanol.
- the photopolymerization initiator according to the present invention is preferably a compound having a structure represented by the following formula (1) because it is excellent in the reactivity to light of long wavelength, and it is preferable to use one compound per molecule. It is more preferable that the compound has a structure represented by (1), and a compound represented by the following formula (2-1) and / or a compound represented by the following formula (2-2) preferable.
- * is a bonding position
- R is a structure derived from a monofunctional epoxy compound.
- m is an integer of 1 to 5.
- the monofunctional epoxy compound preferably has an aromatic ring having at least one or more substituents having one or more carbon atoms or an aliphatic ring having at least one or more substituents having one or more carbon atoms.
- the aromatic ring or the aliphatic ring include aromatic rings such as benzene ring, naphthalene ring, anthracene ring, cyclobutane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclooctane ring, norbornene ring, tricyclodecane ring, etc. That in which at least one or more hydrogen atoms in an aliphatic ring is substituted by a C 1 or more substituent is mentioned.
- the substituent having one or more carbon atoms may be linear or branched.
- the number of carbon atoms is preferably 6 or more, and more preferably 10 or more.
- the number of carbon atoms is 4 or more.
- carbon number of the C1 or more substituent which the said aromatic ring or the said aliphatic ring has is a number used as the molecular weight of the said monofunctional epoxy compound becomes 300 or less mentioned later.
- an alkyl group is preferable.
- Examples of the monofunctional epoxy compound include alkylphenyl glycidyl ether, toluene sulfonate having a glycidyl group, 2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate and the like.
- Examples of the alkylphenyl glycidyl ether include o-methylphenyl glycidyl ether, m-methylphenyl glycidyl ether, p-methylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether and the like.
- monofunctional epoxy compounds manufactured by Nagase ChemteX Corp. for example, monofunctional epoxy compounds manufactured by Nagase ChemteX Corp., monofunctional epoxy compounds manufactured by ADEKA, monofunctional epoxy compounds manufactured by Mitsubishi Chemical Co., Ltd., Tokyo Chemical Industry Co., Ltd. Examples thereof include monofunctional epoxy compounds manufactured by Co., and monofunctional epoxy compounds manufactured by Daicel. Examples of the monofunctional epoxy compound manufactured by Nagase ChemteX Corp. include Denacol EX-146. Examples of the monofunctional epoxy compound manufactured by ADEKA include ED-509S, ED-509E, ED-529 and the like. Examples of monofunctional epoxy compounds manufactured by Mitsubishi Chemical Corporation include YED-122. Examples of monofunctional epoxy compounds manufactured by Tokyo Chemical Industry Co., Ltd. include glycidyl 2-methoxyphenyl ether, 1-methyl-1,2-epoxycyclohexane and the like. Examples of the monofunctional epoxy compound manufactured by Daicel Corporation include Celoxide 2000, Cyclomer M100 and the like.
- the molecular weight of the monofunctional epoxy compound is preferably 300 or less from the viewpoint of the compatibility of the photopolymerization initiator according to the present invention with the curable resin.
- the compound represented by the above formula (2-1) or the compound represented by the above formula (2-2) is highly recovered when the ratio of the raw material thioxanthone derivative to the above monofunctional epoxy compound is within this range. It can be manufactured at a rate.
- a trivalent organic phosphoric acid compound and / or an amine compound are preferable.
- Specific examples of the above basic catalyst include triphenylphosphine, triethylamine, trypromylamine, tetramethylethylenediamine, dimethyllaurylamine, triethylbenzylammonium chloride, trimethylcetyl ammonium bromide, tetrabutyl ammonium bromide, trimethylbutyl phosphonium bromide. And tetrabutylphosphonium bromide and the like.
- triphenyl phosphine is preferable.
- the above basic catalyst can also be supported on a polymer and used as a polymer-supported basic catalyst.
- Examples of the photopolymerization initiator according to the present invention other than the compound having a structure represented by the above formula (1) include, for example, bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide and the like. .
- the preferable lower limit of the content of the photopolymerization initiator according to the present invention is 0.1 parts by weight and the preferable upper limit is 20 parts by weight with respect to 100 parts by weight in total of the curable resin and the maleimide compound.
- the content of the photopolymerization initiator according to the present invention is 0.1 parts by weight or more, the obtained sealing agent for a liquid crystal display element is excellent in the curability to long wavelength light.
- the content of the photopolymerization initiator according to the present invention is 20 parts by weight or less, the obtained sealing agent for a liquid crystal display element is more excellent in the effect of suppressing the generation of foreign matter.
- the lower limit of the content of the photopolymerization initiator according to the present invention is more preferably 0.2 parts by weight, still more preferably 0.3 parts by weight, still more preferably 0.5 parts by weight, particularly preferably 1 part by weight It is.
- the upper limit of the content of the photopolymerization initiator according to the present invention is more preferably 10 parts by weight, still more preferably 5 parts by weight.
- the sealing agent for a liquid crystal display element of the present invention may contain a thermal polymerization initiator as long as the object of the present invention is not impaired.
- a thermal polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
- a polymeric azo initiator comprising a polymeric azo compound is preferred.
- polymer azo compound refers to a compound having a number average molecular weight of 300 or more which has an azo group and generates a radical capable of curing a (meth) acryloyloxy group by heat. means.
- the preferable lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 1000, and the preferable upper limit is 300,000.
- the number average molecular weight of the high molecular weight azo compound is in this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination.
- a more preferable lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 5,000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a still more preferable upper limit is 90,000.
- the above-mentioned number average molecular weight is a value obtained by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and measuring in terms of polystyrene.
- GPC gel permeation chromatography
- Shodex LF-804 made by Showa Denko
- said high molecular weight azo compound what has the structure which multiple units, such as a polyalkylene oxide and polydimethylsiloxane, couple
- a polymeric azo compound having a structure in which a plurality of units such as a polyalkylene oxide is bonded via the above azo group one having a polyethylene oxide structure is preferable.
- Specific examples of the high molecular weight azo compound include polycondensates of 4,4'-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis (4-cyanopentanoic acid) And polydimethylsiloxanes having a terminal amino group, and the like.
- VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 all are Fujifilm Wako Pure Chemical Industries, Ltd. make
- V-65, V-501 all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
- organic peroxide examples include ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, peroxy dicarbonate and the like.
- a preferable lower limit is 0.05 parts by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight in total of the curable resin and the maleimide compound.
- the sealing agent for a liquid crystal display element of the present invention is more excellent in thermosetting.
- the sealing agent for a liquid crystal display element of the present invention is excellent in low liquid crystal contamination and storage stability.
- the more preferable lower limit of the content of the thermal polymerization initiator is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.
- the sealing agent for a liquid crystal display element of the present invention contains a curable resin. As described later, in the present invention, the maleimide compound is not included in the curable resin.
- the said curable resin contains a (meth) acrylic compound.
- a (meth) acrylic acid ester compound an epoxy (meth) acrylate, urethane (meth) acrylate etc. are mentioned, for example.
- epoxy (meth) acrylate is preferable.
- the said (meth) acrylic compound has 2 or more of (meth) acryloyl groups in a molecule
- numerator from the height of the reactivity is preferable.
- the above “(meth) acrylic” means acrylic or methacrylic
- the above “(meth) acrylic compound” means a compound having a (meth) acryloyl group
- the above “((meth) acrylic compound” "Meth) acryloyl” means acryloyl or methacryloyl.
- the above-mentioned “(meth) acrylate” means an acrylate or a methacrylate.
- the above-mentioned “epoxy (meth) acrylate” represents the compound which made all the epoxy groups in an epoxy compound react with (meth) acrylic acid.
- methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate is mentioned, for example , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, iso Myristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy 2)
- epoxy (meth) acrylate what is obtained by reacting an epoxy compound and (meth) acrylic acid in presence of a basic catalyst according to a conventional method etc. are mentioned, for example.
- epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meta) acrylate for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2,2'-diallyl bisphenol A type epoxy compound Hydrogenated bisphenol epoxy compound, propylene oxide-added bisphenol A epoxy compound, resorcinol epoxy compound, biphenyl epoxy compound, sulfide epoxy compound, diphenyl ether epoxy compound, dicyclopentadiene epoxy compound, naphthalene epoxy compound, phenol Novolak type epoxy compound, ortho cresol novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound, biphenyl Novolac-type epoxy compounds, naphthalene phenol novolac-type epoxy compounds, glycidyl amine type epoxy compounds, alkyl polyol type epoxy compound, a rubber-modified epoxy compounds, glycidyl ester compounds.
- biphenyl type epoxy compounds commercially available ones include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
- examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- commercially available ones include, for example, EP-4088S (manufactured by Adeka).
- Examples of commercially available naphthalene type epoxy compounds include Epiclon HP4032 and Epiclon EXA-4700 (all manufactured by DIC Corporation).
- Examples of the commercially available phenol novolac epoxy compounds include Epiclon N-770 (manufactured by DIC Corporation).
- Examples of commercially available ortho-cresol novolac epoxy compounds include Epiclon N-670-EXP-S (manufactured by DIC Corporation).
- Epiclon HP7200 made by DIC Corporation
- biphenyl novolac epoxy compounds commercially available ones include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.
- examples of commercially available naphthalenephenol novolac epoxy compounds include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- commercially available ones include jER630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.
- alkyl polyol type epoxy compounds commercially available ones are, for example, ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiclon 726 (manufactured by DIC Corporation), Epolight 80 MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Made by Nagase ChemteX) etc. are mentioned.
- commercially available ones include YR-450, YR-207 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and Eporide PB (manufactured by Daicel Co., Ltd.).
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corp.).
- Denacol EX-147 manufactured by Nagase ChemteX Corp.
- YDC-1312, YSLV-80XY, YSLV-90CR all are manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
- XAC4151 manufactured by Asahi Kasei Corp.
- jER1031, jER1032 any one
- Mitsubishi Chemical Corporation EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.), and the like.
- epoxy (meth) acrylates for example, epoxy (meth) acrylate manufactured by Daicel Ornex, epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., epoxy manufactured by Kyoeisha Chemical Examples thereof include meta) acrylates and epoxy (meth) acrylates manufactured by Nagase ChemteX Corporation. Examples of the epoxy (meth) acrylates manufactured by Daicel Ornex Co., Ltd.
- Examples of the epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 and the like. Examples of epoxy (meth) acrylates manufactured by Kyoeisha Chemical Co., Ltd.
- epoxy ester M-600A examples include epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, epoxy ester 1600A, Epoxy ester 3000 M, epoxy ester 3000 A, epoxy ester 200 EA, epoxy ester 400 EA, etc. may be mentioned.
- Examples of the epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation examples include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911 and the like.
- the urethane (meth) acrylate is obtained, for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound be able to.
- isocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), and hydrogenation.
- MDI polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethyl xylylene And isocyanate, 1,6,11-undecanetriisocyanate, etc.
- a chain-extended isocyanate compound obtained by the reaction of a polyol and an excess of an isocyanate compound can also be used.
- the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and the like.
- the (meth) acrylic acid derivative having a hydroxyl group for example, hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of dihydric alcohol, mono (meth) acrylate or di (meth) acrylate of trihydric alcohol And epoxy (meth) acrylates.
- hydroxyalkyl mono (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. It can be mentioned.
- Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like.
- Examples of the trihydric alcohol include trimethylol ethane, trimethylol propane and glycerin.
- As said epoxy (meth) acrylate, bisphenol-A epoxy acrylate etc. are mentioned, for example.
- urethane (meta) acrylates for example, urethane (meta) acrylate by Toagosei Co., Ltd., urethane (meta) acrylate by Daicel Ornex, urethane (meta) by Negami Kogyo Co., Ltd. Acrylate, urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like. Examples of the urethane (meth) acrylate manufactured by Toagosei Co., Ltd.
- urethane (meth) acrylate manufactured by the above-mentioned Daicel Ornex Co., Ltd., for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYLL4852, EBECRYLL5129, EBECRYLL747. It can be mentioned.
- urethane (meth) acrylates manufactured by Shin-Nakamura Chemical Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, and the like.
- urethane (meth) acrylates manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T, etc.
- the said curable resin contains an epoxy compound further in order to improve the adhesiveness of the sealing compound for liquid crystal display elements obtained.
- combining the epoxy (meth) acrylate mentioned above, a partial (meth) acryl modified epoxy compound, etc. are mentioned, for example.
- the above-mentioned partial (meth) acrylic-modified epoxy compound means a compound having one or more epoxy group and one or more (meth) acryloyl group in one molecule, for example, two in one molecule. It can obtain by making the epoxy group of a part of the epoxy compound which has the above epoxy group react with (meth) acrylic acid.
- the sealing compound for a liquid crystal display element of the present invention contains the above-mentioned epoxy compound
- the ratio of (meth) acryloyl group in the total of (meth) acryloyl group and epoxy group in the above curable resin is 30 mol% or more It is preferable to make it less than mol%.
- the ratio of the (meth) acryloyl group is 30 mol% or more, the obtained sealing agent for a liquid crystal display element is excellent in low liquid crystal contamination.
- the sealing agent for liquid crystal display elements obtained by the ratio of the said (meth) acryloyl group being 95 mol% or less will become excellent by adhesiveness.
- the curable resin preferably has a hydrogen bonding unit such as -OH group, -NH- group, and -NH 2 group.
- the sealing agent for a liquid crystal display element of the present invention contains a maleimide compound.
- the sealing agent for a liquid crystal display element of the present invention can suppress the generation of foreign matter even when using the photopolymerization initiator according to the present invention.
- the maleimide compound is not included in the curable resin.
- the preferred lower limit of the molecular weight of the maleimide compound is 400.
- the obtained sealing agent for a liquid crystal display element is excellent due to the effect of achieving both the improvement of the curability to long wavelength light and the suppression of the generation of foreign matter.
- a more preferable lower limit of the molecular weight of the maleimide compound is 500.
- the upper limit of the molecular weight of the maleimide compound is preferably 1,500, and more preferably 1,000.
- the above maleimide compound is preferably a polyfunctional maleimide compound having two or more maleimide groups in one molecule from the viewpoint of reactivity.
- polyfunctional maleimide compound a compound represented by the following formula (3) or a compound represented by the following formula (4) is suitably used.
- R 1 represents an alkylene group having a carbon number of 2 to 3
- n is an integer of 2 to 40.
- R 2 represents a divalent aliphatic group having 1 to 40 carbon atoms.
- the carbon number of R 2 is preferably 12 to 36. Further, R 2 preferably has an aliphatic ring.
- Specific examples of the compound represented by the above formula (4) include 1,4-bis (maleimide) butane, 1,20-bismaleimide-10,11-dioctyl-eicosane (following formula (5-1) ), 1-heptylenemaleimide-2-octylenemaleimide-4-octyl-5-heptylcyclohexane (compound represented by the following formula (5-2)), 1,2-dioc Examples include lenmaleimide-3-octyl-4-hexylcyclohexane (compound represented by the following formula (5-3)) and the like.
- the compound represented by the above formula (4) can be synthesized, for example, by the method described in US Pat. No. 5,973,166.
- maleimide compounds as a monofunctional maleimide compound having one maleimide group in one molecule, for example, N-biotinyl-N '-(3-maleimidopropionyl) -3,6-dioxaoctane-1, 8-diamine and the like can be mentioned.
- the preferable lower limit of the content of the maleimide compound in a total of 100 parts by weight of the curable resin and the maleimide compound is 2 parts by weight, and the preferable upper limit is 50 parts by weight.
- the content of the maleimide compound is 2 parts by weight or more, the obtained sealing agent for a liquid crystal display element is excellent in the effect of suppressing the generation of foreign matter.
- the content of the maleimide compound is 50 parts by weight or less, the obtained sealing agent for a liquid crystal display element is more excellent in photocurability.
- a more preferable lower limit of the content of the maleimide compound is 3 parts by weight, a still more preferable lower limit is 5 parts by weight, and a particularly preferable lower limit is 10 parts by weight.
- the upper limit of the content of the maleimide compound is preferably 45 parts by weight, more preferably 40 parts by weight, still more preferably 35 parts by weight, particularly preferably 30 parts by weight, and most preferably 25 parts by weight.
- the sealing agent for a liquid crystal display element of the present invention may contain a thermosetting agent.
- a thermosetting agent an organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned, for example.
- organic acid hydrazides are preferably used.
- Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
- the organic acid hydrazide by Otsuka Chemical Co., Ltd. As what is marketed among the said organic acid hydrazide, the organic acid hydrazide by Otsuka Chemical Co., Ltd., the organic acid hydrazide by Ajinomoto Fine Techno Co., Ltd., etc. are mentioned, for example.
- Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
- Examples of the organic acid hydrazide manufactured by Ajinomoto Fine Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J and the like.
- the preferable lower limit is 1 part by weight and the preferable upper limit is 50 parts by weight with respect to 100 parts by weight in total of the curable resin and the maleimide compound.
- the thermosetting property can be further improved without deteriorating the coating property and the like of the obtained sealing agent for a liquid crystal display element.
- a more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
- the sealing agent for a liquid crystal display element of the present invention preferably contains a filler for the purpose of improving viscosity, improving adhesion due to a stress dispersion effect, improving linear expansion coefficient, and the like.
- an inorganic filler or an organic filler can be used as the filler.
- the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide And calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
- the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles. The above fillers may be used alone or in combination of two or more.
- the preferable lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight.
- the content of the above-mentioned filler is in this range, the effect of improving the adhesiveness and the like becomes excellent without deteriorating the coatability and the like.
- the more preferable lower limit of the content of the filler is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.
- the sealing agent for a liquid crystal display element of the present invention preferably contains a silane coupling agent.
- the above-mentioned silane coupling agent mainly serves as an adhesion aiding agent for favorably bonding the sealing agent and the substrate and the like.
- silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are suitably used. These are excellent in the effect of improving the adhesion to a substrate or the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin.
- the preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the liquid crystal display element sealing agent of the present invention is 0.1 parts by weight, and the preferable upper limit is 10 parts by weight.
- the content of the silane coupling agent is in this range, the occurrence of liquid crystal contamination is suppressed, and the adhesive property is improved.
- a more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.
- the sealant for a liquid crystal display element of the present invention further contains, as necessary, additives such as a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor. May be
- a curable resin and a curable resin using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a 3-roll mill.
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a 3-roll mill.
- the method etc. which mix the photoinitiator concerning this invention, a maleimide compound, and the silane coupling agent etc. which are added as needed are mentioned.
- a vertical conduction material can be manufactured by mix
- a vertical conduction material containing such a sealing agent for a liquid crystal display element of the present invention and conductive fine particles is also one of the present invention.
- electroconductive fine particle what formed the conductive metal layer in the surface of a metal ball and resin fine particles etc. can be used.
- those in which a conductive metal layer is formed on the surface of resin fine particles are preferable because the excellent elasticity of the resin fine particles allows conductive connection without damaging the transparent substrate and the like.
- a liquid crystal display device using the sealing agent for a liquid crystal display device of the present invention or the vertical conduction material of the present invention is also one of the present invention.
- a liquid crystal dropping method is suitably used, and specifically, for example, a method having the following respective steps can be mentioned.
- the sealing agent for a liquid crystal display element of the present invention is applied by screen printing, dispenser coating, or the like to one of two substrates such as a glass substrate with an electrode such as ITO thin film and a polyethylene terephthalate substrate.
- the process of forming a pattern is performed.
- a step of applying minute droplets of liquid crystal to the inside of the frame of the seal pattern of the substrate by a drop in a state where the sealing agent for a liquid crystal display element of the present invention is uncured is dropped, and another substrate is superposed under vacuum.
- the seal pattern portion of the sealing agent for a liquid crystal display element of the present invention is irradiated with light through a 420 nm cut filter or the like to perform a step of photocuring the sealing agent with long wavelength light. You can get In addition to the step of photocuring the sealing agent, the step of heating and thermally curing the sealing agent may be performed.
- the sealing compound for liquid crystal display elements which is excellent in the sclerosis
- PS-PPh 3 a basic catalyst in which triphenylphosphine is supported on polystyrene (PS) manufactured by Biotage Japan Ltd.
- PS-PPh 3 a basic catalyst in which triphenylphosphine is supported on polystyrene (PS) manufactured by Biotage Japan Ltd.
- a basic catalyst comprising 69 parts by weight of 2-hydroxy-9H-thioxanthen-9-one and 62 parts by weight of p-tert-butylphenyl glycidyl ether ("ED-509S" manufactured by ADEKA Corporation) as a monofunctional epoxy compound
- ED-509S p-tert-butylphenyl glycidyl ether
- a basic catalyst 5.2 parts by weight of PS-PPh 3 (a basic catalyst in which triphenylphosphine is supported on polystyrene (PS) manufactured by Biotage Japan Ltd.) was used.
- Examples 1 to 9 and Comparative Examples 1 to 3 According to the compounding ratio described in Tables 1 and 2, after mixing each material using a planetary stirrer ("Awatori Neritaro" manufactured by Shinky Co., Ltd.), mixing is further performed using three rolls. Sealing agents for liquid crystal display devices of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared.
- a spectrophotometer the Hitachi High-Tech Science company make, "U-3900" The extinction coefficient at a wavelength of 430 nm was measured using this.
- a light of 100 mW / cm 2 was irradiated to the sealant portion of the bonded glass substrate for 10 seconds using a metal halide lamp.
- Light irradiation performed two patterns, the case without a 420 nm cut filter, and the case with a 420 nm cut filter.
- Evaluation of curability by performing FT-IR measurement of the sealing agent using an infrared spectrometer (manufactured by BIORAD, "FTS 3000") and measuring the amount of change of the (meth) acryloyl group-derived peak before and after light irradiation Did.
- the sealing compound for liquid crystal display elements which is excellent in the sclerosis
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Abstract
Description
滴下工法では、まず、2枚の電極付き透明基板の一方に、ディスペンスにより枠状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下し、すぐに他方の透明基板を貼り合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、液晶アニール時に加熱して本硬化を行い、液晶表示素子を作製する。基板の貼り合わせを減圧下で行うようにすれば、極めて高い効率で液晶表示素子を製造することができ、現在この滴下工法が液晶表示素子の製造方法の主流となっている。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell or the like, a photo-thermal combination curing seal as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using an agent is used.
In the dropping method, first, a frame-like seal pattern is formed on one of the two transparent substrates with electrodes by dispensing. Next, while the sealing agent is in an uncured state, minute droplets of liquid crystal are dropped over the entire surface of the frame of the transparent substrate, the other transparent substrate is immediately bonded, and light such as ultraviolet light is irradiated on the sealing portion to perform temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If bonding of the substrates is performed under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency, and the dropping method is currently the mainstream of the manufacturing method of the liquid crystal display element.
以下に本発明を詳述する。 The present invention contains a curable resin, a photopolymerization initiator and a maleimide compound, and the photopolymerization initiator has a light absorption coefficient at a wavelength of 430 nm of 0.8 × 10 2 mL / g · cm or more. It is a sealing agent.
The present invention will be described in detail below.
上記光重合開始剤は、波長430nmにおける吸光係数が0.8×102mL/g・cm以上である。以下、波長430nmにおける吸光係数が0.8×102mL/g・cm以上である光重合開始剤を、「本発明にかかる光重合開始剤」ともいう。
本発明にかかる光重合開始剤は、波長430nmにおける吸光係数が0.8×102mL/g・cm以上であることにより、本発明の液晶表示素子用シール剤が長波長の光に対する硬化性に優れるものとなる。本発明にかかる光重合開始剤の波長430nmにおける吸光係数の好ましい下限は1.0×102mL/g・cmである。
また、本発明にかかる光重合開始剤の波長430nmにおける吸光係数の好ましい上限は1.0×104mL/g・cmである。
なお、上記吸光係数は、濃度が0.1mg/mLとなるように測定対象の化合物を溶媒に溶解した後、分光光度計を用いて測定することができる。
上記溶媒は、測定対象の化合物を溶解することができ、かつ、測定する吸収波長での吸光がないものであれば特に限定されず、例えば、アセトニトリル、メタノール等が挙げられる。 The sealing agent for a liquid crystal display element of the present invention contains a photopolymerization initiator.
The photopolymerization initiator has an absorption coefficient of at least 0.8 × 10 2 mL / g · cm at a wavelength of 430 nm. Hereinafter, the photopolymerization initiator having an absorption coefficient of 0.8 × 10 2 mL / g · cm or more at a wavelength of 430 nm is also referred to as “the photopolymerization initiator according to the present invention”.
The photopolymerization initiator according to the present invention has a light absorption coefficient at a wavelength of 430 nm of 0.8 × 10 2 mL / g · cm or more, so that the sealing agent for a liquid crystal display element of the present invention is curable to long wavelength light. Excellent. The preferable lower limit of the absorption coefficient at a wavelength of 430 nm of the photopolymerization initiator according to the present invention is 1.0 × 10 2 mL / g · cm.
Moreover, the preferable upper limit of the light absorption coefficient in wavelength 430nm of the photoinitiator concerning this invention is 1.0 * 10 < 4 > mL / g * cm.
In addition, the said absorption coefficient can be measured using a spectrophotometer, after melt | dissolving the compound to be measured in a solvent so that a density | concentration may be 0.1 mg / mL.
The solvent is not particularly limited as long as it can dissolve the compound to be measured and does not absorb light at the absorption wavelength to be measured, and examples thereof include acetonitrile and methanol.
また、上記(2-2)で表される化合物を製造する方法としては、例えば、塩基性触媒の存在下で、2-ヒドロキシ-9H-チオキサンテン-9-オンと単官能エポキシ化合物とを80℃以上130℃以下の条件で6~72時間撹拌しながら反応させる方法等が挙げられる。
以下、2-(カルボキシメトキシ)-9H-チオキサンテン-9-オンと2-ヒドロキシ-9H-チオキサンテン-9-オンとについては、「原料チオキサントン誘導体」ともいう。 As a method for producing the compound represented by the above (2-1), for example, 2- (carboxymethoxy) -9H-thioxanthen-9-one and a monofunctional epoxy compound in the presence of a basic catalyst The reaction may be carried out while stirring for 6 to 72 hours under conditions of 80 ° C. or more and 130 ° C. or less.
Moreover, as a method for producing the compound represented by the above (2-2), for example, 2-hydroxy-9H-thioxanthen-9-one and a monofunctional epoxy compound in the presence of a basic catalyst may be used. The reaction may be carried out while stirring for 6 to 72 hours under the conditions of not less than 130 ° C. and the like.
Hereinafter, 2- (carboxymethoxy) -9H-thioxanthen-9-one and 2-hydroxy-9H-thioxanthen-9-one are also referred to as “raw material thioxanthone derivatives”.
上記芳香族環又は上記脂肪族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、シクロブタン環、シクロペンタン環、シクロヘキサン環、シクロオクタン環、ノルボルネン環、トリシクロデカン環等の芳香族環又は脂肪族環における少なくとも1つ以上の水素原子が炭素数1以上の置換基に置換されたものが挙げられる。 The monofunctional epoxy compound preferably has an aromatic ring having at least one or more substituents having one or more carbon atoms or an aliphatic ring having at least one or more substituents having one or more carbon atoms.
Examples of the aromatic ring or the aliphatic ring include aromatic rings such as benzene ring, naphthalene ring, anthracene ring, cyclobutane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclooctane ring, norbornene ring, tricyclodecane ring, etc. That in which at least one or more hydrogen atoms in an aliphatic ring is substituted by a C 1 or more substituent is mentioned.
上記芳香族環又は上記脂肪族環の有する炭素数1以上の置換基としては、アルキル基が好ましい。 The substituent having one or more carbon atoms may be linear or branched. When the substituent having 1 or more carbon atoms is linear, the number of carbon atoms is preferably 6 or more, and more preferably 10 or more. When the substituent having 1 or more carbon atoms is branched, it is preferable that the number of carbon atoms is 4 or more. Moreover, it is preferable that carbon number of the C1 or more substituent which the said aromatic ring or the said aliphatic ring has is a number used as the molecular weight of the said monofunctional epoxy compound becomes 300 or less mentioned later.
As a substituent having one or more carbon atoms which the aromatic ring or the aliphatic ring has, an alkyl group is preferable.
上記アルキルフェニルグリシジルエーテルとしては、例えば、o-メチルフェニルグリシジルエーテル、m-メチルフェニルグリシジルエーテル、p-メチルフェニルグリシジルエーテル、p-tert-ブチルフェニルグリシジルエーテル等が挙げられる。 Examples of the monofunctional epoxy compound include alkylphenyl glycidyl ether, toluene sulfonate having a glycidyl group, 2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate and the like.
Examples of the alkylphenyl glycidyl ether include o-methylphenyl glycidyl ether, m-methylphenyl glycidyl ether, p-methylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether and the like.
上記ナガセケムテックス社製の単官能エポキシ化合物としては、例えば、デナコールEX-146等が挙げられる。
上記ADEKA社製の単官能エポキシ化合物としては、例えば、ED-509S、ED-509E、ED-529等が挙げられる。
上記三菱ケミカル社製の単官能エポキシ化合物としては、例えば、YED-122等が挙げられる。
上記東京化成工業社製の単官能エポキシ化合物としては、例えば、グリシジル2-メトキシフェニルエーテル、1-メチル-1,2-エポキシシクロヘキサン等が挙げられる。
上記ダイセル社製の単官能エポキシ化合物としては、例えば、セロキサイド2000、サイクロマーM100等が挙げられる。 Among the above monofunctional epoxy compounds, for example, monofunctional epoxy compounds manufactured by Nagase ChemteX Corp., monofunctional epoxy compounds manufactured by ADEKA, monofunctional epoxy compounds manufactured by Mitsubishi Chemical Co., Ltd., Tokyo Chemical Industry Co., Ltd. Examples thereof include monofunctional epoxy compounds manufactured by Co., and monofunctional epoxy compounds manufactured by Daicel.
Examples of the monofunctional epoxy compound manufactured by Nagase ChemteX Corp. include Denacol EX-146.
Examples of the monofunctional epoxy compound manufactured by ADEKA include ED-509S, ED-509E, ED-529 and the like.
Examples of monofunctional epoxy compounds manufactured by Mitsubishi Chemical Corporation include YED-122.
Examples of monofunctional epoxy compounds manufactured by Tokyo Chemical Industry Co., Ltd. include glycidyl 2-methoxyphenyl ether, 1-methyl-1,2-epoxycyclohexane and the like.
Examples of the monofunctional epoxy compound manufactured by Daicel Corporation include Celoxide 2000, Cyclomer M100 and the like.
上記塩基性触媒としては、具体的には例えば、トリフェニルホスフィン、トリエチルアミン、トリプロミルアミン、テトラメチルエチレンジアミン、ジメチルラウリルアミン、トリエチルベンジルアンモニウムクロライド、トリメチルセチルアンモニウムブロマイド、テトラブチルアンモニウムブロマイド、トリメチルブチルホスホニウムブロマイド、テトラブチルホスホニウムブロマイド等が挙げられる。なかでも、トリフェニルホスフィンが好ましい。
また、上記塩基性触媒は、ポリマーに担持させて、ポリマー担持塩基性触媒として使用することもできる。 As a basic catalyst used when making the said raw material thioxanthone derivative and the said monofunctional epoxy compound react, a trivalent organic phosphoric acid compound and / or an amine compound are preferable.
Specific examples of the above basic catalyst include triphenylphosphine, triethylamine, trypromylamine, tetramethylethylenediamine, dimethyllaurylamine, triethylbenzylammonium chloride, trimethylcetyl ammonium bromide, tetrabutyl ammonium bromide, trimethylbutyl phosphonium bromide. And tetrabutylphosphonium bromide and the like. Among them, triphenyl phosphine is preferable.
The above basic catalyst can also be supported on a polymer and used as a polymer-supported basic catalyst.
上記熱重合開始剤としては、例えば、アゾ化合物、有機過酸化物等からなるものが挙げられる。なかでも、高分子アゾ化合物からなる高分子アゾ開始剤が好ましい。
なお、本明細書において上記「高分子アゾ化合物」とは、アゾ基を有し、熱によって(メタ)アクリロイルオキシ基を硬化させることができるラジカルを生成する、数平均分子量が300以上の化合物を意味する。 The sealing agent for a liquid crystal display element of the present invention may contain a thermal polymerization initiator as long as the object of the present invention is not impaired.
As said thermal-polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among them, a polymeric azo initiator comprising a polymeric azo compound is preferred.
In the present specification, the above-mentioned "polymer azo compound" refers to a compound having a number average molecular weight of 300 or more which has an azo group and generates a radical capable of curing a (meth) acryloyloxy group by heat. means.
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で溶媒としてテトラヒドロフランを用いて測定を行い、ポリスチレン換算により求められる値である。GPCによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Shodex LF-804(昭和電工社製)等が挙げられる。 The preferable lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the high molecular weight azo compound is in this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination. A more preferable lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 5,000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a still more preferable upper limit is 90,000.
In the present specification, the above-mentioned number average molecular weight is a value obtained by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and measuring in terms of polystyrene. As a column at the time of measuring the number average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko) etc. are mentioned, for example.
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ化合物としては、ポリエチレンオキサイド構造を有するものが好ましい。
上記高分子アゾ化合物としては、具体的には例えば、4,4’-アゾビス(4-シアノペンタン酸)とポリアルキレングリコールの重縮合物や、4,4’-アゾビス(4-シアノペンタン酸)と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられる。
上記高分子アゾ化合物のうち市販されているものとしては、例えば、VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001(いずれも富士フイルム和光純薬社製)等が挙げられる。
また、高分子ではないアゾ化合物としては、例えば、V-65、V-501(いずれも富士フイルム和光純薬社製)等が挙げられる。 As said high molecular weight azo compound, what has the structure which multiple units, such as a polyalkylene oxide and polydimethylsiloxane, couple | bonded via an azo group is mentioned, for example.
As a polymeric azo compound having a structure in which a plurality of units such as a polyalkylene oxide is bonded via the above azo group, one having a polyethylene oxide structure is preferable.
Specific examples of the high molecular weight azo compound include polycondensates of 4,4'-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis (4-cyanopentanoic acid) And polydimethylsiloxanes having a terminal amino group, and the like.
As what is marketed among the said polymeric azo compounds, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all are Fujifilm Wako Pure Chemical Industries, Ltd. make) etc. are mentioned, for example. Be
Further, as an azo compound which is not a polymer, for example, V-65, V-501 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), etc. may be mentioned.
後述するように、本発明においてマレイミド化合物は、上記硬化性樹脂には含まない。 The sealing agent for a liquid crystal display element of the present invention contains a curable resin.
As described later, in the present invention, the maleimide compound is not included in the curable resin.
上記(メタ)アクリル化合物としては、例えば、(メタ)アクリル酸エステル化合物、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート等が挙げられる。なかでも、エポキシ(メタ)アクリレートが好ましい。また、上記(メタ)アクリル化合物は、反応性の高さから分子中に(メタ)アクリロイル基を2個以上有するものが好ましい。
なお、本明細書において、上記「(メタ)アクリル」とは、アクリル又はメタクリルを意味し、上記「(メタ)アクリル化合物」とは、(メタ)アクリロイル基を有する化合物を意味し、上記「(メタ)アクリロイル」とは、アクリロイル又はメタクリロイルを意味する。また、上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味する。更に、上記「エポキシ(メタ)アクリレート」とは、エポキシ化合物中の全てのエポキシ基を(メタ)アクリル酸と反応させた化合物のことを表す。 It is preferable that the said curable resin contains a (meth) acrylic compound.
As said (meth) acrylic compound, a (meth) acrylic acid ester compound, an epoxy (meth) acrylate, urethane (meth) acrylate etc. are mentioned, for example. Among these, epoxy (meth) acrylate is preferable. Moreover, what the said (meth) acrylic compound has 2 or more of (meth) acryloyl groups in a molecule | numerator from the height of the reactivity is preferable.
In the present specification, the above “(meth) acrylic” means acrylic or methacrylic, and the above “(meth) acrylic compound” means a compound having a (meth) acryloyl group, and the above “((meth) acrylic compound” "Meth) acryloyl" means acryloyl or methacryloyl. Moreover, the above-mentioned "(meth) acrylate" means an acrylate or a methacrylate. Furthermore, the above-mentioned "epoxy (meth) acrylate" represents the compound which made all the epoxy groups in an epoxy compound react with (meth) acrylic acid.
上記ビスフェノールF型エポキシ化合物のうち市販されているものとしては、例えば、jER806、jER4004(いずれも三菱ケミカル社製)等が挙げられる。
上記ビスフェノールS型エポキシ化合物のうち市販されているものとしては、例えば、エピクロンEXA1514(DIC社製)等が挙げられる。
上記2,2’-ジアリルビスフェノールA型エポキシ化合物のうち市販されているものとしては、例えば、RE-810NM(日本化薬社製)等が挙げられる。
上記水添ビスフェノール型エポキシ化合物のうち市販されているものとしては、例えば、エピクロンEXA7015(DIC社製)等が挙げられる。
上記プロピレンオキシド付加ビスフェノールA型エポキシ化合物のうち市販されているものとしては、例えば、EP-4000S(ADEKA社製)等が挙げられる。
上記レゾルシノール型エポキシ化合物のうち市販されているものとしては、例えば、EX-201(ナガセケムテックス社製)等が挙げられる。
上記ビフェニル型エポキシ化合物のうち市販されているものとしては、例えば、jER YX-4000H(三菱ケミカル社製)等が挙げられる。
上記スルフィド型エポキシ化合物のうち市販されているものとしては、例えば、YSLV-50TE(新日鉄住金化学社製)等が挙げられる。
上記ジフェニルエーテル型エポキシ化合物のうち市販されているものとしては、例えば、YSLV-80DE(新日鉄住金化学社製)等が挙げられる。
上記ジシクロペンタジエン型エポキシ化合物のうち市販されているものとしては、例えば、EP-4088S(ADEKA社製)等が挙げられる。
上記ナフタレン型エポキシ化合物のうち市販されているものとしては、例えば、エピクロンHP4032、エピクロンEXA-4700(いずれもDIC社製)等が挙げられる。
上記フェノールノボラック型エポキシ化合物のうち市販されているものとしては、例えば、エピクロンN-770(DIC社製)等が挙げられる。
上記オルトクレゾールノボラック型エポキシ化合物のうち市販されているものとしては、例えば、エピクロンN-670-EXP-S(DIC社製)等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ化合物のうち市販されているものとしては、例えば、エピクロンHP7200(DIC社製)等が挙げられる。
上記ビフェニルノボラック型エポキシ化合物のうち市販されているものとしては、例えば、NC-3000P(日本化薬社製)等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ化合物のうち市販されているものとしては、例えば、ESN-165S(新日鉄住金化学社製)等が挙げられる。
上記グリシジルアミン型エポキシ化合物のうち市販されているものとしては、例えば、jER630(三菱ケミカル社製)、エピクロン430(DIC社製)、TETRAD-X(三菱ガス化学社製)等が挙げられる。
上記アルキルポリオール型エポキシ化合物のうち市販されているものとしては、例えば、ZX-1542(新日鉄住金化学社製)、エピクロン726(DIC社製)、エポライト80MFA(共栄社化学社製)、デナコールEX-611(ナガセケムテックス社製)等が挙げられる。
上記ゴム変性型エポキシ化合物のうち市販されているものとしては、例えば、YR-450、YR-207(いずれも新日鉄住金化学社製)、エポリードPB(ダイセル社製)等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールEX-147(ナガセケムテックス社製)等が挙げられる。
上記エポキシ化合物のうちその他に市販されているものとしては、例えば、YDC-1312、YSLV-80XY、YSLV-90CR(いずれも新日鉄住金化学社製)、XAC4151(旭化成社製)、jER1031、jER1032(いずれも三菱ケミカル社製)、EXA-7120(DIC社製)、TEPIC(日産化学社製)等が挙げられる。 As what is marketed among the said bisphenol A epoxy compounds, jER 828 EL, j ER 1004 (all are Mitsubishi Chemical Co., Ltd. make), Epiclon 850 CRP (made by DIC company) etc. are mentioned, for example.
As what is marketed among the said bisphenol F-type epoxy compounds, jER806, jER4004 (all are Mitsubishi Chemical Co., Ltd. make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy compounds, Epiclon EXA1514 (made by DIC company) etc. are mentioned, for example.
Among the above 2,2′-diallyl bisphenol A epoxy compounds, commercially available ones include RE-810 NM (manufactured by Nippon Kayaku Co., Ltd.) and the like.
As what is marketed among the said hydrogenated bisphenol epoxy compounds, Epiclon EXA7015 (made by DIC company) etc. are mentioned, for example.
Among the above-mentioned propylene oxide-added bisphenol A type epoxy compounds, commercially available ones include, for example, EP-4000S (manufactured by ADEKA Corporation).
Examples of commercially available resorcinol type epoxy compounds include EX-201 (manufactured by Nagase ChemteX Corp.).
Among the above-mentioned biphenyl type epoxy compounds, commercially available ones include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Among the above dicyclopentadiene type epoxy compounds, commercially available ones include, for example, EP-4088S (manufactured by Adeka).
Examples of commercially available naphthalene type epoxy compounds include Epiclon HP4032 and Epiclon EXA-4700 (all manufactured by DIC Corporation).
Examples of the commercially available phenol novolac epoxy compounds include Epiclon N-770 (manufactured by DIC Corporation).
Examples of commercially available ortho-cresol novolac epoxy compounds include Epiclon N-670-EXP-S (manufactured by DIC Corporation).
As what is marketed among the said dicyclopentadiene novolak-type epoxy compounds, Epiclon HP7200 (made by DIC Corporation) etc. are mentioned, for example.
Among the above biphenyl novolac epoxy compounds, commercially available ones include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.
Examples of commercially available naphthalenephenol novolac epoxy compounds include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Among the above glycidyl amine type epoxy compounds, commercially available ones include jER630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.
Among the above alkyl polyol type epoxy compounds, commercially available ones are, for example, ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiclon 726 (manufactured by DIC Corporation), Epolight 80 MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Made by Nagase ChemteX) etc. are mentioned.
Among the above rubber-modified epoxy compounds, commercially available ones include YR-450, YR-207 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and Eporide PB (manufactured by Daicel Co., Ltd.).
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corp.).
Among the above epoxy compounds, as other commercially available ones, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all are manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corp.), jER1031, jER1032 (any one) Also available from Mitsubishi Chemical Corporation, EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.), and the like.
上記ダイセル・オルネクス社製のエポキシ(メタ)アクリレートとしては、例えば、EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182等が挙げられる。
上記新中村化学工業社製のエポキシ(メタ)アクリレートとしては、例えば、EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020等が挙げられる。
上記共栄社化学社製のエポキシ(メタ)アクリレートとしては、例えば、エポキシエステルM-600A、エポキシエステル40EM、エポキシエステル70PA、エポキシエステル200PA、エポキシエステル80MFA、エポキシエステル3002M、エポキシエステル3002A、エポキシエステル1600A、エポキシエステル3000M、エポキシエステル3000A、エポキシエステル200EA、エポキシエステル400EA等が挙げられる。
上記ナガセケムテックス社製のエポキシ(メタ)アクリレートとしては、例えば、デナコールアクリレートDA-141、デナコールアクリレートDA-314、デナコールアクリレートDA-911等が挙げられる。 As what is marketed among the above-mentioned epoxy (meth) acrylates, for example, epoxy (meth) acrylate manufactured by Daicel Ornex, epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., epoxy manufactured by Kyoeisha Chemical Examples thereof include meta) acrylates and epoxy (meth) acrylates manufactured by Nagase ChemteX Corporation.
Examples of the epoxy (meth) acrylates manufactured by Daicel Ornex Co., Ltd. include, for example, EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3702, EBECRYL 3702, EBECRYL 3703, EBECRYL E800 ECL EHL
Examples of the epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 and the like.
Examples of epoxy (meth) acrylates manufactured by Kyoeisha Chemical Co., Ltd. include epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, epoxy ester 1600A, Epoxy ester 3000 M, epoxy ester 3000 A, epoxy ester 200 EA, epoxy ester 400 EA, etc. may be mentioned.
Examples of the epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911 and the like.
上記ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、グリセリン、ソルビトール、トリメチロールプロパン、カーボネートジオール、ポリエーテルジオール、ポリエステルジオール、ポリカプロラクトンジオール等が挙げられる。 Moreover, as the above-mentioned isocyanate compound, a chain-extended isocyanate compound obtained by the reaction of a polyol and an excess of an isocyanate compound can also be used.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and the like.
上記ヒドロキシアルキルモノ(メタ)アクリレートとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等が挙げられる。
上記二価のアルコールとしては、例えば、エチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ポリエチレングリコール等が挙げられる。
上記三価のアルコールとしては、例えば、トリメチロールエタン、トリメチロールプロパン、グリセリン等が挙げられる。
上記エポキシ(メタ)アクリレートとしては、例えば、ビスフェノールA型エポキシアクリレート等が挙げられる。 As the (meth) acrylic acid derivative having a hydroxyl group, for example, hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of dihydric alcohol, mono (meth) acrylate or di (meth) acrylate of trihydric alcohol And epoxy (meth) acrylates.
Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. It can be mentioned.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like.
Examples of the trihydric alcohol include trimethylol ethane, trimethylol propane and glycerin.
As said epoxy (meth) acrylate, bisphenol-A epoxy acrylate etc. are mentioned, for example.
上記東亞合成社製のウレタン(メタ)アクリレートとしては、例えば、M-1100、M-1200、M-1210、M-1600等が挙げられる。
上記ダイセル・オルネクス社製のウレタン(メタ)アクリレートとしては、例えば、EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、EBECRYL8803、EBECRYL8804、EBECRYL8807、EBECRYL9260等が挙げられる。
上記根上工業社製のウレタン(メタ)アクリレートとしては、例えば、アートレジンUN-330、アートレジンSH-500B、アートレジンUN-1200TPK、アートレジンUN-1255、アートレジンUN-3320HB、アートレジンUN-7100、アートレジンUN-9000A、アートレジンUN-9000H等が挙げられる。
上記新中村化学工業社製のウレタン(メタ)アクリレートとしては、例えば、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等が挙げられる。
上記共栄社化学社製のウレタン(メタ)アクリレートとしては、例えば、AH-600、AI-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T等が挙げられる。 As what is marketed among the above-mentioned urethane (meta) acrylates, for example, urethane (meta) acrylate by Toagosei Co., Ltd., urethane (meta) acrylate by Daicel Ornex, urethane (meta) by Negami Kogyo Co., Ltd. Acrylate, urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.
Examples of the urethane (meth) acrylate manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210 and M-1600.
As the urethane (meth) acrylate manufactured by the above-mentioned Daicel Ornex Co., Ltd., for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYLL4852, EBECRYLL5129, EBECRYLL747. It can be mentioned.
Examples of urethane (meth) acrylates manufactured by Negami Chemical Industries, Ltd. include art resin UN-330, art resin SH-500B, art resin UN-1200TPK, art resin UN-1255, art resin UN-3320 HB, art resin UN- 7100, Art resin UN-9000A, Art resin UN-9000H and the like.
Examples of urethane (meth) acrylates manufactured by Shin-Nakamura Chemical Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, and the like. U-15 HA, U-108, U-108 A, U-122 A, U-122 P, U-324 A, U-340 A, U-340 P, U-1084 A, U-2061 BA, UA-340 P, UA-4000, UA- 4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A and the like.
Examples of urethane (meth) acrylates manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T, etc. Be
なお、本明細書において上記部分(メタ)アクリル変性エポキシ化合物とは、1分子中にエポキシ基と(メタ)アクリロイル基とをそれぞれ1つ以上有する化合物を意味し、例えば、1分子中に2つ以上のエポキシ基を有するエポキシ化合物の一部分のエポキシ基を(メタ)アクリル酸と反応させることによって得ることができる。 It is preferable that the said curable resin contains an epoxy compound further in order to improve the adhesiveness of the sealing compound for liquid crystal display elements obtained. As said epoxy compound, the epoxy compound used as the raw material for synthesize | combining the epoxy (meth) acrylate mentioned above, a partial (meth) acryl modified epoxy compound, etc. are mentioned, for example.
In the present specification, the above-mentioned partial (meth) acrylic-modified epoxy compound means a compound having one or more epoxy group and one or more (meth) acryloyl group in one molecule, for example, two in one molecule. It can obtain by making the epoxy group of a part of the epoxy compound which has the above epoxy group react with (meth) acrylic acid.
上記マレイミド化合物を用いることにより、本発明の液晶表示素子用シール剤は、本発明にかかる光重合開始剤を用いても異物の発生を抑制できるものとなる。
なお、本発明において上記マレイミド化合物は、硬化性樹脂には含まない。 The sealing agent for a liquid crystal display element of the present invention contains a maleimide compound.
By using the maleimide compound, the sealing agent for a liquid crystal display element of the present invention can suppress the generation of foreign matter even when using the photopolymerization initiator according to the present invention.
In the present invention, the maleimide compound is not included in the curable resin.
また、反応性の観点から、上記マレイミド化合物の分子量の好ましい上限は1500、より好ましい上限は1000である。 The preferred lower limit of the molecular weight of the maleimide compound is 400. When the molecular weight of the maleimide compound is 400 or more, the obtained sealing agent for a liquid crystal display element is excellent due to the effect of achieving both the improvement of the curability to long wavelength light and the suppression of the generation of foreign matter. A more preferable lower limit of the molecular weight of the maleimide compound is 500.
Further, from the viewpoint of reactivity, the upper limit of the molecular weight of the maleimide compound is preferably 1,500, and more preferably 1,000.
上記式(4)で表される化合物としては、具体的には例えば、1,4-ビス(マレイミド)ブタン、1,20-ビスマレイミド-10,11-ジオクチル-エイコサン(下記式(5-1)で表される化合物)、1-ヘプチレンマレイミド-2-オクチレンマレイミド-4-オクチル-5-ヘプチルシクロヘキサン(下記式(5-2)で表される化合物)、1,2-ジオクチレンマレイミド-3-オクチル-4-ヘキシルシクロヘキサン(下記式(5-3)で表される化合物)等が挙げられる。
上記式(4)で表される化合物は、例えば、米国特許第5973166号明細書に記載の方法等によって合成することができる。 In the above formula (4), the carbon number of R 2 is preferably 12 to 36. Further, R 2 preferably has an aliphatic ring.
Specific examples of the compound represented by the above formula (4) include 1,4-bis (maleimide) butane, 1,20-bismaleimide-10,11-dioctyl-eicosane (following formula (5-1) ), 1-heptylenemaleimide-2-octylenemaleimide-4-octyl-5-heptylcyclohexane (compound represented by the following formula (5-2)), 1,2-dioc Examples include lenmaleimide-3-octyl-4-hexylcyclohexane (compound represented by the following formula (5-3)) and the like.
The compound represented by the above formula (4) can be synthesized, for example, by the method described in US Pat. No. 5,973,166.
上記熱硬化剤としては、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。 The sealing agent for a liquid crystal display element of the present invention may contain a thermosetting agent.
As said thermosetting agent, an organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned, for example. Among these, organic acid hydrazides are preferably used.
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、大塚化学社製の有機酸ヒドラジド、味の素ファインテクノ社製の有機酸ヒドラジド等が挙げられる。
上記大塚化学社製の有機酸ヒドラジドとしては、例えば、SDH、ADH等が挙げられる。
上記味の素ファインテクノ社製の有機酸ヒドラジドとしては、例えば、アミキュアVDH、アミキュアVDH-J、アミキュアUDH、アミキュアUDH-J等が挙げられる。 Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
As what is marketed among the said organic acid hydrazide, the organic acid hydrazide by Otsuka Chemical Co., Ltd., the organic acid hydrazide by Ajinomoto Fine Techno Co., Ltd., etc. are mentioned, for example.
Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J and the like.
上記無機充填剤としては、例えば、シリカ、タルク、ガラスビーズ、石綿、石膏、珪藻土、スメクタイト、ベントナイト、モンモリロナイト、セリサイト、活性白土、アルミナ、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、水酸化アルミニウム、窒化アルミニウム、窒化珪素、硫酸バリウム、珪酸カルシウム等が挙げられる。
上記有機充填剤としては、例えば、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等が挙げられる。
上記充填剤は、単独で用いられてもよいし、2種以上が組み合わせて用いられてもよい。 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, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide And 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, vinyl polymer fine particles, and acrylic polymer fine particles.
The above fillers may be used alone or in combination of two or more.
まず、ITO薄膜等の電極付きのガラス基板やポリエチレンテレフタレート基板等の2枚の基板の一方に、本発明の液晶表示素子用シール剤を、スクリーン印刷、ディスペンサー塗布等により塗布して枠状のシールパターンを形成する工程を行う。次いで、本発明の液晶表示素子用シール剤が未硬化の状態で液晶の微小滴を基板のシールパターンの枠内に滴下塗布し、真空下で別の基板を重ね合わせる工程を行う。その後、本発明の液晶表示素子用シール剤のシールパターン部分に420nmカットフィルター等を介して光を照射することにより、長波長の光によってシール剤を光硬化させる工程を行う方法により、液晶表示素子を得ることができる。また、上記シール剤を光硬化させる工程に加えて、シール剤を加熱して熱硬化させる工程を行ってもよい。 As a method of manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method is suitably used, and specifically, for example, a method having the following respective steps can be mentioned.
First, the sealing agent for a liquid crystal display element of the present invention is applied by screen printing, dispenser coating, or the like to one of two substrates such as a glass substrate with an electrode such as ITO thin film and a polyethylene terephthalate substrate. The process of forming a pattern is performed. Next, a step of applying minute droplets of liquid crystal to the inside of the frame of the seal pattern of the substrate by a drop in a state where the sealing agent for a liquid crystal display element of the present invention is uncured is dropped, and another substrate is superposed under vacuum. Thereafter, the seal pattern portion of the sealing agent for a liquid crystal display element of the present invention is irradiated with light through a 420 nm cut filter or the like to perform a step of photocuring the sealing agent with long wavelength light. You can get In addition to the step of photocuring the sealing agent, the step of heating and thermally curing the sealing agent may be performed.
2-(カルボキシメトキシ)-9H-チオキサンテン-9-オン87重量部と、単官能エポキシ化合物としてp-tert-ブチルフェニルグリシジルエーテル(ADEKA社製、「ED-509S」)62重量部とを、塩基性触媒の存在下で、110℃で48時間撹拌しながら反応させることにより、上記式(2-1)で表される化合物(m=1)を得た。塩基性触媒としては、PS-PPh3(バイオタージ・ジャパン社製、ポリスチレン(PS)にトリフェニルホスフィンを担持した塩基性触媒)5.2重量部を用いた。
なお、得られた上記式(2-1)で表される化合物の構造は、1H-NMR、13C-NMR、及び、FT-IRにより確認した。
また、2-(カルボキシメトキシ)-9H-チオキサンテン-9-オンとp-tert-ブチルフェニルグリシジルエーテルとの配合割合は、モル比で、2-(カルボキシメトキシ)-9H-チオキサンテン-9-オン:p-tert-ブチルフェニルグリシジルエーテル=1:1である。 (Preparation of a Compound Represented by Formula (2-1))
87 parts by weight of 2- (carboxymethoxy) -9H-thioxanthen-9-one and 62 parts by weight of p-tert-butylphenyl glycidyl ether (manufactured by ADEKA, "ED-509S") as a monofunctional epoxy compound, The reaction was carried out while stirring at 110 ° C. for 48 hours in the presence of a basic catalyst to obtain a compound (m = 1) represented by the above formula (2-1). As a basic catalyst, 5.2 parts by weight of PS-PPh 3 (a basic catalyst in which triphenylphosphine is supported on polystyrene (PS) manufactured by Biotage Japan Ltd.) was used.
The structure of the obtained compound represented by the above formula (2-1) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.
Further, the mixing ratio of 2- (carboxymethoxy) -9H-thioxanthen-9-one and p-tert-butylphenyl glycidyl ether is, in molar ratio, 2- (carboxymethoxy) -9H-thioxanthene-9- On: p-tert-butylphenyl glycidyl ether = 1: 1.
2-ヒドロキシ-9H-チオキサンテン-9-オン69重量部と、単官能エポキシ化合物としてp-tert-ブチルフェニルグリシジルエーテル(ADEKA社製、「ED-509S」)62重量部とを、塩基性触媒の存在下で、110℃で48時間撹拌しながら反応させることにより、上記式(2-2)で表される化合物を得た。塩基性触媒としては、PS-PPh3(バイオタージ・ジャパン社製、ポリスチレン(PS)にトリフェニルホスフィンを担持した塩基性触媒)5.2重量部を用いた。
なお、得られた上記式(2-2)で表される化合物の構造は、1H-NMR、13C-NMR、及び、FT-IRにより確認した。
また、2-ヒドロキシ-9H-チオキサンテン-9-オンとp-tert-ブチルフェニルグリシジルエーテルとの配合割合は、モル比で、2-ヒドロキシ-9H-チオキサンテン-9-オン:p-tert-ブチルフェニルグリシジルエーテル=1:1である。 (Preparation of a Compound Represented by Formula (2-2))
A basic catalyst comprising 69 parts by weight of 2-hydroxy-9H-thioxanthen-9-one and 62 parts by weight of p-tert-butylphenyl glycidyl ether ("ED-509S" manufactured by ADEKA Corporation) as a monofunctional epoxy compound The reaction was carried out with stirring at 110 ° C. for 48 hours in the presence of to give a compound represented by the above formula (2-2). As a basic catalyst, 5.2 parts by weight of PS-PPh 3 (a basic catalyst in which triphenylphosphine is supported on polystyrene (PS) manufactured by Biotage Japan Ltd.) was used.
The structure of the obtained compound represented by the above formula (2-2) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.
The mixing ratio of 2-hydroxy-9H-thioxanthen-9-one and p-tert-butylphenyl glycidyl ether is, in molar ratio, 2-hydroxy-9H-thioxanthen-9-one: p-tert- Butylphenyl glycidyl ether = 1: 1.
表1、2に記載された配合比に従い、各材料を遊星式撹拌機(シンキー社製、「あわとり練太郎」)を用いて混合した後、更に3本ロールを用いて混合することにより実施例1~9及び比較例1~3の液晶表示素子用シール剤を調製した。
なお、実施例及び比較例で用いた光重合開始剤について、濃度が0.1mg/mLとなるようにアクリロニトリルに溶解した後、分光光度計(日立ハイテクサイエンス社製、「U-3900」)を用いて波長430nmおける吸光係数を測定した。結果を表1、2に示した。
また、マレイミド化合物として表中に記載したポリテトラメチレンエーテルグリコールのジマレイミド酢酸エステル(DIC社製、「LUMICURE MIA200」)は、上記式(3)で表される化合物である。 (Examples 1 to 9 and Comparative Examples 1 to 3)
According to the compounding ratio described in Tables 1 and 2, after mixing each material using a planetary stirrer ("Awatori Neritaro" manufactured by Shinky Co., Ltd.), mixing is further performed using three rolls. Sealing agents for liquid crystal display devices of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared.
In addition, about the photoinitiator used by the Example and the comparative example, after melt | dissolving in an acrylonitrile so that a density | concentration may be 0.1 mg / mL, a spectrophotometer (the Hitachi High-Tech Science company make, "U-3900") The extinction coefficient at a wavelength of 430 nm was measured using this. The results are shown in Tables 1 and 2.
Moreover, the dimaleimidoacetic acid ester ("LUMICURE MIA200" by DIC Corporation) described in the table as a maleimide compound is a compound represented by the above-mentioned formula (3).
実施例及び比較例で得られた各液晶表示素子用シール剤について以下の評価を行った。結果を表1、2に示した。 <Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
実施例及び比較例で得られた各液晶表示素子用シール剤100重量部にスペーサ微粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を分散させた。次いで、シール剤をディスペンス用のシリンジ(武蔵エンジニアリング社製、「PSY-10E」)に充填し、脱泡処理を行ってから、ディスペンサー(武蔵エンジニアリング社製、「SHOTMASTER300」)にてガラス基板上に塗布した。その基板に真空貼り合わせ装置にて5Paの減圧下にて同サイズのガラス基板を貼り合わせた。貼り合わせたガラス基板のシール剤部分にメタルハライドランプを用いて100mW/cm2の光を10秒照射した。光照射は420nmカットフィルター無しの場合と420nmカットフィルター有りの場合との2パターンを行った。
赤外分光装置(BIORAD社製、「FTS3000」)を用いてシール剤のFT-IR測定を行い、(メタ)アクリロイル基由来ピークの光照射前後での変化量を測定することで硬化性の評価を行った。光照射後に(メタ)アクリロイル基由来のピークが80%以上減少した場合を「◎」、70%以上80%未満減少した場合を「○」、50%以上70%未満減少した場合を「△」、光照射後の(メタ)アクリロイル基由来のピークの減少が50%未満であった場合を「×」として光硬化性を評価した。 (Photo-curable)
One part by weight of spacer fine particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Co., Ltd.) was dispersed in 100 parts by weight of the sealing agent for each liquid crystal display element obtained in Examples and Comparative Examples. Next, the sealing agent is filled in a syringe for dispensing (Musashi Engineering Co., Ltd., “PSY-10E”), and after defoaming treatment, it is placed on a glass substrate with a dispenser (Mousashi Engineering Co., Ltd., “SHOTMASTER 300”) It applied. A glass substrate of the same size was bonded to the substrate under a reduced pressure of 5 Pa by a vacuum bonding apparatus. A light of 100 mW / cm 2 was irradiated to the sealant portion of the bonded glass substrate for 10 seconds using a metal halide lamp. Light irradiation performed two patterns, the case without a 420 nm cut filter, and the case with a 420 nm cut filter.
Evaluation of curability by performing FT-IR measurement of the sealing agent using an infrared spectrometer (manufactured by BIORAD, "FTS 3000") and measuring the amount of change of the (meth) acryloyl group-derived peak before and after light irradiation Did. The case where the peak derived from (meth) acryloyl group decreases by 80% or more after light irradiation is "◎", the case where it decreases by 70% or more and less than 80% is "」 ", the case where it decreases 50% or more and less than 70% is" Δ " The photocurability was evaluated as “×” when the decrease in the peak derived from the (meth) acryloyl group after light irradiation was less than 50%.
実施例及び比較例で得られた各液晶表示素子用シール剤100重量部にスペーサ微粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を分散させ、蛍光灯直下で3時間放置した。次いで、シール剤をディスペンス用のシリンジ(武蔵エンジニアリング社製、「PSY-10E」)に充填し、脱泡処理を行ってから、ディスペンサー(武蔵エンジニアリング社製、「SHOTMASTER300」)にてガラス基板上に塗布した。その基板に真空貼り合わせ装置にて5Paの減圧下にて同サイズのガラス基板を貼り合わせた。この際、先の蛍光灯直下で放置した際にシール剤中に異物が発生していると、その異物が基板間に噛みこむことにより、ギャップ不良が発生することになる。
貼り合わせた基板を確認し、ギャップ不良が全く発生していなかった場合を「○」、ギャップ不良が僅かに発生していた場合を「△」、ギャップ不良が明らかに発生していた場合を「×」として異物防止性を評価した。 (Foreign substance prevention)
One part by weight of spacer fine particles ("Micropearl SI-H050" manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of the sealing agent for each liquid crystal display element obtained in Examples and Comparative Examples, and 3 hours under fluorescent lamp I left it. Next, the sealing agent is filled in a syringe for dispensing (Musashi Engineering Co., Ltd., “PSY-10E”), and after defoaming treatment, it is placed on a glass substrate with a dispenser (Mousashi Engineering Co., Ltd., “SHOTMASTER 300”) It applied. A glass substrate of the same size was bonded to the substrate under a reduced pressure of 5 Pa by a vacuum bonding apparatus. At this time, if foreign matter is generated in the sealing agent when left immediately below the above-mentioned fluorescent lamp, the foreign matter bites between the substrates to cause gap defects.
The bonded substrates were checked, and if no gap failure occurred at all, "○", a slight gap failure occurred, "△", and gap failure apparently occurred. Foreign substance prevention was evaluated as "x".
Claims (8)
- 硬化性樹脂と光重合開始剤とマレイミド化合物とを含有し、
前記光重合開始剤は、波長430nmにおける吸光係数が0.8×102mL/g・cm以上である
ことを特徴とする液晶表示素子用シール剤。 Containing a curable resin, a photopolymerization initiator and a maleimide compound,
The sealing agent for a liquid crystal display element, wherein the photopolymerization initiator has an absorption coefficient at a wavelength of 430 nm of 0.8 × 10 2 mL / g · cm or more. - 光重合開始剤は、下記式(1)で表される構造を有する化合物である請求項1記載の液晶表示素子用シール剤。
- 式(1)で表される構造を有する化合物は、1分子中に1個の該式(1)で表される構造を有する化合物である請求項2記載の液晶表示素子用シール剤。 The sealing compound for a liquid crystal display element according to claim 2, wherein the compound having a structure represented by the formula (1) is a compound having a structure represented by the formula (1) in one molecule.
- 式(1)で表される構造を有する化合物は、下記式(2-1)で表される化合物及び/又は下記式(2-2)で表される化合物である請求項3記載の液晶表示素子用シール剤。
- マレイミド化合物は、1分子中に2個以上のマレイミド基を有する多官能マレイミド化合物である請求項1、2、3又は4記載の液晶表示素子用シール剤。 The sealing agent for a liquid crystal display element according to claim 1, 2, 3 or 4, wherein the maleimide compound is a polyfunctional maleimide compound having two or more maleimide groups in one molecule.
- マレイミド化合物は、分子量が400以上である請求項1、2、3、4又は5記載の液晶表示素子用シール剤。 The sealing compound for a liquid crystal display element according to claim 1, wherein the maleimide compound has a molecular weight of 400 or more.
- 請求項1、2、3、4、5又は6記載の液晶表示素子用シール剤と導電性微粒子とを含有する上下導通材料。 An upper and lower conducting material comprising the sealing agent for a liquid crystal display element according to claim 1, 2, 3, 4, 5 or 6 and conductive fine particles.
- 請求項1、2、3、4、5若しくは6記載の液晶表示素子用シール剤又は請求項7記載の上下導通材料を用いてなる液晶表示素子。 A liquid crystal display device comprising the sealing agent for a liquid crystal display device according to claim 1, 2, 3, 4, 5, or 6, or the vertical conduction material according to claim 7.
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JP2014532083A (en) * | 2011-09-15 | 2014-12-04 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co.KGaA | Sealant composition |
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