JP4532883B2 - Photocurable resin composition, liquid crystal display element sealing agent, liquid crystal display element sealing agent, liquid crystal display element vertical conduction material, and liquid crystal display device - Google Patents
Photocurable resin composition, liquid crystal display element sealing agent, liquid crystal display element sealing agent, liquid crystal display element vertical conduction material, and liquid crystal display device Download PDFInfo
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- JP4532883B2 JP4532883B2 JP2003394616A JP2003394616A JP4532883B2 JP 4532883 B2 JP4532883 B2 JP 4532883B2 JP 2003394616 A JP2003394616 A JP 2003394616A JP 2003394616 A JP2003394616 A JP 2003394616A JP 4532883 B2 JP4532883 B2 JP 4532883B2
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- Prior art keywords
- liquid crystal
- crystal display
- resin
- display element
- sealing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 108
- 239000003795 chemical substances by application Substances 0.000 title claims description 53
- 239000011342 resin composition Substances 0.000 title claims description 51
- 238000007789 sealing Methods 0.000 title claims description 42
- 239000000463 material Substances 0.000 title claims description 30
- 229920005989 resin Polymers 0.000 claims description 80
- 239000011347 resin Substances 0.000 claims description 80
- 239000010419 fine particle Substances 0.000 claims description 44
- 230000009477 glass transition Effects 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 27
- 229920001187 thermosetting polymer Polymers 0.000 claims description 23
- 239000007771 core particle Substances 0.000 claims description 21
- 125000000524 functional group Chemical group 0.000 claims description 17
- 239000000565 sealant Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- 150000004292 cyclic ethers Chemical group 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000000691 measurement method Methods 0.000 claims description 7
- 239000007870 radical polymerization initiator Substances 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 5
- 239000000758 substrate Substances 0.000 description 41
- 239000011521 glass Substances 0.000 description 26
- 229920000647 polyepoxide Polymers 0.000 description 17
- 238000001723 curing Methods 0.000 description 16
- 239000003822 epoxy resin Substances 0.000 description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- -1 methacryloyl group Chemical group 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
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- 238000004519 manufacturing process Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 244000028419 Styrax benzoin Species 0.000 description 4
- 235000000126 Styrax benzoin Nutrition 0.000 description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 235000019382 gum benzoic Nutrition 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 239000000919 ceramic Substances 0.000 description 3
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 125000003566 oxetanyl group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
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- 239000010409 thin film Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- QLGYTJLZFZUDFL-UHFFFAOYSA-N 1,3-bis[1-(1h-imidazol-2-yl)propyl]urea Chemical compound N=1C=CNC=1C(CC)NC(=O)NC(CC)C1=NC=CN1 QLGYTJLZFZUDFL-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- BRXKVEIJEXJBFF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)C(CO)(CO)CO BRXKVEIJEXJBFF-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- VDAIJDKQXDCJSI-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethylurea Chemical compound CC1=NC=CN1CCNC(N)=O VDAIJDKQXDCJSI-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- VLJFHOQFPSGZPC-UHFFFAOYSA-N 2-[2-hydroxy-5-(2-methylprop-2-enoyloxy)pentoxy]carbonylbenzoic acid Chemical compound CC(=C)C(=O)OCCCC(O)COC(=O)C1=CC=CC=C1C(O)=O VLJFHOQFPSGZPC-UHFFFAOYSA-N 0.000 description 1
- VIYWVRIBDZTTMH-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 VIYWVRIBDZTTMH-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- YQZZHMXSIYMFDK-UHFFFAOYSA-N 2-[bis(2-prop-2-enoyloxyethoxy)phosphoryloxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOP(=O)(OCCOC(=O)C=C)OCCOC(=O)C=C YQZZHMXSIYMFDK-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BJDUIGDNWNRBMW-UHFFFAOYSA-N 2-phenyl-1h-imidazole-4,5-diol Chemical class N1C(O)=C(O)N=C1C1=CC=CC=C1 BJDUIGDNWNRBMW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- NPYMXLXNEYZTMQ-UHFFFAOYSA-N 3-methoxybutyl prop-2-enoate Chemical compound COC(C)CCOC(=O)C=C NPYMXLXNEYZTMQ-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WMONOXOCMIPNNU-UHFFFAOYSA-N C=CC(=O)OCCCC(O)COC(=O)C1=CC=CC=C1C(O)=O Chemical compound C=CC(=O)OCCCC(O)COC(=O)C1=CC=CC=C1C(O)=O WMONOXOCMIPNNU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- FEXQDZTYJVXMOS-UHFFFAOYSA-N Isopropyl benzoate Chemical compound CC(C)OC(=O)C1=CC=CC=C1 FEXQDZTYJVXMOS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
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- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
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- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 125000005641 methacryl group Chemical group 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- BLGWXSOTAXXXDE-UHFFFAOYSA-N n'-[1-(1h-imidazol-2-yl)propyl]hexanediamide Chemical compound NC(=O)CCCCC(=O)NC(CC)C1=NC=CN1 BLGWXSOTAXXXDE-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000007704 transition Effects 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
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、液晶表示素子のガラス基板との接着性に優れた光硬化性樹脂組成物、液晶表示素子用シール剤、液晶表示素子用封口剤、液晶表示素子用上下導通材料、及び、これを用いてなる液晶表示装置に関する。 The present invention relates to a photocurable resin composition having excellent adhesion to a glass substrate of a liquid crystal display element, a sealing agent for a liquid crystal display element, a sealing agent for a liquid crystal display element, a vertical conduction material for a liquid crystal display element, and The present invention relates to a liquid crystal display device used.
従来、液晶表示セル等の液晶表示素子は、２枚の電極付き透明ガラス基板を、所定の間隔をおいて対向させ、その周囲をシール剤で封着してセルを形成し、その一部に設けられた液晶注入口からセル内に液晶を注入し、その液晶注入口をシール剤又は封口剤を用いて封止することにより作製されていた。
この方法では、まず、２枚の電極付き透明ガラス基板のいずれか一方に、スクリーン印刷により熱硬化性シール剤を用いた液晶注入口を設けたシールパターンを形成し、６０〜１００℃でプリベイクを行いシール剤中の溶剤を乾燥させる。次いで、スペーサーを挟んで２枚の基板を対向させてアライメントを行い貼り合わせ、１１０〜２２０℃で１０〜９０分間熱プレスを行いシール近傍のギャップを調整した後、オーブン中で１１０〜２２０℃で１０〜１２０分間加熱しシール剤を本硬化させる。次いで、液晶注入口から液晶を注入し、最後に封口剤を用いて液晶注入口を封止して、液晶表示素子を作製していた。
Conventionally, a liquid crystal display element such as a liquid crystal display cell forms a cell by making two transparent glass substrates with electrodes face each other at a predetermined interval and sealing the periphery with a sealant, and forming a cell The liquid crystal was prepared by injecting liquid crystal into the cell from the provided liquid crystal injection port and sealing the liquid crystal injection port with a sealing agent or a sealing agent.
In this method, first, a seal pattern provided with a liquid crystal injection port using a thermosetting sealant is formed by screen printing on one of two transparent glass substrates with electrodes, and prebaked at 60 to 100 ° C. The solvent in the sealant is dried. Next, alignment is performed with the two substrates facing each other with a spacer interposed therebetween, and the gap in the vicinity of the seal is adjusted by performing hot pressing at 110 to 220 ° C. for 10 to 90 minutes, and then at 110 to 220 ° C. in an oven. Heat for 10 to 120 minutes to fully cure the sealant. Next, liquid crystal was injected from the liquid crystal injection port, and finally, the liquid crystal injection port was sealed using a sealing agent to produce a liquid crystal display element.
しかし、この作製方法によると、熱歪により位置ズレ、ギャップのバラツキ、シール剤と基板との密着性の低下等が発生する；残留溶剤が熱膨張して気泡が発生しギャップのバラツキやシールパスが発生する；シール硬化時間が長い；プリベイクプロセスが煩雑；溶剤の揮発によりシール剤の使用可能時間が短い；液晶の注入に時間がかかる等の問題があった。とりわけ、近年の大型の液晶表示装置にあっては、液晶の注入に非常に時間がかかることが大きな問題となっていた。 However, according to this manufacturing method, positional displacement, gap variation, and decrease in adhesion between the sealing agent and the substrate occur due to thermal strain; residual solvent thermally expands to generate bubbles, resulting in gap variation and seal path. The seal curing time is long; the prebaking process is complicated; the usable time of the sealant is short due to the volatilization of the solvent; and it takes time to inject liquid crystal. In particular, in a large liquid crystal display device in recent years, it takes a very long time to inject liquid crystal.
これに対して、紫外線硬化型の樹脂組成物からなるシール剤を用いた滴下工法と呼ばれる液晶表示素子の製造方法が検討されている。滴下工法では、まず、２枚の電極付き透明ガラス基板の一方に、スクリーン印刷により長方形状のシールパターンを形成する。次いで、シール剤未硬化の状態で液晶の微小滴をガラス基板の枠内全面に滴下塗布し、すぐに他方のガラス基板を重ねあわせ、シール部に紫外線を照射して硬化を行う。その後、必要に応じて液晶アニール時に加熱して更に硬化を行い、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る。今後はこの滴下工法が液晶表示装置の製造方法の主流となると期待されている。 On the other hand, a manufacturing method of a liquid crystal display element called a dripping method using a sealing agent made of an ultraviolet curable resin composition has been studied. In the dropping method, first, a rectangular seal pattern is formed on one of two transparent glass substrates with electrodes by screen printing. Next, fine droplets of liquid crystal are dropped onto the entire surface of the glass substrate in an uncured state, and the other glass substrate is immediately overlaid, and the seal portion is cured by irradiating with ultraviolet rays. Then, if necessary, it is heated at the time of liquid crystal annealing and further cured to produce a liquid crystal display element. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency. In the future, this dripping method is expected to become the mainstream of liquid crystal display manufacturing methods.
しかし、紫外線硬化型の樹脂組成物からなるシール剤は、従来の熱硬化型の樹脂組成物からなるシール剤に比べてガラス基板との接着力が低いという問題点があり、この改善が強く求められていた。また、このようなシール剤は、その耐熱性を向上させるために樹脂のガラス転移温度を上げる方向に改良されているが、樹脂のガラス転移温度が高くなることで、ガラス基板との接着性が更に低下するという別の問題点もあった。
ガラス基板との接着性を向上させる方法としては、従来よりシランカップリング剤の添加等の方法が知られていたが、接着性向上効果は不充分なだけでなく、液晶を汚染するという問題もあった。
また、シール剤と同様の硬化性樹脂組成物を用いて上下導通材料とした場合にも、シール剤と同様の問題があった。
However, a sealing agent made of an ultraviolet curable resin composition has a problem that it has a lower adhesive force with a glass substrate than a sealing agent made of a conventional thermosetting resin composition, and this improvement is strongly demanded. It was done. In addition, such a sealing agent has been improved in the direction of increasing the glass transition temperature of the resin in order to improve its heat resistance, but the adhesion to the glass substrate is improved by the increase of the glass transition temperature of the resin. There was another problem of further reduction.
As a method for improving the adhesion to the glass substrate, a method such as the addition of a silane coupling agent has been conventionally known. However, the effect of improving the adhesion is not sufficient, and there is a problem that the liquid crystal is contaminated. there were.
In addition, when the curable resin composition similar to that of the sealing agent is used as the vertical conduction material, there is a problem similar to that of the sealing agent.
一方、特許文献１には、ガラス転移温度が４５℃の樹脂からなるコア層とガラス転移温度が１０５℃の樹脂からなるシェル層からなるコアシェル粒子を含有するエポキシ樹脂性接着剤組成物が開示されている。これはエポキシ樹脂の熱硬化反応時に、コアシェル粒子のゴム成分が熱により膨潤することによって、これが外部からの衝撃を吸収して樹脂硬化物の耐衝撃性が向上し、その結果剥離接着力が向上するというものである。しかしながら、この方法は加熱によるコアシェル粒子の膨潤が前提となっていることから、紫外線硬化型の樹脂組成物（又は紫外線硬化型と熱硬化型とが併用された組成物においては、紫外線硬化を先に行うプロセスのもの）の接着性の向上には効果がないと考えられていた。 On the other hand, Patent Document 1 discloses an epoxy resin adhesive composition containing a core layer made of a resin having a glass transition temperature of 45 ° C and a shell layer made of a resin having a glass transition temperature of 105 ° C. ing. This is because the rubber component of the core-shell particles swells due to heat during the thermosetting reaction of the epoxy resin, which absorbs external impact and improves the impact resistance of the cured resin, resulting in improved peel adhesion It is to do. However, since this method is based on the premise that the core-shell particles are swollen by heating, an ultraviolet curable resin composition (or an ultraviolet curable resin is used in combination with an ultraviolet curable resin and a thermosetting resin). It was thought that there was no effect in improving the adhesiveness of the process performed in the above.
本発明は、上記現状に鑑み、液晶表示素子のガラス基板との接着性に優れた光硬化性樹脂組成物、液晶表示素子用シール剤、液晶表示素子用封口剤、液晶表示素子用上下導通材料、及び、これを用いてなる液晶表示装置を提供することを目的とする。 In view of the above situation, the present invention provides a photocurable resin composition excellent in adhesiveness to a glass substrate of a liquid crystal display element, a sealing agent for a liquid crystal display element, a sealing agent for a liquid crystal display element, and a vertical conduction material for a liquid crystal display element An object of the present invention is to provide a liquid crystal display device using the same.
本発明は、ラジカル重合性官能基を有する光硬化性樹脂、環状エーテル基を有する熱硬化性樹脂、光ラジカル重合開始剤及び樹脂微粒子を含有する光硬化性樹脂組成物からなる液晶表示素子用シール剤であって、前記樹脂微粒子は、ゴム弾性を有しガラス転移温度が−１０℃以下である樹脂からなるコア粒子と、前記コア粒子の表面に形成されたガラス転移温度が５０〜１５０℃である樹脂からなるシェル層とを有するものであり、前記コア粒子は、ｎ−ブチルアクリレートを含有する重合体からなり、かつ、前記シェル層はメチルメタクリレートを含有する重合体からなり、昇温速度５℃／分、周波数１０Ｈｚの条件で動的粘弾性測定法（ＤＭＡ法）により測定した硬化物のガラス転移温度が１２０℃以上である液晶表示素子用シール剤である。
本発明は、また、ラジカル重合性官能基を有する光硬化性樹脂、環状エーテル基を有する熱硬化性樹脂、光ラジカル重合開始剤及び樹脂微粒子を含有する光硬化性樹脂組成物からなる液晶表示素子用封口剤であって、前記樹脂微粒子は、ゴム弾性を有しガラス転移温度が−１０℃以下である樹脂からなるコア粒子と、前記コア粒子の表面に形成されたガラス転移温度が５０〜１５０℃である樹脂からなるシェル層とを有するものであり、前記コア粒子は、ｎ−ブチルアクリレートを含有する重合体からなり、かつ、前記シェル層はメチルメタクリレートを含有する重合体からなり、昇温速度５℃／分、周波数１０Ｈｚの条件で動的粘弾性測定法（ＤＭＡ法）により測定した硬化物のガラス転移温度が１２０℃以上である液晶表示素子用封口剤である。
本発明は、また、ラジカル重合性官能基を有する光硬化性樹脂、環状エーテル基を有する熱硬化性樹脂、光ラジカル重合開始剤及び樹脂微粒子を含有する光硬化性樹脂組成物と導電性微粒子とを含む液晶表示素子用上下導通材料であって、前記樹脂微粒子は、ゴム弾性を有しガラス転移温度が−１０℃以下である樹脂からなるコア粒子と、前記コア粒子の表面に形成されたガラス転移温度が５０〜１５０℃である樹脂からなるシェル層とを有するものであり、前記コア粒子は、ｎ−ブチルアクリレートを含有する重合体からなり、かつ、前記シェル層はメチルメタクリレートを含有する重合体からなり、昇温速度５℃／分、周波数１０Ｈｚの条件で動的粘弾性測定法（ＤＭＡ法）により測定した硬化物のガラス転移温度が１２０℃以上である液晶表示素子用上下導通材料である。
以下に本発明を詳述する。
The present invention relates to a seal for a liquid crystal display device comprising a photocurable resin having a radical polymerizable functional group, a thermosetting resin having a cyclic ether group, a photo radical polymerization initiator, and a photo curable resin composition containing resin fine particles. The resin fine particles have a rubber elasticity and a core particle made of a resin having a glass transition temperature of −10 ° C. or less, and a glass transition temperature formed on the surface of the core particle is 50 to 150 ° C. The core particles are made of a polymer containing n-butyl acrylate, and the shell layer is made of a polymer containing methyl methacrylate, and the heating rate is 5 A sealant for liquid crystal display elements in which the glass transition temperature of a cured product measured by a dynamic viscoelasticity measurement method (DMA method) under the conditions of ° C / min and a frequency of 10 Hz is 120 ° C or higher. That.
The present invention also provides a liquid crystal display device comprising a photocurable resin having a radical polymerizable functional group, a thermosetting resin having a cyclic ether group, a photo radical polymerization initiator, and a photo curable resin composition containing resin fine particles. The resin fine particles have rubber elasticity and core particles made of a resin having a glass transition temperature of −10 ° C. or lower, and a glass transition temperature formed on the surface of the core particles is 50 to 150. The core particles are made of a polymer containing n-butyl acrylate, and the shell layer is made of a polymer containing methyl methacrylate. Sealant for liquid crystal display element having a glass transition temperature of 120 ° C. or higher of a cured product measured by a dynamic viscoelasticity measurement method (DMA method) under conditions of a speed of 5 ° C./minute and a frequency of 10 Hz A.
The present invention also includes a photocurable resin having a radical polymerizable functional group, a thermosetting resin having a cyclic ether group, a photo radical polymerization initiator and a resin fine particle, and a photocurable resin composition and conductive fine particles. The resin fine particles include a core particle made of a resin having rubber elasticity and a glass transition temperature of −10 ° C. or less, and glass formed on the surface of the core particle. A shell layer made of a resin having a transition temperature of 50 to 150 ° C., wherein the core particles are made of a polymer containing n-butyl acrylate, and the shell layer is a heavy layer containing methyl methacrylate. The glass transition temperature of the cured product is 120 ° C. or higher as measured by a dynamic viscoelasticity measurement method (DMA method) under conditions of a heating rate of 5 ° C./min and a frequency of 10 Hz. It is a vertically conducting material for crystal display device.
The present invention is described in detail below.
本発明者らは、鋭意検討の結果、硬化後の硬化物のガラス転移温度が特定の値であるような光硬化性樹脂組成物に、特定のコアシェル構造を有する樹脂微粒子を配合することにより、加熱を行わず光により硬化した場合であっても、顕著なガラス基板との接着性の向上効果が得られることを見出し、本発明を完成するに至った。
本発明の光硬化性樹脂組成物は、光硬化性樹脂、光ラジカル重合開始剤及び樹脂微粒子を含有する。
As a result of intensive studies, the inventors have formulated resin fine particles having a specific core-shell structure into a photocurable resin composition having a specific value for the glass transition temperature of the cured product after curing, Even when it is cured by light without heating, it has been found that a remarkable effect of improving adhesion to a glass substrate can be obtained, and the present invention has been completed.
The photocurable resin composition of the present invention contains a photocurable resin, a radical photopolymerization initiator, and resin fine particles.
上記光硬化性樹脂は、ラジカル重合性官能基を有し紫外線等の光を照射することよにより重合して硬化するものである。
上記ラジカル重合性官能基とは、紫外線などの活性エネルギー線によって重合しうる官能基を意味し、例えば、アリル基、アクリロイル基、メタクリロイル基等が挙げられる。
上記ラジカル重合性官能基を有する光硬化性樹脂としては、例えば、（メタ）アクリル樹脂、不飽和ポリエステル樹脂等が挙げられる。これらの樹脂は単独で用いてもよく、２種以上を併用してもよい。
なお、本明細書において（メタ）アクリルとは、アクリル又はメタクリルのことをいう。
The photocurable resin has a radical polymerizable functional group and is cured by being polymerized by irradiation with light such as ultraviolet rays.
The radical polymerizable functional group means a functional group that can be polymerized by active energy rays such as ultraviolet rays, and examples thereof include an allyl group, an acryloyl group, and a methacryloyl group.
Examples of the photocurable resin having a radical polymerizable functional group include (meth) acrylic resins and unsaturated polyester resins. These resins may be used alone or in combination of two or more.
In addition, in this specification, (meth) acryl means acryl or methacryl.
上記（メタ）アクリル基を有する樹脂としては、単官能、２官能又は３官能以上の（メタ）アクリル酸エステル類を重合することにより得ることができる。
上記単官能（メタ）アクリル酸エステル類としては、例えば、２−ヒドロキシエチルアクリレート、ジエチレングリコールモノエチルエーテルアクリレート、イソボロニルアクリレート、３−メトキシブチルアクリレート、２−アクリロイルオキシエチル−２−ヒドロキシプロピルフタレート、２−メタクロイルオキシエチル−２−ヒドロキシルプロピルフタレート等が挙げられる。
上記２官能（メタ）アクリル酸エステル類としては、例えば、エチレングリコールジアクリレート、ジエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、１，６−ヘキサンジオールジメタクリレート、１，９−ノナンジオールジアクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、２，２−ビス［４−（メタクリロキシエトキシ）フェニル］プロパンジ（メタ）アクリレート等が挙げられる。
上記３官能以上の（メタ）アクリル酸エステル類としては、例えは、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、トリ（２−アクリロイルオキシエチル）フォスフェート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールプロパンテトラ（メタ）アクリレート、トリアリルイソシアヌレート及びその誘導体等が挙げられる。これらの（メタ）アクリル酸エステル類は単独で用いてもよく、２種以上を併用してもよい。
The resin having a (meth) acrylic group can be obtained by polymerizing monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid esters.
Examples of the monofunctional (meth) acrylic acid esters include 2-hydroxyethyl acrylate, diethylene glycol monoethyl ether acrylate, isobornyl acrylate, 3-methoxybutyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, Examples include 2-methacryloyloxyethyl-2-hydroxylpropyl phthalate.
Examples of the bifunctional (meth) acrylic acid esters include ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and polytetra Methylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane di (meth) acrylate, etc. Is mentioned.
Examples of the trifunctional or higher functional (meth) acrylic acid esters include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate. , Tri (2-acryloyloxyethyl) phosphate, tetramethylolmethane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, triallyl isocyanurate and derivatives thereof. These (meth) acrylic acid esters may be used alone or in combination of two or more.
上記光硬化性樹脂は、（メタ）アクリル基等のラジカル重合性官能基の他に、更に、エポキシ基やオキセタン基等の環状エーテル基等の熱により反応する官能基を１分子中に有していてもよい。このような官能基を有する場合には、本発明の光硬化性樹脂組成物は、光硬化型と熱硬化型との併用タイプとなり、滴下工法により液晶表示素子を作製する際に、予め光硬化で仮留めした後、熱硬化で完全に硬化させることができ、より高精度かつ容易な作業が可能となるほか、液晶の汚染も防止することができる。
このような１分子内に（メタ）アクリル基とエポキシ基とを有する樹脂としては特に限定されず、例えば、（メタ）アクリル酸変性エポキシ樹脂、ウレタン変性（メタ）アクリルエポキシ樹脂等が挙げられる。
In addition to radically polymerizable functional groups such as (meth) acrylic groups, the above-mentioned photocurable resin further has functional groups that react with heat such as cyclic ether groups such as epoxy groups and oxetane groups in one molecule. It may be. In the case of having such a functional group, the photocurable resin composition of the present invention is a combined type of a photocurable type and a thermosetting type, and is preliminarily photocured when a liquid crystal display element is produced by a dropping method. After being temporarily fastened, it can be completely cured by heat curing, and more accurate and easy work can be performed and contamination of the liquid crystal can be prevented.
Such a resin having a (meth) acryl group and an epoxy group in one molecule is not particularly limited, and examples thereof include (meth) acrylic acid-modified epoxy resins and urethane-modified (meth) acryl epoxy resins.
上記光ラジカル重合開始剤としては、光照射により上記ラジカル重合性官能基を反応させるものであれば特に限定されず、ベンゾフェノン、２，２−ジエトキシアセトフェノン、ベンジル、ベンゾイルイソプロピルエーテル、ベンジルジメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、チオキサントン等が挙げられるが、反応性二重結合と光反応開始部とを有するものを用いれば、光ラジカル重合開始剤の液晶への溶出を防止できることから好ましい。なかでも、（メタ）アクリル残基等の反応性二重結合と、水酸基及び／又はウレタン結合とを有するベンゾイン（エーテル）類化合物が好適である。なお、ベンゾイン（エーテル）類化合物とは、ベンゾイン類及びベンゾインエーテル類を表す。 The radical photopolymerization initiator is not particularly limited as long as it reacts with the radical polymerizable functional group by light irradiation. Benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoylisopropyl ether, benzyldimethyl ketal, Examples thereof include 1-hydroxycyclohexyl phenyl ketone and thioxanthone, but it is preferable to use a compound having a reactive double bond and a photoreaction initiation part because elution of the photoradical polymerization initiator to the liquid crystal can be prevented. Of these, benzoin (ether) compounds having a reactive double bond such as a (meth) acryl residue and a hydroxyl group and / or a urethane bond are preferable. The benzoin (ether) compounds represent benzoins and benzoin ethers.
上記光ラジカル重合開始剤の配合量の好ましい下限は、上記光硬化性樹脂１００重量部に対して０．１重量部、好ましい上限は１０重量部である。０．１重量部未満であると、光ラジカル重合を開始する能力が不足して効果が得られないことがあり、１０重量部を超えると、未反応の光ラジカル重合開始剤が多く残ることがあり、耐候性が悪くなることがある。より好ましい下限は１重量部、より好ましい上限は５重量部である。 The minimum with the preferable compounding quantity of the said radical photopolymerization initiator is 0.1 weight part with respect to 100 weight part of said photocurable resins, and a preferable upper limit is 10 weight part. If the amount is less than 0.1 parts by weight, the ability to initiate photoradical polymerization may be insufficient and the effect may not be obtained. If the amount exceeds 10 parts by weight, a large amount of unreacted photoradical polymerization initiator may remain. Yes, weather resistance may deteriorate. A more preferred lower limit is 1 part by weight, and a more preferred upper limit is 5 parts by weight.
上記樹脂微粒子は、ゴム弾性を有しガラス転移温度が−１０℃以下である樹脂からなるコア粒子と、上記コア粒子の表面に形成されたガラス転移温度が５０〜１５０℃である樹脂からなるシェル層とを有するものである。
なお、本明細書においてガラス転移温度は、特に限定しない限りは通常のＤＳＣ法により昇温速度１０℃／分の条件で測定したものを意味する。
The resin fine particles include a core particle made of a resin having rubber elasticity and a glass transition temperature of −10 ° C. or less, and a shell made of a resin formed on the surface of the core particle and having a glass transition temperature of 50 to 150 ° C. And a layer.
In the present specification, the glass transition temperature means a value measured by a normal DSC method under a temperature rising rate of 10 ° C./min unless otherwise specified.
上記ゴム弾性を有しガラス転移温度が−１０℃以下である樹脂としては特に限定されないが、（メタ）アクリルモノマーの重合体が好適である。
上記（メタ）アクリルモノマーとしては、例えば、エチルアクリレート、プロピルアクリレート、ｎ−ブチルアクリレート、シクロヘキシルアクリレート、２−エチルヘキシルアクリレート、エチルメタクリレート、ブチルメタクリレート等が挙げられる。これらの（メタ）アクリルモノマーは単独で重合してもよく、二種以上を共重合してもよい。
The resin having rubber elasticity and a glass transition temperature of −10 ° C. or lower is not particularly limited, but a polymer of (meth) acrylic monomer is preferable.
Examples of the (meth) acrylic monomer include ethyl acrylate, propyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, and butyl methacrylate. These (meth) acrylic monomers may be polymerized alone or in combination of two or more.
上記ガラス転移温度が５０〜１５０℃である樹脂としては特に限定されず、例えば、イソプロピルメタクリレート、ｔ−ブチルメタクリレート、シクロヘキシルメタクリレート、フェニルメタクリレート、メチルメタクリレート、スチレン、４−クロロスチレン、２−エチルスチレン、アクリロニトリル、塩化ビニル等を重合した重合体が挙げられる。これらのモノマーは単独で用いてもよく、２種以上を併用してもよい。 The resin having a glass transition temperature of 50 to 150 ° C. is not particularly limited. For example, isopropyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methyl methacrylate, styrene, 4-chlorostyrene, 2-ethylstyrene, Examples thereof include polymers obtained by polymerizing acrylonitrile, vinyl chloride and the like. These monomers may be used independently and may use 2 or more types together.
上記樹脂微粒子の粒子径は使用される目的により適宜選択されるが、液晶表示素子用シール剤に用いられる場合、好ましい下限は０．０１μｍ、好ましい上限は５μｍである。この範囲内であると、上記光硬化性樹脂に対する樹脂微粒子の表面積が充分に大きく、効果的なコア層の膨潤効果が現れ、更に液晶表示素子用シール剤として用いたときの基板間のギャップ出し作業性も確保することができる。 The particle diameter of the resin fine particles is appropriately selected depending on the purpose of use, but when used for a sealing agent for liquid crystal display elements, the preferred lower limit is 0.01 μm and the preferred upper limit is 5 μm. Within this range, the surface area of the resin fine particles with respect to the photocurable resin is sufficiently large, and an effective swelling effect of the core layer appears. Further, when used as a sealant for liquid crystal display elements, the gap between the substrates is increased. Workability can also be secured.
上記樹脂微粒子を製造する方法としては特に限定されず、例えば、コアを構成するモノマーのみを用いて乳化重合法によりコア粒子を形成させた後、更にシェルを構成するモノマーを加えて重合してコア粒子の表面にシェル層を形成させる方法等が挙げられる。 The method for producing the resin fine particles is not particularly limited. For example, after forming the core particles by an emulsion polymerization method using only the monomer constituting the core, the core is further polymerized by adding the monomer constituting the shell. Examples thereof include a method of forming a shell layer on the surface of the particles.
本発明の光硬化性樹脂組成物における上記樹脂微粒子の配合量の好ましい下限は、上記光硬化性樹脂１００重量部に対して１５重量部、好ましい上限は５０重量部である。１５重量部未満であると、充分な接着性向上効果が得られないことがあり、５０重量部を超えると、必要以上に増粘してしまうことがある。より好ましい上限は２０重量部である。 The minimum with the preferable compounding quantity of the said resin fine particle in the photocurable resin composition of this invention is 15 weight part with respect to 100 weight part of said photocurable resins, and a preferable upper limit is 50 weight part. If the amount is less than 15 parts by weight, a sufficient adhesive improvement effect may not be obtained. If the amount exceeds 50 parts by weight, the viscosity may increase more than necessary. A more preferred upper limit is 20 parts by weight.
本発明の光硬化性樹脂組成物は、汚染性、接着性をより向上させるために、更に、熱硬化性樹脂を含有してもよい。熱硬化性樹脂を含有することにより、熱硬化性を付与することができる。
上記熱硬化性樹脂としては特に限定されず、例えば、エポキシ基やオキセタニル基等の環状エーテル基を有する樹脂等が挙げられる。上記エポキシ基を有する樹脂としては、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、カテコール型エポキシ樹脂等が挙げられる。
The photocurable resin composition of the present invention may further contain a thermosetting resin in order to further improve the contamination and adhesiveness. By containing a thermosetting resin, thermosetting can be imparted.
The thermosetting resin is not particularly limited, and examples thereof include a resin having a cyclic ether group such as an epoxy group or an oxetanyl group. Examples of the resin having an epoxy group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, catechol type epoxy resin and the like. Can be mentioned.
上記光硬化性樹脂が環状エーテル基を含有し熱硬化性を有する場合や、上記熱硬化性樹脂を含有する場合には、本発明の光硬化性樹脂組成物は、更に硬化剤を含有してもよい。上記硬化剤は、硬化物の接着性、耐湿性を向上させることができる。
上記硬化剤としては、融点が１００℃以上の潜在性硬化剤が好適に用いられる。融点が１００℃以下の硬化剤を使用すると保存安定性が著しく悪くなることがある。このような硬化剤としては、例えば、１，３−ビス［ヒドラジノカルボノエチル−５−イソプロピルヒダントイン］等のヒドラジド化合物、ジシアンジアミド、グアニジン誘導体、１−シアノエチル−２−フェニルイミダゾール、Ｎ−［２−（２−メチル−１−イミダゾリル）エチル］尿素、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジン、Ｎ，Ｎ’−ビス（２−メチル−１−イミダゾリルエチル）尿素、Ｎ，Ｎ’−（２−メチル−１−イミダゾリルエチル）−アジポアミド、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール等のイミダゾール誘導体、変性脂肪族ポリアミン、テトラヒドロ無水フタル酸、エチレングリコール−ビス（アンヒドロトリメリテート）等の酸無水物、各種アミンとエポキシ樹脂との付加生成物等が挙げられる。また、上記硬化剤としては、固体硬化剤粒子の表面が微粒子により被覆されている被覆硬化剤を用いてもよい。
When the photocurable resin contains a cyclic ether group and has thermosetting properties, or when the photocurable resin contains the thermosetting resin, the photocurable resin composition of the present invention further contains a curing agent. Also good. The said hardening | curing agent can improve the adhesiveness and moisture resistance of hardened | cured material.
As the curing agent, a latent curing agent having a melting point of 100 ° C. or higher is preferably used. When a curing agent having a melting point of 100 ° C. or lower is used, the storage stability may be remarkably deteriorated. Examples of such a curing agent include hydrazide compounds such as 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin], dicyandiamide, guanidine derivatives, 1-cyanoethyl-2-phenylimidazole, N- [2 -(2-Methyl-1-imidazolyl) ethyl] urea, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, N, N'-bis (2- Methyl-1-imidazolylethyl) urea, N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxy Imidazole derivatives such as methylimidazole, modified aliphatic polyamines, tetrahydrophthalic anhydride, ethylene glycol -Acid anhydrides such as bis (anhydrotrimellitate), addition products of various amines and epoxy resins, and the like. Further, as the curing agent, a coating curing agent in which the surface of the solid curing agent particles is coated with fine particles may be used.
上記硬化剤の配合量の好ましい下限は、上記光硬化性樹脂１００重量部に対して５重量部、好ましい上限は６０重量部である。この範囲外であると、硬化物の接着性が低下し、高温高湿動作試験での液晶の特性劣化が早まることがある。より好ましい下限は１０重量部、より好ましい上限は５０重量部である。 A preferable lower limit of the amount of the curing agent is 5 parts by weight with respect to 100 parts by weight of the photocurable resin, and a preferable upper limit is 60 parts by weight. If it is out of this range, the adhesiveness of the cured product is lowered, and the liquid crystal characteristic deterioration in the high temperature and high humidity operation test may be accelerated. A more preferred lower limit is 10 parts by weight, and a more preferred upper limit is 50 parts by weight.
本発明の光硬化性樹脂組成物は、更にシランカップリング剤を含有してもよい。シランカップリング剤は、ガラス基板等との接着性を向上させる接着助剤としての役割を有する。
上記シランカップリング剤としては特に限定されないが、ガラス基板等との接着性向上効果に優れ、反応性樹脂と化学結合することにより液晶中への流出を防止するとができることから、例えば、γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−イソシアネートプロピルトリメトキシシラン等や、スペーサー基を介してイミダゾール骨格とアルコキシシリル基とが結合した構造を有するイミダゾールシラン化合物からなるもの等が好適に用いられる。これらのシランカップリング剤は単独で用いてもよく、２種以上を併用してもよい。
The photocurable resin composition of the present invention may further contain a silane coupling agent. The silane coupling agent has a role as an adhesion aid that improves adhesion to a glass substrate or the like.
Although it does not specifically limit as said silane coupling agent, Since it is excellent in the adhesive improvement effect with a glass substrate etc. and it can prevent the outflow in a liquid crystal by chemically bonding with a reactive resin, for example, (gamma) -amino Propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, etc., and the structure in which the imidazole skeleton and alkoxysilyl group are bonded via a spacer group What consists of the imidazole silane compound which has is used suitably. These silane coupling agents may be used alone or in combination of two or more.
本発明の光硬化性樹脂組成物は、応力分散効果による接着性の改善、線膨張率の改善等の目的にフィラーを含有してもよい。上記フィラーとしては特に限定されず、例えば、シリカ粒子、アルミナ、タルク等が挙げられる。 The photocurable resin composition of the present invention may contain a filler for the purpose of improving the adhesiveness due to the stress dispersion effect and improving the linear expansion coefficient. The filler is not particularly limited, and examples thereof include silica particles, alumina, talc and the like.
本発明の光硬化性樹脂組成物は、更に、必要に応じて、粘度調整の為の反応性希釈剤、チクソ性を調整する揺変剤、パネルギャップ調整の為のポリマービーズ等のスペーサー、３−Ｐ−クロロフェニル−１，１−ジメチル尿素等の硬化促進剤、消泡剤、レベリング剤、重合禁止剤、その他添加剤等を含有してもよい。 The photo-curable resin composition of the present invention further includes a spacer such as a reactive diluent for adjusting the viscosity, a thixotropic agent for adjusting thixotropy, a polymer bead for adjusting the panel gap, if necessary. It may contain a curing accelerator such as -P-chlorophenyl-1,1-dimethylurea, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives.
本発明の光硬化性樹脂組成物は、昇温速度５℃／分、周波数１０Ｈｚの条件で動的粘弾性測定法（ＤＭＡ法）により測定した硬化物のガラス転移温度が１２０℃以上である。１２０℃未満であると、上記樹脂微粒子を添加してもガラス基板との接着性の向上効果が得られない。ガラス転移温度の上限は特にないが、好ましい上限は１８０℃である。１８０℃を超えると、接着性を充分に得られないことがある。より好ましい上限は１５０℃である。 The photocurable resin composition of the present invention has a glass transition temperature of 120 ° C. or higher as measured by a dynamic viscoelasticity measurement method (DMA method) under conditions of a temperature rising rate of 5 ° C./min and a frequency of 10 Hz. When the temperature is lower than 120 ° C., the effect of improving the adhesion to the glass substrate cannot be obtained even if the resin fine particles are added. There is no particular upper limit for the glass transition temperature, but a preferred upper limit is 180 ° C. If it exceeds 180 ° C., sufficient adhesion may not be obtained. A more preferred upper limit is 150 ° C.
本発明の光硬化性樹脂組成物は、ガラス基板を接着し、硬化させたときの接着強度が１５０Ｎ／ｃｍ2以上であることが好ましい。１５０Ｎ／ｃｍ2未満であると、得られる液晶表示装置の強度が不足することがある。
なお、上記接着強度は、例えば、本発明の光硬化性樹脂組成物を用いて２枚のガラス基板を接着し硬化させた後、２枚のガラス基板を剥離するのに要する引張強度から求めることができる。
The photocurable resin composition of the present invention preferably has an adhesive strength of 150 N / cm 2 or more when the glass substrate is bonded and cured. If it is less than 150 N / cm 2 , the strength of the obtained liquid crystal display device may be insufficient.
In addition, the said adhesive strength is calculated | required, for example from the tensile strength required to peel off two glass substrates, after adhering and hardening two glass substrates using the photocurable resin composition of this invention. Can do.
本発明の光硬化性樹脂組成物は、硬化物の体積抵抗値が１×１０13Ω・ｃｍ、１００ｋＨｚにおける誘電率が３以上であることが好ましい。体積抵抗値が１×１０13Ω・ｃｍ未満であると、本発明の光硬化性樹脂組成物がイオン性の不純物を含有していることを意味し、シール剤、封口剤又は上下導通材料として用いた場合に通電時にイオン性不純物が液晶中に溶出し、液晶駆動電圧に影響を与え、表示ムラの原因となることがある。また、液晶の誘電率は、通常ε//（パラレル）が１０、ε⊥（垂直）が３．５程度であることから、誘電率が３未満であると、硬化性樹脂組成物が液晶中に溶出し、液晶駆動電圧に影響を与え、表示ムラの原因となることがある。 The photocurable resin composition of the present invention preferably has a cured product having a volume resistance of 1 × 10 13 Ω · cm and a dielectric constant of 3 or more at 100 kHz. When the volume resistance value is less than 1 × 10 13 Ω · cm, it means that the photocurable resin composition of the present invention contains ionic impurities, and as a sealing agent, a sealing agent, or a vertical conduction material When used, ionic impurities may elute into the liquid crystal when energized, affecting the liquid crystal drive voltage and causing display unevenness. In addition, the dielectric constant of the liquid crystal is usually about ε // (parallel) is about 10 and ε⊥ (vertical) is about 3.5. Therefore, when the dielectric constant is less than 3, the curable resin composition is in the liquid crystal. May affect the liquid crystal driving voltage and cause display unevenness.
本発明の光硬化性樹脂組成物を製造する方法としては特に限定されず、例えば、上記光硬化性樹脂、光カチオン重合開始剤、樹脂微粒子及び必要に応じて配合される添加剤を、従来公知の方法により混合する方法等が挙げられる。このとき、イオン性の不純物を除去するために層状珪酸塩鉱物等のイオン吸着性固体と接触させてもよい。 The method for producing the photocurable resin composition of the present invention is not particularly limited. For example, the above-described photocurable resin, photocationic polymerization initiator, resin fine particles, and additives blended as necessary are conventionally known. And the like. At this time, in order to remove ionic impurities, it may be brought into contact with an ion-adsorbing solid such as a layered silicate mineral.
本発明の光硬化性樹脂組成物は、光硬化型でありながらガラス基板に対する接着性が高いことから、例えば、滴下工法等により液晶表示装置を作製する場合に液晶表示素子用シール剤や、液晶表示素子用封口剤に好適である。
本発明の光硬化性樹脂組成物を用いてなる液晶表示素子用シール剤、液晶表示素子用封口剤もまた、本発明の１つである。
Since the photocurable resin composition of the present invention has a high adhesiveness to a glass substrate while being photocurable, for example, when a liquid crystal display device is produced by a dropping method or the like, a sealing agent for a liquid crystal display element or a liquid crystal It is suitable for a sealant for display elements.
The sealing agent for liquid crystal display elements and the sealing agent for liquid crystal display elements which use the photocurable resin composition of this invention are also one of this invention.
また、液晶表示装置には、一般的に、２枚の透明基板上の対向する電極間を上下導通させるために、上下導通材料が使用されている。上記上下導通材料は通常、硬化性樹脂組成物に導電性微粒子が含有されて構成されている。
本発明の光硬化性樹脂組成物と導電性微粒子とを含む液晶表示素子用上下導通材料もまた、本発明の１つである。
In addition, in the liquid crystal display device, a vertical conduction material is generally used in order to make vertical conduction between opposing electrodes on two transparent substrates. The vertical conduction material is usually configured by containing conductive fine particles in a curable resin composition.
The vertical conduction material for a liquid crystal display element comprising the photocurable resin composition of the present invention and conductive fine particles is also one aspect of the present invention.
上記導電性微粒子としては特に限定されず、例えば、金属微粒子；樹脂基材微粒子に金属メッキを施したもの（以下、金属メッキ微粒子という）；樹脂基材微粒子に金属メッキを施した後樹脂等で被覆したもの（以下、被覆金属メッキ微粒子という）；更にこれらの金属微粒子、金属メッキ微粒子、被覆金属メッキ微粒子で表面に突起を有するもの等が挙げられる。なかでも、樹脂組成物中への均一分散性や導電性に優れることから、金メッキを施した金属メッキ微粒子や被覆金属メッキ微粒子が好ましい。 The conductive fine particles are not particularly limited. For example, metal fine particles; those obtained by subjecting resin substrate fine particles to metal plating (hereinafter referred to as metal plating fine particles); Those coated (hereinafter referred to as coated metal plated fine particles); and those metal fine particles, metal plated fine particles, and coated metal plated fine particles having protrusions on the surface. Especially, since it is excellent in the uniform dispersibility in a resin composition and electroconductivity, the metal plating fine particle and covering metal plating fine particle which gave gold plating are preferable.
上記導電性微粒子の、上記光硬化性樹脂組成物１００重量部に対する配合量の好ましい下限は０．２重量部、好ましい上限は５重量部である。 The minimum with the preferable compounding quantity with respect to 100 weight part of the said photocurable resin compositions of the said electroconductive fine particles is 0.2 weight part, and a preferable upper limit is 5 weight part.
本発明の液晶表示素子用上下導通材料を製造する方法としては特に限定されず、例えば、上記光硬化性樹脂組成物、上記導電性微粒子等を所定の配合量となるように配合し、真空遊星式攪拌装置等で混合する方法等が挙げられる。 The method for producing the vertical conduction material for a liquid crystal display element of the present invention is not particularly limited. For example, the photocurable resin composition, the conductive fine particles and the like are blended so as to have a predetermined blending amount, and a vacuum planetary The method of mixing with a type | formula stirring apparatus etc. is mentioned.
本発明の液晶表示素子用シール剤、本発明の液晶表示素子用封口剤、及び本発明の液晶表示素子用上下導通材料の少なくとも一つを用いて液晶表示装置を製造する方法としては特に限定されず、例えば、以下の方法により製造することができる。
まず、ＩＴＯ薄膜等の２枚の電極付き透明ガラス基板の何れか一方に、本発明の液晶表示素子用シール剤を液晶注入口が解放された所定のパターンとなるように塗布する。塗布方法としては、スクリーン印刷、ディスペンサー塗布等が挙げられる。更に、もう一方の透明基板に、本発明の液晶表示素子用上下導通材料を所定の電極上に塗布する。塗布方法としては、スクリーン印刷、ディスペンサー塗布等が挙げられる。なお、上下導通材料を用いる代わりにシール剤に導電性微粒子を含有させ、上下導通を図ることも可能である。次いで、上記２枚の透明基板をスペーサーを介して対向させ、位置合わせを行いながら重ね合わせる。その後、ガラス基板のシール部及び上下導通材料部に紫外線を照射して硬化させる。本発明の液晶表示素子用シール剤及び本発明の液晶表示素子用上下導通材料が熱硬化性を有する場合には、更に１００〜２００℃のオーブン中で１時間加熱硬化させて硬化を完了させる。最後に液晶注入口より液晶を注入し、本発明の液晶表示素子用封口剤を用いて注入口を塞ぎ、液晶表示装置を作製する。
A method for producing a liquid crystal display device using at least one of the sealing agent for liquid crystal display elements of the present invention, the sealing agent for liquid crystal display elements of the present invention, and the vertical conduction material for liquid crystal display elements of the present invention is particularly limited. For example, it can be manufactured by the following method.
First, the sealing agent for liquid crystal display elements of the present invention is applied to one of two transparent glass substrates with electrodes, such as an ITO thin film, so as to form a predetermined pattern in which the liquid crystal inlet is released. Examples of the application method include screen printing and dispenser application. Furthermore, the vertical conduction material for a liquid crystal display element of the present invention is applied onto a predetermined electrode on the other transparent substrate. Examples of the application method include screen printing and dispenser application. Instead of using a vertical conduction material, it is possible to incorporate conductive fine particles in the sealant to achieve vertical conduction. Next, the two transparent substrates are opposed to each other via a spacer, and are overlapped while aligning. Thereafter, the sealing portion and the vertical conduction material portion of the glass substrate are cured by irradiating with ultraviolet rays. When the sealing agent for liquid crystal display elements of the present invention and the vertical conduction material for liquid crystal display elements of the present invention have thermosetting properties, they are further cured by heating in an oven at 100 to 200 ° C. for 1 hour to complete the curing. Finally, liquid crystal is injected from the liquid crystal injection port, and the injection port is closed using the sealing agent for a liquid crystal display element of the present invention to produce a liquid crystal display device.
また、滴下工法による液晶表示装置の製造方法としては、例えば、ＩＴＯ薄膜等の２枚の電極付き透明基板の一方に、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長方形状のシールパターンを形成する。更に、もう一方の透明基板に、本発明の液晶表示素子用上下導通材料をスクリーン印刷、ディスペンサー塗布等により所定の電極上に上下導通用パターンを形成する。なお、上下導通材料を用いる代わりにシール剤に導電性微粒子を含有させ、上下導通を図ることも可能である。次いで、シール剤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塗布し、すぐに他方の透明基板を上下導通材料未硬化の状態で重ねあわせ、シール部及び上下導通材料部に紫外線を照射して硬化させる。本発明の液晶表示素子用シール剤及び本発明の液晶表示素子用上下導通材料が熱硬化性を有する場合には、更に１００〜２００℃のオーブン中で１時間加熱硬化させて硬化を完了させ、液晶表示装置を作製する。
本発明の液晶表示素子用シール剤、本発明の液晶表示素子用封口剤、及び本発明の液晶表示素子用上下導通材料の少なくとも一つを用いてなる液晶表示装置もまた、本発明の１つである。
Moreover, as a manufacturing method of the liquid crystal display device by a dripping method, for example, the liquid crystal display element sealant of the present invention is formed into a rectangular shape by screen printing, dispenser application, etc. on one of two transparent substrates with electrodes such as an ITO thin film. The seal pattern is formed. Further, a vertical conduction pattern is formed on a predetermined electrode on the other transparent substrate by screen printing, dispenser application or the like of the vertical conduction material for a liquid crystal display element of the present invention. Instead of using a vertical conduction material, it is possible to incorporate conductive fine particles in the sealant to achieve vertical conduction. Next, a liquid crystal micro-droplet is dropped onto the entire surface of the transparent substrate frame in an uncured state of the sealant, and the other transparent substrate is immediately overlapped in an uncured state of the vertically conductive material, and the seal portion and the vertically conductive material portion The material is cured by irradiating it with ultraviolet rays. When the sealing agent for liquid crystal display elements of the present invention and the vertical conduction material for liquid crystal display elements of the present invention have thermosetting properties, the curing is further completed by heating and curing in an oven at 100 to 200 ° C. for 1 hour, A liquid crystal display device is manufactured.
A liquid crystal display device using at least one of the sealing agent for liquid crystal display elements of the present invention, the sealing agent for liquid crystal display elements of the present invention, and the vertical conduction material for liquid crystal display elements of the present invention is also one aspect of the present invention. It is.
本発明によれば、液晶表示素子のガラス基板との接着性に優れた光硬化性樹脂組成物、液晶表示素子用シール剤、液晶表示素子用封口剤、液晶表示素子用上下導通材料、及び、これを用いてなる液晶表示装置を提供できる。 According to the present invention, a photocurable resin composition excellent in adhesiveness with a glass substrate of a liquid crystal display element, a sealing agent for a liquid crystal display element, a sealing agent for a liquid crystal display element, a vertical conduction material for a liquid crystal display element, and A liquid crystal display device using this can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
（１）光硬化性樹脂組成物の作製
ラジカル重合性官能基を有する樹脂として、ビスフェノールＡ型エポキシアクリレート（ダイセルＵＣＢ社製：ＥＢ３７００）６０重量部、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン社製：エピコート８２８）１０重量部、光ラジカル重合開始剤（チバ・スペシャリティケミカルズ社製：ＩＲ−６５１）２重量部を配合し、これを７０℃に加熱して光ラジカル重合開始剤を溶解させた後、遊星式攪拌装置にて混合攪拌して混合物を得た。
Example 1
(1) Preparation of photocurable resin composition As resin having a radical polymerizable functional group, 60 parts by weight of bisphenol A type epoxy acrylate (manufactured by Daicel UCB: EB3700), bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: Epicoat 828) 10 parts by weight, 2 parts by weight of a radical photopolymerization initiator (Ciba Specialty Chemicals: IR-651) were blended and heated to 70 ° C. to dissolve the radical photopolymerization initiator, The mixture was obtained by mixing and stirring with a planetary stirrer.
この混合物にコアシェル構造微粒子（日本ゼオン社製：Ｆ−３５１）１０量部、球状シリカ（アドマファイン社製：ＳＯ−Ｃ１）１６重量部、熱硬化剤（大塚化学社製：ＡＤＨ）２重量部を配合し、遊星式攪拌装置にて混合攪拌した後、セラミックス３本ロールにて分散させて、光硬化性樹脂組成物を得た。 In this mixture, 10 parts by weight of core-shell structured fine particles (manufactured by Nippon Zeon: F-351), 16 parts by weight of spherical silica (manufactured by Admafine: SO-C1), 2 parts by weight of thermosetting agent (manufactured by Otsuka Chemical: ADH) Were mixed and stirred with a planetary stirrer, and then dispersed with three ceramic rolls to obtain a photocurable resin composition.
（２）硬化物のガラス転移温度の測定
得られた光硬化性樹脂組成物を５×３５×０．３５ｍｍの短冊状の薄片状に塗布し、これを１００ｍＷの強度の紫外線を３０秒間照射した後に、更に１２０℃、６０分間熱処理して硬化させ、測定用試験片を得た。
動的粘弾性測定装置（ＤＭＡ）にて２０℃〜１８０℃の温度範囲で弾性率Ｅ’とｔａｎδを求め、この値から光硬化性樹脂組成物の硬化物のガラス転移温度を測定したところ、１５０℃であった。
(2) Measurement of glass transition temperature of cured product The obtained photocurable resin composition was applied to a strip-like thin piece of 5 × 35 × 0.35 mm, and this was irradiated with ultraviolet rays having an intensity of 100 mW for 30 seconds. Thereafter, it was further cured by heat treatment at 120 ° C. for 60 minutes to obtain a test specimen for measurement.
When the elastic modulus E ′ and tan δ were determined in a temperature range of 20 ° C. to 180 ° C. with a dynamic viscoelasticity measuring device (DMA), and the glass transition temperature of the cured product of the photocurable resin composition was measured from this value, It was 150 ° C.
（３）接着試験
得られた光硬化性樹脂組成物１００重量部に対し、５μｍのガラス短繊維スペーサー５重量部を配合、混合したものを、無アルカリガラス基板（コーニング社製：♯１７３７）に微小滴下し、これに同じガラス基板を十字状に貼り合わせた。１００ｍＷの強度の紫外線を３０秒間照射した後に、更に１２０℃、６０分間熱処理して硬化させ、測定用試験片を得た。
各々のガラス基板を上下に配したチャックに固定し、引張速度５ｍｍ／ｓｅｃの条件で引張強度を求め、これを接着強度とした。接着強度は１８０Ｎ／ｃｍ2であった。
(3) Adhesion test 100 parts by weight of the obtained photocurable resin composition was blended with 5 parts by weight of a 5 μm short glass fiber spacer, and the resulting mixture was added to an alkali-free glass substrate (Corning Corporation: # 1737). A minute drop was made, and the same glass substrate was bonded in a cross shape. After irradiating ultraviolet rays having an intensity of 100 mW for 30 seconds, it was further cured by heat treatment at 120 ° C. for 60 minutes to obtain a test specimen for measurement.
Each glass substrate was fixed to a chuck arranged vertically, and the tensile strength was determined under the condition of a tensile speed of 5 mm / sec. The adhesive strength was 180 N / cm 2 .
（比較例１）
ラジカル重合性官能基を有する樹脂としてビスフェノールＡ型エポキシアクリレート（ダイセルＵＣＢ社製：ＥＢ３７００）６０重量部、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン社製：エピコート８２８）１０重量部、光ラジカル重合開始剤（チバ・スペシャリティケミカルズ社製：ＩＲ−６５１）２重量部を配合し、これを７０℃に加熱して光ラジカル重合開始剤を溶解させた後、遊星式攪拌装置にて混合攪拌して混合物を得た。この混合物に球状シリカ（アドマファイン社製：ＳＯ−Ｃ１）２６重量部、熱硬化剤（大塚化学社製：ＡＤＨ）２重量部を配合し、遊星式攪拌装置にて混合攪拌した後、セラミックス３本ロールにて分散させて、光硬化性樹脂組成物を得た。
(Comparative Example 1)
As a resin having a radical polymerizable functional group, 60 parts by weight of bisphenol A type epoxy acrylate (manufactured by Daicel UCB: EB3700), 10 parts by weight of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin: Epicoat 828), photo radical polymerization initiator (Ciba Specialty Chemicals Co., Ltd .: IR-651) 2 parts by weight were blended and heated to 70 ° C. to dissolve the radical photopolymerization initiator, and then mixed and stirred with a planetary stirrer. Obtained. This mixture was mixed with 26 parts by weight of spherical silica (manufactured by Admafine: SO-C1) and 2 parts by weight of a thermosetting agent (manufactured by Otsuka Chemical Co., Ltd .: ADH). After mixing and stirring with a planetary stirrer, ceramic 3 It was made to disperse | distribute with this roll and the photocurable resin composition was obtained.
得られた光硬化性樹脂組成物について、実施例１と同様の方法により硬化物のガラス転移温度及び接着強度を測定したところ、ガラス転移温度は１５０℃、接着強度は８０Ｎ／ｃｍ2であった。 About the obtained photocurable resin composition, when the glass transition temperature and adhesive strength of hardened | cured material were measured by the method similar to Example 1, glass transition temperature was 150 degreeC and adhesive strength was 80 N / cm < 2 >. .
（比較例２）
ラジカル重合性官能基を有する樹脂としてプロピレンオキサイド付加ビスフェノールＡ型エポキシアクリレート（共栄社化学社製：３００２Ａ）６０重量部、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン社製：エピコート８２８）１０重量部、光ラジカル重合開始剤（チバ・スペシャリティケミカルズ社製：ＩＲ−６５１）２重量部を配合し、これを７０℃に加熱して光ラジカル重合開始剤を溶解させた後、遊星式攪拌装置にて混合攪拌して混合物を得た。この混合物にコアシェル構造微粒子（日本ゼオン社製：Ｆ−３５１）１０重量部、球状シリカ（アドマファイン社製：ＳＯ−Ｃ１）１６重量部、熱硬化剤（大塚化学社製：ＡＤＨ）２重量部を配合し、遊星式攪拌装置にて混合攪拌した後、セラミックス３本ロールにて分散させて、光硬化性樹脂組成物を得た。
(Comparative Example 2)
As a resin having a radical polymerizable functional group, 60 parts by weight of propylene oxide-added bisphenol A type epoxy acrylate (manufactured by Kyoeisha Chemical Co., Ltd .: 3002A), 10 parts by weight of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: Epicoat 828), photo radical 2 parts by weight of a polymerization initiator (manufactured by Ciba Specialty Chemicals: IR-651) is blended, heated to 70 ° C. to dissolve the photoradical polymerization initiator, and then mixed and stirred with a planetary stirrer. To obtain a mixture. In this mixture, 10 parts by weight of core-shell structured fine particles (manufactured by Zeon Corporation: F-351), 16 parts by weight of spherical silica (manufactured by Admafine: SO-C1), 2 parts by weight of thermosetting agent (manufactured by Otsuka Chemical Co., Ltd .: ADH) Were mixed and stirred with a planetary stirrer, and then dispersed with three ceramic rolls to obtain a photocurable resin composition.
得られた光硬化性樹脂組成物について、実施例１と同様の方法により硬化物のガラス転移温度及び接着強度を測定したところ、ガラス転移温度は１００℃、接着強度は９０Ｎ／ｃｍ2であった。 About the obtained photocurable resin composition, when the glass transition temperature and adhesive strength of hardened | cured material were measured by the method similar to Example 1, glass transition temperature was 100 degreeC and adhesive strength was 90 N / cm < 2 >. .
（実施例２）
実施例１と同様にして得られた光硬化性樹脂組成物を均一な液となるように三本ロールを用いて充分に混合した後、光硬化性樹脂組成物１００重量部に対して、導電性微粒子として金メッキを施した金属メッキ微粒子（積水化学工業社製、ミクロパールＡＵ−２０６）２重量部を配合し、真空遊星式攪拌装置で混合して、液晶表示素子用上下導通材料を作製した。
(Example 2)
The photocurable resin composition obtained in the same manner as in Example 1 was sufficiently mixed using a three roll so as to form a uniform liquid, and then conductive with respect to 100 parts by weight of the photocurable resin composition. 2 parts by weight of metal-plated fine particles (Sekisui Chemical Co., Ltd., Micropearl AU-206) with gold plating as the conductive fine particles were mixed and mixed with a vacuum planetary stirrer to produce a vertical conduction material for liquid crystal display elements. .
透明電極付きの２枚の透明基板の一方に、実施例１で得られた光硬化性樹脂組成物をシール剤として長方形の枠を描く様にディスペンサーで塗布した。更に、もう一方の透明基板に、得られた上下導通材料をディスペンサー塗布により上下導通用の電極上に上下導通用パターンを形成した。続いて、液晶（チッソ社製、ＪＣ−５００４ＬＡ）の微小滴をシール剤塗布した透明基板の枠内全面に滴下塗布し、直ぐに他方の透明基板を重ねあわせてシール部及び上下導通材料部に高圧水銀ランプを用い紫外線を５０ｍＷ／ｃｍ2で６０秒照射した。その後、液晶アニールを１２０℃にて１時間行い熱硬化させ、液晶表示装置を作製した。
得られた液晶表示装置は導通性が良好であった。
On one of two transparent substrates with a transparent electrode, the photocurable resin composition obtained in Example 1 was applied as a sealant with a dispenser so as to draw a rectangular frame. Furthermore, a pattern for vertical conduction was formed on the electrode for vertical conduction by applying the obtained vertical conduction material to the other transparent substrate by a dispenser. Subsequently, liquid droplets (manufactured by Chisso Co., Ltd., JC-5004LA) are applied dropwise onto the entire surface of the transparent substrate frame coated with a sealant, and the other transparent substrate is immediately overlaid to apply high pressure to the seal portion and the vertical conduction material portion. Using a mercury lamp, ultraviolet rays were irradiated at 50 mW / cm 2 for 60 seconds. Thereafter, liquid crystal annealing was performed at 120 ° C. for 1 hour for thermosetting to produce a liquid crystal display device.
The obtained liquid crystal display device had good conductivity.
本発明によれば、液晶表示素子のガラス基板との接着性に優れた光硬化性樹脂組成物、液晶表示素子用シール剤、液晶表示素子用封口剤、液晶表示素子用上下導通材料、及び、これを用いてなる液晶表示装置を提供できる。
According to the present invention, a photocurable resin composition excellent in adhesiveness with a glass substrate of a liquid crystal display element, a sealing agent for a liquid crystal display element, a sealing agent for a liquid crystal display element, a vertical conduction material for a liquid crystal display element, and A liquid crystal display device using this can be provided.
Claims (4)
前記樹脂微粒子は、ゴム弾性を有しガラス転移温度が−１０℃以下である樹脂からなるコア粒子と、前記コア粒子の表面に形成されたガラス転移温度が５０〜１５０℃である樹脂からなるシェル層とを有するものであり、
前記コア粒子は、ｎ−ブチルアクリレートを含有する重合体からなり、かつ、前記シェル層はメチルメタクリレートを含有する重合体からなり、
昇温速度５℃／分、周波数１０Ｈｚの条件で動的粘弾性測定法（ＤＭＡ法）により測定した硬化物のガラス転移温度が１２０℃以上である
ことを特徴とする液晶表示素子用シール剤。 A sealant for a liquid crystal display element comprising a photocurable resin having a radical polymerizable functional group, a thermosetting resin having a cyclic ether group, a photo radical polymerization initiator, and a photo curable resin composition containing resin fine particles. ,
The resin fine particles include a core particle made of a resin having rubber elasticity and a glass transition temperature of −10 ° C. or less, and a shell made of a resin having a glass transition temperature of 50 to 150 ° C. formed on the surface of the core particle. And having a layer,
The core particle is made of a polymer containing n-butyl acrylate, and the shell layer is made of a polymer containing methyl methacrylate,
A liquid crystal display element , wherein a glass transition temperature of a cured product measured by a dynamic viscoelasticity measurement method (DMA method) under conditions of a temperature rising rate of 5C / min and a frequency of 10Hz is 120C or more. Sealing agent.
前記樹脂微粒子は、ゴム弾性を有しガラス転移温度が−１０℃以下である樹脂からなるコア粒子と、前記コア粒子の表面に形成されたガラス転移温度が５０〜１５０℃である樹脂からなるシェル層とを有するものであり、
前記コア粒子は、ｎ−ブチルアクリレートを含有する重合体からなり、かつ、前記シェル層はメチルメタクリレートを含有する重合体からなり、
昇温速度５℃／分、周波数１０Ｈｚの条件で動的粘弾性測定法（ＤＭＡ法）により測定した硬化物のガラス転移温度が１２０℃以上である
ことを特徴とする液晶表示素子用封口剤。 A sealing agent for a liquid crystal display device comprising a photocurable resin having a radical polymerizable functional group, a thermosetting resin having a cyclic ether group, a photo radical polymerization initiator, and a photo curable resin composition containing resin fine particles. ,
The resin fine particles include a core particle made of a resin having rubber elasticity and a glass transition temperature of −10 ° C. or less, and a shell made of a resin having a glass transition temperature of 50 to 150 ° C. formed on the surface of the core particle. And having a layer,
The core particle is made of a polymer containing n-butyl acrylate, and the shell layer is made of a polymer containing methyl methacrylate,
A liquid crystal display element , wherein a glass transition temperature of a cured product measured by a dynamic viscoelasticity measurement method (DMA method) under conditions of a temperature rising rate of 5C / min and a frequency of 10Hz is 120C or more. Sealing agent.
前記樹脂微粒子は、ゴム弾性を有しガラス転移温度が−１０℃以下である樹脂からなるコア粒子と、前記コア粒子の表面に形成されたガラス転移温度が５０〜１５０℃である樹脂からなるシェル層とを有するものであり、
前記コア粒子は、ｎ−ブチルアクリレートを含有する重合体からなり、かつ、前記シェル層はメチルメタクリレートを含有する重合体からなり、
昇温速度５℃／分、周波数１０Ｈｚの条件で動的粘弾性測定法（ＤＭＡ法）により測定した硬化物のガラス転移温度が１２０℃以上である
ことを特徴とする液晶表示素子用上下導通材料。 For a liquid crystal display device comprising a photocurable resin having a radical polymerizable functional group, a thermosetting resin having a cyclic ether group, a photo curable resin composition containing a photo radical polymerization initiator and resin fine particles, and conductive fine particles A vertical conduction material,
The resin fine particles include a core particle made of a resin having rubber elasticity and a glass transition temperature of −10 ° C. or less, and a shell made of a resin having a glass transition temperature of 50 to 150 ° C. formed on the surface of the core particle. And having a layer,
The core particle is made of a polymer containing n-butyl acrylate, and the shell layer is made of a polymer containing methyl methacrylate,
A liquid crystal display element , wherein a glass transition temperature of a cured product measured by a dynamic viscoelasticity measurement method (DMA method) under conditions of a temperature rising rate of 5C / min and a frequency of 10Hz is 120C or more. For vertical conduction material.
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003394616A JP4532883B2 (en) | 2003-06-04 | 2003-11-25 | Photocurable resin composition, liquid crystal display element sealing agent, liquid crystal display element sealing agent, liquid crystal display element vertical conduction material, and liquid crystal display device |
| KR1020057023184A KR100935774B1 (en) | 2003-06-04 | 2004-06-04 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| CN 200810214942 CN101367982B (en) | 2003-06-04 | 2004-06-04 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| KR1020097014851A KR100952263B1 (en) | 2003-06-04 | 2004-06-04 | Curing resin composition |
| CN2008102149439A CN101369098B (en) | 2003-06-04 | 2004-06-04 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| PCT/JP2004/007811 WO2004108790A1 (en) | 2003-06-04 | 2004-06-04 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| TW099125906A TWI509015B (en) | 2003-06-04 | 2004-06-04 | A hardened resin composition, a sealant for a liquid crystal display element, and a liquid crystal display element |
| EP04745587A EP1640396A1 (en) | 2003-06-04 | 2004-06-04 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| KR1020097014852A KR101180600B1 (en) | 2003-06-04 | 2004-06-04 | Method for producing curing resin composition |
| TW102143740A TWI504667B (en) | 2003-06-04 | 2004-06-04 | A hardened resin composition, a sealant for a liquid crystal display element, and a liquid crystal display element |
| US10/559,529 US20060240198A1 (en) | 2003-06-04 | 2004-06-04 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| TW093116052A TW200508314A (en) | 2003-06-04 | 2004-06-04 | A liquid crystal display device and curing resin composition, sealing material for the same |
| US12/273,403 US20090093562A1 (en) | 2003-06-04 | 2008-11-18 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
| US12/274,103 US20090134358A1 (en) | 2003-06-04 | 2008-11-19 | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device |
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| JP2003394616A JP4532883B2 (en) | 2003-06-04 | 2003-11-25 | Photocurable resin composition, liquid crystal display element sealing agent, liquid crystal display element sealing agent, liquid crystal display element vertical conduction material, and liquid crystal display device |
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| KR101050702B1 (en) * | 2005-05-09 | 2011-07-20 | 세키스이가가쿠 고교가부시키가이샤 | Sealing material for the liquid crystal dispensing method, transferring material and liquid crystal display devices |
| JP2006343558A (en) * | 2005-06-09 | 2006-12-21 | Seiko Epson Corp | Liquid crystal apparatus and electronic device |
| JP2009134293A (en) * | 2007-11-08 | 2009-06-18 | Sekisui Chem Co Ltd | Sealing agent for liquid crystal installation method, vertical conduction material and liquid crystal display element |
| JP5503134B2 (en) * | 2008-11-21 | 2014-05-28 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| US8859642B2 (en) | 2009-01-15 | 2014-10-14 | Kaneka Corporation | Curable composition, cured article obtained therefrom and process for preparation of the same |
| US8822570B2 (en) | 2009-10-28 | 2014-09-02 | Kaneka Corporation | Photocurable coating composition and coating film formed by hardening same |
| TW201420735A (en) * | 2012-07-12 | 2014-06-01 | Nippon Kayaku Kk | Liquid crystal sealing agent and liquid crystal display cell using same |
| JP5503763B2 (en) * | 2013-02-20 | 2014-05-28 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| KR20220123426A (en) | 2020-02-06 | 2022-09-06 | 미쓰이 가가쿠 가부시키가이샤 | Photothermosetting resin composition and liquid crystal sealing agent comprising same, and liquid crystal display panel and manufacturing method thereof |
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