JP4875441B2 - Sealant composition for liquid crystal dropping method and method for producing liquid crystal display panel using the same - Google Patents
Sealant composition for liquid crystal dropping method and method for producing liquid crystal display panel using the same Download PDFInfo
- Publication number
- JP4875441B2 JP4875441B2 JP2006243056A JP2006243056A JP4875441B2 JP 4875441 B2 JP4875441 B2 JP 4875441B2 JP 2006243056 A JP2006243056 A JP 2006243056A JP 2006243056 A JP2006243056 A JP 2006243056A JP 4875441 B2 JP4875441 B2 JP 4875441B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- mol
- meth
- acrylic resin
- crystal dropping
- 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.)
- Active
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 110
- 238000000034 method Methods 0.000 title claims description 73
- 239000000203 mixture Substances 0.000 title claims description 44
- 239000000565 sealant Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 65
- 229920000178 Acrylic resin Polymers 0.000 claims description 65
- 239000003795 chemical substances by application Substances 0.000 claims description 43
- 125000000524 functional group Chemical group 0.000 claims description 37
- 239000003822 epoxy resin Substances 0.000 claims description 36
- 229920000647 polyepoxide Polymers 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 20
- 239000004593 Epoxy Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 230000015572 biosynthetic process Effects 0.000 description 25
- 238000003786 synthesis reaction Methods 0.000 description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- 229910021642 ultra pure water Inorganic materials 0.000 description 23
- 239000012498 ultrapure water Substances 0.000 description 23
- -1 acrylic ester Chemical class 0.000 description 22
- 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 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000126 substance Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000113 methacrylic resin Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000000569 multi-angle light scattering Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 125000003700 epoxy group Chemical group 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 238000000746 purification Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 9
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000012847 fine chemical Substances 0.000 description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 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 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 5
- 210000002858 crystal cell Anatomy 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 4
- 208000035475 disorder Diseases 0.000 description 4
- 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 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011403 purification operation Methods 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 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 4
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- WORJRXHJTUTINR-UHFFFAOYSA-N 1,4-dioxane;hydron;chloride Chemical compound Cl.C1COCCO1 WORJRXHJTUTINR-UHFFFAOYSA-N 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
- UFYHEYBENRVKPM-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;oxepan-2-one Chemical compound O=C1CCCCCO1.CC(=C)C(=O)OCCO UFYHEYBENRVKPM-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- IXHBSOXJLNEOPY-UHFFFAOYSA-N 2'-anilino-6'-(n-ethyl-4-methylanilino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C=C(C2(C3=CC=CC=C3C(=O)O2)C2=CC(NC=3C=CC=CC=3)=C(C)C=C2O2)C2=CC=1N(CC)C1=CC=C(C)C=C1 IXHBSOXJLNEOPY-UHFFFAOYSA-N 0.000 description 1
- XNDAGYLOQWQWIM-UHFFFAOYSA-N 2,2-dimethylpropyl 3-hydroxy-2,2-dimethylpropanoate Chemical class CC(C)(C)COC(=O)C(C)(C)CO XNDAGYLOQWQWIM-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- QDNSOJDSRJOUHB-UHFFFAOYSA-N 2-methyloxirane;phenol Chemical compound CC1CO1.OC1=CC=CC=C1.OC1=CC=CC=C1 QDNSOJDSRJOUHB-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
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- ZKLXCVFIJWMPSV-UHFFFAOYSA-N OCC1=CC(CC(C=C2CO)=CC(CO)=C2OCC2OC2)=CC(CO)=C1OCC1OC1 Chemical compound OCC1=CC(CC(C=C2CO)=CC(CO)=C2OCC2OC2)=CC(CO)=C1OCC1OC1 ZKLXCVFIJWMPSV-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QDJVFJYVZPRPDP-UHFFFAOYSA-N carbonic acid;3-methyl-4-[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl]-7-oxabicyclo[4.1.0]heptane Chemical compound OC(O)=O.C1C2OC2CC(C)C1CC1CC2OC2CC1C QDJVFJYVZPRPDP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- UBPGILLNMDGSDS-UHFFFAOYSA-N diethylene glycol diacetate Chemical compound CC(=O)OCCOCCOC(C)=O UBPGILLNMDGSDS-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004898 kneading Methods 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Description
本発明は液晶滴下工法用シール剤に関するものであり、詳細には粘度安定性や高温高湿下に長時間放置した場合の接着信頼性が良好な液晶滴下工法用シール剤に関する。 The present invention relates to a sealing agent for a liquid crystal dropping method, and more particularly to a sealing agent for a liquid crystal dropping method having good viscosity stability and good adhesion reliability when left under a high temperature and high humidity for a long time.
現在の液晶表示パネルは、貼り合わせを行なう一方のガラス基板上に液晶の注入孔を形成するようにメインシール剤を塗布し、熱硬化により貼り合わせを行なう。その後、真空中にて液晶の注入孔より液晶を注入した後、液晶注入部を紫外線硬化型エンドシール剤により封止をし作製される。上記の液晶表示パネルの作成方法は、液晶を注入する工程時間が長く、熱硬化する際の150℃前後の高温による熱歪でガラス基板の密着性が低下したり、位置ずれ、ギャップのバラツキ、シール剤からの染み出しが生じるなどの問題点がある。
これらを解決する方法として、アクリル酸エステルまたはメタクリル酸エステルを主成分とする光硬化型のアクリル系接着剤(特許文献1)、光硬化型のエポキシ系接着剤とアクリル樹脂の混合系(特許文献2)、エポキシ樹脂の部分アクリル化または部分メタクリル化物を主成分とし他原料の配合等を限定し光硬化と熱硬化を併用するもの(特許文献3、4)が提案されている。これら光硬化型シール剤は液晶滴下方式のシール剤として、光の照射により常温・短時間で硬化するため、パネル作成の工程時間が短縮できる。また、液晶用ガラス基板が速やかに固定されるため、上記の熱硬化型エポキシ樹脂を用いたパネル作成方法の問題点が解消される。
In a current liquid crystal display panel, a main sealant is applied so as to form a liquid crystal injection hole on one glass substrate to be bonded, and bonding is performed by thermosetting. Thereafter, liquid crystal is injected through a liquid crystal injection hole in a vacuum, and then the liquid crystal injection portion is sealed with an ultraviolet curable end sealant. The above-mentioned liquid crystal display panel production method has a long process time for injecting liquid crystal, the thermal strain due to a high temperature of around 150 ° C. when thermosetting is performed, the adhesion of the glass substrate is lowered, the position shift, the gap variation, There are problems such as seepage from the sealant.
As a method for solving these problems, a photocurable acrylic adhesive mainly composed of acrylic ester or methacrylic ester (Patent Document 1), a mixed system of a photocurable epoxy adhesive and an acrylic resin (Patent Document) 2) The thing which uses the partially acrylated or partially methacrylated product of the epoxy resin as a main component and limits the blending of other raw materials and uses both photocuring and thermosetting (Patent Documents 3 and 4) has been proposed. Since these photo-curing sealants are liquid crystal dripping sealants, they are cured at room temperature and in a short time by light irradiation, so that the process time for panel preparation can be shortened. Moreover, since the glass substrate for liquid crystals is fixed rapidly, the problem of the panel preparation method using said thermosetting epoxy resin is eliminated.
しかし、アクリル酸エステルまたはメタクリル酸エステルを主成分とする光硬化型のアクリル系接着剤、光硬化型のエポキシ系接着剤とアクリル樹脂の混合系は、本来要求される接着性および高温高湿下に長時間放置した場合の接着信頼性、液晶の電気光学特性の維持、配向乱れを起こさない等の要求が満足されない。エポキシ樹脂の部分アクリル化または部分メタクリル化物を主成分とする光硬化と熱硬化を併用するものは、接着性および高温高湿下に長時間放置した場合の接着信頼性、液晶の電気光学特性の維持、配向乱れを起こさない等の課題は改善するが、粘度安定性が悪く、粘度上昇にともない塗布時に線幅が細くなる問題や、ディスペンサーに液晶滴下工法用シール剤を入れ替える回数が増加するなどの問題、これらに起因する液晶滴下工法用シール剤および液晶表示パネルの歩留まりが低下する等の問題がある。
一方で、液晶シール剤成分の液晶材料中への溶け込みを防ぐことを目的とした液晶シール剤(特許文献5、6、7)や有機EL用シール剤(特許文献8)が提案されているが、粘度安定性や本来要求される接着性および高温高湿下に長時間放置した場合の接着信頼性等で満足できるものは得られていなかった。
On the other hand, liquid crystal sealants (Patent Documents 5, 6, and 7) and organic EL sealants (Patent Document 8) for the purpose of preventing the liquid crystal sealant component from dissolving into the liquid crystal material have been proposed. However, no satisfactory products were obtained in terms of viscosity stability, originally required adhesion, and adhesion reliability when left for a long time under high temperature and high humidity.
本発明の目的は、粘度安定性、塗工適正、液晶パネルの電気光学特性、配向乱れを起こさない等の表示特性が優れ、液晶表示パネルの接着強度および高温高湿下に長時間放置した場合の接着強度に優れた液晶滴下工法用シール剤組成物、液晶滴下工法用シール剤を提供することである。 The purpose of the present invention is excellent in display properties such as viscosity stability, coating suitability, electro-optical properties of liquid crystal panels, and alignment disorder, and when left for a long time under the adhesive strength of liquid crystal display panels and high temperature and high humidity It is providing the sealing compound for liquid crystal dropping methods, and the sealing agent for liquid crystal dropping methods excellent in the adhesive strength of this.
本発明者らは、上記の事情に鑑み、鋭意検討を行った結果、水素結合性官能基量が0mol/gより大きく1.5×10−3mol/g未満である(メタ)アクリル樹脂(A)を必須とする液晶滴下工法用シール剤組成物を見出した。即ち
[1]水素結合性官能基量が0mol/gより大きく1.5×10−3mol/g未満である(メタ)アクリル樹脂(A)を必須とする液晶滴下工法用シール剤組成物。
[2]水素結合性官能基量が0mol/gより大きく1.5×10−3mol/g未満である(メタ)アクリル樹脂(A)100重量部に対して、水素結合性官能基量が1.5×10−3mol/g以上である(メタ)アクリル樹脂(a) 0〜30重量部
エポキシ樹脂(b) 1〜60重量部
潜在性エポキシ硬化剤(c) 1〜30重量部
光開始剤(d) 0.5〜10重量部
フィラー(e) 1〜40重量部
含有することを特徴とする請求項1記載の液晶滴下工法用シール剤組成物。
[3]水素結合性官能基量が0mol/gより大きく1.5×10−3mol/g未満である(メタ)アクリル樹脂(A)の数平均分子量が667以上であることを特徴とする[1]又は[2]に記載の液晶滴下工法用シール剤組成物。
[4][1]〜[3]の何れかに記載の(メタ)アクリル樹脂(A)が、少なくともカプロラクトン誘導体で変性された(メタ)アクリル樹脂を含有することを特徴とする液晶滴下工法用シール剤組成物。
[5][1]〜[4]の何れかに記載の液晶滴下工法用シール剤組成物をセル基板上に塗布し液晶を滴下後、対のセル基板を貼り合わせることを特徴とする液晶表示パネルの製造方法。
[6][5]に記載の製造方法により作製した液晶表示パネル。
である。
As a result of intensive studies in view of the above circumstances, the inventors of the present invention have a (meth) acrylic resin having a hydrogen bonding functional group amount of more than 0 mol / g and less than 1.5 × 10 −3 mol / g ( The sealing agent composition for liquid crystal dropping methods which makes A) essential was discovered. That is
[1] A sealing agent composition for a liquid crystal dropping method, which essentially comprises a (meth) acrylic resin (A) having a hydrogen bonding functional group amount of greater than 0 mol / g and less than 1.5 × 10 −3 mol / g.
[2] The amount of the hydrogen bonding functional group is 100 parts by weight of the (meth) acrylic resin (A) having a hydrogen bonding functional group amount of more than 0 mol / g and less than 1.5 × 10 −3 mol / g. (Meth) acrylic resin (a) which is 1.5 × 10 −3 mol / g or more 0 to 30 parts by weight
Epoxy resin (b) 1-60 parts by weight Latent epoxy curing agent (c) 1-30 parts by weight Photoinitiator (d) 0.5-10 parts by weight Filler (e) 1-40 parts by weight The sealant composition for liquid crystal dropping method according to claim 1.
[3] The number average molecular weight of the (meth) acrylic resin (A) having a hydrogen bonding functional group amount of more than 0 mol / g and less than 1.5 × 10 −3 mol / g is 667 or more. The sealing agent composition for liquid crystal dropping method according to [1] or [2].
[4] The liquid crystal dropping method, wherein the (meth) acrylic resin (A) according to any one of [1] to [3] contains at least a (meth) acrylic resin modified with a caprolactone derivative Sealant composition.
[5] A liquid crystal display characterized in that the sealing composition for liquid crystal dropping method according to any one of [1] to [4] is applied onto a cell substrate, the liquid crystal is dropped, and then a pair of cell substrates are bonded together. Panel manufacturing method.
[6] A liquid crystal display panel produced by the production method according to [5].
It is.
本発明の液晶滴下工法用シール剤組成物は、接着性および高温高湿下に長時間放置した場合の接着信頼性が良好でまた、液晶の電気光学特性の維持、配向乱れを起こさない等の液晶表示パネルの表示信頼性を向上させる。更に、使用時の粘度安定性に優れるため、液晶滴下工法用シール剤の歩留りや液晶表示パネルの歩留まりを向上させることができる。従って、本発明の液晶シール剤組成物は特に、液晶滴下工法用シール剤として好適である。 The sealing composition for the liquid crystal dropping method of the present invention has good adhesion and adhesion reliability when left for a long time under high temperature and high humidity, maintains the electro-optical characteristics of the liquid crystal, does not cause alignment disorder, etc. Improve display reliability of LCD panels. Furthermore, since the viscosity stability at the time of use is excellent, the yield of the sealing agent for liquid crystal dropping method and the yield of the liquid crystal display panel can be improved. Therefore, the liquid crystal sealant composition of the present invention is particularly suitable as a sealant for a liquid crystal dropping method.
以下、本発明における液晶滴下工法用シール剤組成物に関して詳細に説明する。
(メタ)アクリル樹脂とエポキシ樹脂の定義
近年、エポキシ基と(メタ)アクリル基を有する樹脂が多く合成されているが、アクリル化エポキシ樹脂のようにエポキシ樹脂に分類したり、エポキシアクリレートと称しアクリル樹脂に分類したりしており明確な定義がされていない。そこで、本発明では合理的につぎのような基準で記載している。
Hereinafter, the sealing agent composition for liquid crystal dropping method in the present invention will be described in detail.
Definition of (meth) acrylic resin and epoxy resin In recent years, many resins having epoxy groups and (meth) acrylic groups have been synthesized, but they can be classified as epoxy resins such as acrylated epoxy resins, or epoxy resins. They are called acrylates and are classified as acrylic resins, and are not clearly defined. Therefore, in the present invention, the following criteria are rationally described.
本発明における(メタ)アクリル樹脂は、エポキシ基を含有しない樹脂を意味する。また、エポキシ樹脂については、少なくとも1つエポキシ基を含有する樹脂を意味する。さらに、本発明の(メタ)アクリル樹脂は、光や熱などで硬化させる前の化合物を意味し、(メタ)アクリレートとも表記する。また、本発明のエポキシ樹脂は、硬化させる前の化合物を意味し、硬化させたものはエポキシ樹脂硬化物、エポキシ硬化物として区別する。 The (meth) acrylic resin in the present invention means a resin containing no epoxy group. The epoxy resin means a resin containing at least one epoxy group. Furthermore, the (meth) acrylic resin of this invention means the compound before hardening with light, a heat | fever, etc., and it describes with (meth) acrylate. Moreover, the epoxy resin of this invention means the compound before making it harden | cure, and what hardened | cured is distinguished as an epoxy resin hardened | cured material and an epoxy hardened | cured material.
[水素結合性官能基量が0mol/gより大きく1.5×10 −3 mol/g未満である(メタ)アクリル樹脂(A)]
本発明における液晶滴下工法用シール剤組成物は、水素結合性官能基量が0mol/gより大きく1.5×10−3mol/g未満である(メタ)アクリル樹脂(A)を必須とする。(メタ)アクリル樹脂の水素結合性官能基量が1.5×10−3mol/g以上の場合、接着性および高温高湿下に長時間放置した場合の接着信頼性が低下しやすい。なお、本発明における(メタ)アクリル樹脂とは、アクリル樹脂、メタクリル樹脂、アクリル樹脂およびメタクリル樹脂を示す。
[ (Meth) acrylic resin (A) having a hydrogen bondable functional group content of greater than 0 mol / g and less than 1.5 × 10 −3 mol / g ]
The sealing agent composition for a liquid crystal dropping method in the present invention essentially comprises a (meth) acrylic resin (A) having a hydrogen bonding functional group amount of more than 0 mol / g and less than 1.5 × 10 −3 mol / g. . When the amount of the hydrogen bonding functional group of the (meth) acrylic resin is 1.5 × 10 −3 mol / g or more, the adhesiveness and the adhesive reliability when left for a long time under high temperature and high humidity are likely to be lowered. In addition, the (meth) acrylic resin in this invention shows an acrylic resin, a methacrylic resin, an acrylic resin, and a methacrylic resin.
本発明における水素結合性官能基とは、硬化性樹脂中の水素結合性官能基のことを意味し、水素結合性を有する官能基又は残基等である。具体的には、−OH基、−NH2基、−NHR基(Rは、脂肪族炭化水素、芳香族、これらの誘導体を表す)、−CONH2基、−NHOH基や、硬化性樹脂中に存在する−NHCO−結合、−NH−結合、−CONHCO−結合、−NH−NH−結合の残基を有する官能基等が挙げられる。これらの中で本発明における水素結合性官能基としては、−OH基が最も好ましく挙げられる。 The hydrogen bondable functional group in the present invention means a hydrogen bondable functional group in the curable resin, such as a functional group or a residue having hydrogen bondability. Specifically, —OH group, —NH 2 group, —NHR group (R represents an aliphatic hydrocarbon, aromatic, or a derivative thereof), —CONH 2 group, —NHOH group, or curable resin And a functional group having a residue of —NHCO— bond, —NH— bond, —CONHCO— bond, —NH—NH— bond, and the like. Among these, the —OH group is most preferred as the hydrogen bonding functional group in the present invention.
また、本発明における水素結合性官能基量とは、硬化性樹脂1分子中の水素合性官能基の数を硬化性樹脂の分子量で除したものである。なお、硬化性樹脂とは、(メタ)アクリル樹脂およびエポキシ樹脂を意味している。
水素結合性官能基量が0mol/gより大きく1.5×10−3mol/g未満の(メタ)アクリル樹脂の具体例として、例えば、トリス(2−ヒドロキシエチル)イソシアヌレートのモノ或いはジ(メタ)アクリレート;トリメチロールプロパン1モルに6モル以上のエチレンオキサイド若しくはプロピレンオキサイドを付加して得たトリオールのモノ或いはジ(メタ)アクリレート;ジペンタエリスリトールのポリ(メタ)アクリレート、カプロラクトン変性トリメチロールプロパンのモノ或いはジ(メタ)アクリレート;カプロラクトン変性トリス[(メタ)アクリロキシエチル]イソシアヌレート;カプロラクトン変性ジペンタエリスリトールのポリ(メタ)アクリレート;カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールジ(メタ)アクリレートが挙げられる。また、ビスフェノールAジグリシリジルエーテルなどのビスフェノール類のジグリシジルエーテルと、無水フタル酸、イソフタル酸、テレフタル酸、ピロメリット酸などで代表される芳香族ジカルボン酸のなどの(メタ)アクリレート或いはその誘導体との反応物とを反応させること得られる(メタ)アクリル樹脂などが挙げられる。このうち本発明で液晶滴下工法用シール剤組成物として用いる場合はシール剤中での分散性を高めるため25℃で液状であることが好ましい。また、1分子内に(メタ)アクリル基とエポキシ基を少なくとも1個有する(メタ)アクリル樹脂も好ましく挙げられる。これらのうち、少なくともカプロラクトン誘導体で変性された(メタ)アクリル樹脂が接着強度を著しく向上させるため好ましい。
Moreover, the amount of hydrogen bondable functional groups in the present invention is obtained by dividing the number of hydrogen bondable functional groups in one molecule of the curable resin by the molecular weight of the curable resin. The curable resin means (meth) acrylic resin and epoxy resin.
Specific examples of the (meth) acrylic resin having a hydrogen bonding functional group amount of more than 0 mol / g and less than 1.5 × 10 −3 mol / g include, for example, tris (2-hydroxyethyl) isocyanurate mono or di ( (Meth) acrylate; mono- or di (meth) acrylate of triol obtained by adding 6 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane; poly (meth) acrylate of dipentaerythritol, caprolactone-modified trimethylolpropane Mono- or di (meth) acrylates; caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate; poly (meth) acrylates of caprolactone-modified dipentaerythritol; caprolactone-modified neopentyl hydroxypivalate Examples include recall di (meth) acrylate. In addition, diglycidyl ethers of bisphenols such as bisphenol A diglycidyl ether, and (meth) acrylates such as aromatic dicarboxylic acids typified by phthalic anhydride, isophthalic acid, terephthalic acid, pyromellitic acid, or derivatives thereof And (meth) acrylic resin obtained by reacting with the reaction product. Among these, when used as a sealing agent composition for a liquid crystal dropping method in the present invention, it is preferably liquid at 25 ° C. in order to enhance dispersibility in the sealing agent. A (meth) acrylic resin having at least one (meth) acrylic group and epoxy group in one molecule is also preferred. Among these, at least a (meth) acrylic resin modified with a caprolactone derivative is preferable because the adhesive strength is remarkably improved.
さらに、(メタ)アクリル樹脂(A)のGPCによる数平均分子量は、667以上であり、好ましくは667〜4000であり、更に好ましくは690〜2000である。これにより液晶滴下工法用シール剤組成物とした際に液晶表示パネルの高い表示特性を確保できる。
[水素結合性官能基量が1.5×10 −3 mol/g以上である(メタ)アクリル樹脂(a)]
本発明における水素結合性官能基量が1.5×10−3mol/g以上である(メタ)アクリル樹脂(a)の具体例として、例えば、ヒドロキシエチルアクリレート、ヒドロキシブチルアクリレート等のヒドロキシアルキルアクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ソルビトールトリ(メタ)アクリレートなどの多価アルコールと(メタ)アクリル酸との反応で得られた(メタ)アクリル樹脂、ビスフェノールA、ビスフェノールS、ビスフェノールF、ビスフェノールADなどに代表される芳香族ジオール類のごとき多価グリシジルエーテル化合物と(メタ)アクリル酸との反応で得られた(メタ)アクリル樹脂などが挙げられる。また、1分子内に(メタ)アクリル基とエポキシ基を少なくとも1個有する(メタ)アクリル樹脂も好ましく挙げられる。
この中で、多価グリシジルエーテル化合物と(メタ)アクリル酸との反応で得られた(メタ)アクリル樹脂であって、分子内に(メタ)アクリル基およびエポキシ基を少なくとも1個有する水素結合性官能基量が1.5×10−3mol/g以上である(メタ)アクリル樹脂なども好ましく挙げられる。
Furthermore, the number average molecular weight by GPC of (meth) acrylic resin (A) is 667 or more, Preferably it is 667-4000, More preferably, it is 690-2000. Thereby, when it is set as the sealing compound composition for liquid crystal dropping methods, the high display characteristic of a liquid crystal display panel is securable.
[ (Meth) acrylic resin (a) having a hydrogen bonding functional group amount of 1.5 × 10 −3 mol / g or more ]
Specific examples of the (meth) acrylic resin (a) having a hydrogen bondable functional group amount of 1.5 × 10 −3 mol / g or more in the present invention include hydroxyalkyl acrylates such as hydroxyethyl acrylate and hydroxybutyl acrylate. , (Meth) acrylic resin, bisphenol A, bisphenol S, bisphenol F, bisphenol AD obtained by the reaction of polyhydric alcohols such as pentaerythritol tri (meth) acrylate and sorbitol tri (meth) acrylate with (meth) acrylic acid And (meth) acrylic resins obtained by reaction of polyvalent glycidyl ether compounds such as aromatic diols represented by (meth) acrylic acid and the like. A (meth) acrylic resin having at least one (meth) acrylic group and epoxy group in one molecule is also preferred.
Among these, a (meth) acrylic resin obtained by a reaction between a polyvalent glycidyl ether compound and (meth) acrylic acid, which has at least one (meth) acrylic group and epoxy group in the molecule. A (meth) acrylic resin having a functional group amount of 1.5 × 10 −3 mol / g or more is also preferred.
本発明における水素結合性官能基量が1.5×10−3mol/g以上である(メタ)アクリル樹脂(a)の使用量は、水素結合性官能基量が0mol/gより大きく1.5×10−3mol/g未満である(メタ)アクリル樹脂(A)100重量部に対して0〜30重量部が好ましい。これにより、液晶滴下工法用シール剤組成物とした際、優れた粘度安定性を示す。
さらに、水素結合性官能基量が1.5×10−3mol/g以上である(メタ)アクリル樹脂(a)の数平均分子量は、520以上であり、好ましくは520〜2000である。これにより液晶滴下工法用シール剤組成物とした際に液晶表示パネルの高い表示特性を確保できる。
In the present invention, the amount of the hydrogen-bonding functional group is 1.5 × 10 −3 mol / g or more. The amount of the (meth) acrylic resin (a) used is such that the amount of the hydrogen-bonding functional group is greater than 0 mol / g. 0-30 weight part is preferable with respect to 100 weight part of (meth) acrylic resin (A) which is less than 5 * 10 < -3 > mol / g. Thereby, when it is set as the sealing compound composition for liquid crystal dropping methods, the outstanding viscosity stability is shown.
Furthermore, the number average molecular weight of the (meth) acrylic resin (a) having a hydrogen bondable functional group amount of 1.5 × 10 −3 mol / g or more is 520 or more, preferably 520 to 2000. Thereby, when it is set as the sealing compound composition for liquid crystal dropping methods, the high display characteristic of a liquid crystal display panel is securable.
[エポキシ樹脂(b)]
本発明に使用するエポキシ樹脂(b)は、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコールなどのポリアルキレングリコール類、ジメチロールプロパン、トリメチロールプロパン、スピログリコール、グリセリンなどに代表される多価アルコール類と、エピクロルヒドリンとの反応で得られた脂肪族多価グリシジルエーテル化合物;ビスフェノールA、ビスフェノールS、ビスフェノールF、ビスフェノールADなどに代表される芳香族ジオール類およびそれらをエチレングリコール、プロピレングリコール、アルキレングリコール変性したジオール類と、エピクロルヒドリンとの反応で得られた芳香族多価グリシジルエーテル化合物;アジピン酸、イタコン酸などに代表される脂肪族ジカルボン酸とエピクロルヒドリンとの反応で得られた脂肪族多価グリシジルエステル化合物;イソフタル酸、テレフタル酸、ピロメリット酸などで代表される芳香族ジカルボン酸とエピクロルヒドリンとの反応で得られた芳香族多価グリシジルエステル化合物;ヒドロキシジカルボン酸化合物とエピクロルヒドリンとの反応で得られた脂肪族多価グリシジルエーテルエステル化合物または芳香族多価グリシジルエーテルエステル化合物;脂環式多価グリシジルエーテル化合物、ポリエチレンジアミンなどに代表される脂肪族ジアミンと、エピクロルヒドリンとの反応で得られた脂肪族多価グリシジルアミン化合物;ジアミノジフェニルメタン、アニリン、メタキシリレンジアミン等で代表される芳香族ジアミンとエピクロルヒドリンとの反応で得られた芳香族多価グリシジルアミン化合物;ヒダントインならびにその誘導体とエピクロルヒドリンとの反応で得られたヒダントイン型多価グリシジル化合物;フェノールまたはクレゾールとホルムアルデヒドとから誘導されたノボラック樹脂;ポリアルケニルフェノールやそのコポリマーなどに代表されるポリフェノール類とエピクロルヒドリンとの反応で得られたノボラック型多価グリシジルエーテル化合物;エポキシ化ポリブタジエン、エポキシ化ポリイソプレンなどのエポキシ化ジエン重合体;3,4ーエポキシー6ーメチルシクロヘキシルメチルー3,4ーエポキシー6ーメチルシクロヘキサンカーボネート、ビス(2,3ーエポキシシクロペンチル)エーテルなどが具体的な例として挙げられる。
[ Epoxy resin (b) ]
The epoxy resin (b) used in the present invention includes, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and other polyalkylene glycols, dimethylolpropane, Aliphatic polyvalent glycidyl ether compounds obtained by reaction of polyhydric alcohols typified by trimethylolpropane, spiroglycol, glycerin and the like and epichlorohydrin; typified by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, etc. Aromatic diols, diols modified with ethylene glycol, propylene glycol, and alkylene glycol, and epichlorohydride Aromatic polyvalent glycidyl ether compound obtained by reaction with azodihydride; Aliphatic polyvalent glycidyl ester compound obtained by reaction of aliphatic dicarboxylic acid typified by adipic acid, itaconic acid and epichlorohydrin; isophthalic acid, terephthalic acid Aromatic polyvalent glycidyl ester compound obtained by reaction of aromatic dicarboxylic acid represented by acid, pyromellitic acid and epichlorohydrin; aliphatic polyvalent glycidyl ether obtained by reaction of hydroxydicarboxylic acid compound and epichlorohydrin Ester compound or aromatic polyvalent glycidyl ether ester compound; Aliphatic polyvalent glycidyl ether compound, aliphatic polyvalent glycidyl amine compound obtained by reaction of aliphatic diamine typified by polyethylene diamine and epichlorohydrin; Aromatic polyvalent glycidylamine compounds obtained by the reaction of aromatic diamines such as nylmethane, aniline, metaxylylenediamine, etc. with epichlorohydrin; hydantoin-type polyvalent obtained by the reaction of hydantoin and its derivatives with epichlorohydrin Glycidyl compounds; novolak resins derived from phenol or cresol and formaldehyde; novolac polyvalent glycidyl ether compounds obtained by reaction of polyphenols typified by polyalkenylphenols and copolymers thereof with epichlorohydrin; epoxidized polybutadiene, Epoxidized diene polymers such as epoxidized polyisoprene; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carbonate, bis Specific examples include (2,3-epoxycyclopentyl) ether.
分子量について、特に限定されないが、通常、数平均分子量300〜2000のエポキシ樹脂を用いることができる。これらのエポキシ樹脂は、分子蒸留法などにより高純度化を行なっているものを使用することが好ましい。
本発明のエポキシ樹脂の使用量は、水素結合性官能基量が0mol/gより大きく1.5×10−3mol/g未満である(メタ)アクリル樹脂(A)100重量部に対して、1〜60重量部が好ましい。エポキシ樹脂をこのような量で使用することにより、相溶性が発現し、液晶滴下法用シール剤組成物とした際に高い接着信頼性を確保できる。
Although it does not specifically limit about molecular weight, Usually, the epoxy resin of number average molecular weight 300-2000 can be used. It is preferable to use those epoxy resins that have been highly purified by a molecular distillation method or the like.
The amount of the epoxy resin of the present invention used is 100 parts by weight of the (meth) acrylic resin (A) having a hydrogen bonding functional group amount of more than 0 mol / g and less than 1.5 × 10 −3 mol / g. 1 to 60 parts by weight is preferred. By using the epoxy resin in such an amount, compatibility is developed, and high adhesion reliability can be secured when a sealing agent composition for a liquid crystal dropping method is used.
[潜在性エポキシ硬化剤(c)]
本発明に使用する潜在性エポキシ硬化剤(c)としては、有機酸ジヒドラジド化合物、イミダゾール及びその誘導体、ジシアンジアミド、芳香族アミン等の公知のものが使用できる。これらの中で、ジヒドラジド系熱硬化剤が好ましく、具体的に、アジピン酸ジヒドラジド、イソフタル酸ジヒドラジド、セバシン酸ジヒドラジド、1,3−ビス(ヒドラジノカルボエチル)−5−イソプロピルヒダントインなどが好ましく挙げられる。本発明に使用する潜在性エポキシ硬化剤の量としては、1〜30重量部が好ましい。この範囲であると、高温高湿条件下での接着信頼性が発現し、粘度安定性も確保できる。
[ Latent epoxy curing agent (c) ]
As the latent epoxy curing agent (c) used in the present invention, known ones such as organic acid dihydrazide compounds, imidazole and derivatives thereof, dicyandiamide, aromatic amines and the like can be used. Among these, dihydrazide-based thermosetting agents are preferable, and specific examples include adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin. . The amount of the latent epoxy curing agent used in the present invention is preferably 1 to 30 parts by weight. Within this range, adhesion reliability under high temperature and high humidity conditions is exhibited, and viscosity stability can be secured.
[光開始剤(d)]
本発明に使用する光開始剤(d)としては、特に限定されず、公知の材料を使用することが可能である。具体的に例えば、ベンゾフェノン、2、2ー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、チオキサントン等を挙げることができる。本発明に使用する光開始剤の量としては、25℃において液状かつ水素結合性官能基量が0mol/gより大きく1.5×10−3mol/g未満である(メタ)アクリル樹脂(A)100重量部に対して、0.5〜10重量部が好ましい。この範囲であると、光照射による硬化性、硬化物質の吸湿性を抑えることができる点で好ましい。
[ Photoinitiator (d) ]
It does not specifically limit as a photoinitiator (d) used for this invention, It is possible to use a well-known material. Specific examples include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and thioxanthone. The amount of the photoinitiator used in the present invention is a (meth) acrylic resin (A) whose liquid and hydrogen-bonding functional group amount is greater than 0 mol / g and less than 1.5 × 10 −3 mol / g at 25 ° C. ) 0.5 to 10 parts by weight is preferable with respect to 100 parts by weight. Within this range, it is preferable in that the curability by light irradiation and the hygroscopicity of the cured substance can be suppressed.
[フィラー(e)]
本発明に使用するフィラー(e)は、粘性調整、硬化物の熱応力低減等を目的として使用し、無機材料および有機材料の使用が可能である。無機フィラーは公知の無機化合物の中から選択することができる。具体的に例えば、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、硫酸マグネシウム、珪酸アルミニウム、珪酸ジルコニウム、酸化鉄、酸化チタン、酸化アルミニウム(アルミナ)、酸化亜鉛、二酸化珪素、チタン酸カリウム、カオリン、タルク、アスベスト粉、石英粉、雲母、ガラス繊維等である。無機フィラーとしては、カオリン、タルク、ガラス繊維が好ましい。
有機フィラーは公知の有機化合物の中から選択することができ特に制約は無く、具体的に例えば、ポリメタクリル酸メチル、ポリスチレンおよびこれらと共重合可能なモノマー類を共重合した材料を使用することが可能である。
フィラーの粒子径は、表示パネルに影響を与えない範囲であれば特に制限はないが、2μm以下のものを使用することが好ましい。
フィラーの使用量は、水素結合性官能基量が0mol/gより大きく1.5×10−3mol/g未満である(メタ)アクリル樹脂(A)100重量部に対して、フィラーは1〜40重量部である。この範囲であると、熱応力低減効果が発現し、作業適性粘度に抑えることができる。
[Filler (e)]
The filler (e) used in the present invention is used for the purpose of adjusting the viscosity, reducing the thermal stress of the cured product, and the like, and inorganic materials and organic materials can be used. The inorganic filler can be selected from known inorganic compounds. Specifically, for example, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, kaolin, talc, asbestos Powder, quartz powder, mica, glass fiber, etc. As the inorganic filler, kaolin, talc and glass fiber are preferable.
The organic filler can be selected from known organic compounds, and is not particularly limited. Specifically, for example, a material obtained by copolymerizing polymethyl methacrylate, polystyrene and monomers copolymerizable therewith can be used. Is possible.
The particle diameter of the filler is not particularly limited as long as it does not affect the display panel, but it is preferable to use a filler having a particle diameter of 2 μm or less.
The amount of the filler used is such that the amount of the hydrogen bonding functional group is greater than 0 mol / g and less than 1.5 × 10 −3 mol / g of (meth) acrylic resin (A) 100 parts by weight. 40 parts by weight. Within this range, a thermal stress reduction effect is manifested, and the workability viscosity can be suppressed.
本発明は上述の各成分に以外に必要に応じて熱硬化触媒、カップリング剤、イオントラップ剤、イオン交換剤等の添加剤を使用することができる。 In the present invention, additives such as a thermosetting catalyst, a coupling agent, an ion trap agent, and an ion exchanger can be used as necessary in addition to the above-described components.
本発明では溶剤を含有していても良い。溶剤としては、例えば、シクロヘキサノンの如きケトン溶剤、ジエチレングリコールジメチルエーテルやメチルカルビトールやエチルカルビトールおよびブチルカルビトール等で代表されるエーテル溶剤、ジエチレングリコールジアセテートやアルコキシジエチレングリコールモノアセテート等で代表されるアセテート溶剤、トルエン、ヘキサン等が挙げられる。本発明における液晶滴下工法用シール剤組成物中における溶剤の含有量は、0.1%以下が好ましく、より好ましくは0.03%以下である。この範囲であると、液晶表示パネルの表示特性を確保することができるので好ましい。 In the present invention, a solvent may be contained. Examples of the solvent include ketone solvents such as cyclohexanone, ether solvents represented by diethylene glycol dimethyl ether, methyl carbitol, ethyl carbitol, and butyl carbitol, acetate solvents represented by diethylene glycol diacetate and alkoxy diethylene glycol monoacetate, Examples include toluene and hexane. The content of the solvent in the liquid crystal dropping method sealing agent composition in the present invention is preferably 0.1% or less, more preferably 0.03% or less. This range is preferable because the display characteristics of the liquid crystal display panel can be ensured.
<液晶シール剤組成物の調製方法>
本発明の液晶シール剤組成物の調製方法には特に限定はなく、上記各成分を常法により混合して得ることができる。混合には、例えば、双腕式攪拌機、ロール混練機、2軸押出機、ボールミル混練機等のすでに公知の混練機械を介して行って良く、最終的に真空脱泡処理後にガラス瓶やポリ容器に密封充填され、貯蔵、輸送されて良い。なお、粘度安定性を維持するため、調整時に本発明の液晶滴下工法用シール剤組成物にかかる温度としては、−15℃〜35℃が好ましく、より好ましくは10℃〜30℃未満である。
<Method for Preparing Liquid Crystal Sealant Composition>
There is no particular limitation on the method for preparing the liquid crystal sealant composition of the present invention, and it can be obtained by mixing each of the above components by a conventional method. For mixing, for example, a known kneading machine such as a double-arm stirrer, a roll kneader, a twin screw extruder, a ball mill kneader or the like may be used. It can be hermetically filled, stored and transported. In addition, in order to maintain viscosity stability, as a temperature concerning the sealing compound for liquid crystal dropping methods of this invention at the time of adjustment, -15 degreeC-35 degreeC is preferable, More preferably, it is 10 degreeC-less than 30 degreeC.
本発明の液晶滴下工法用シール剤組成物は、25℃においてE型粘度計による2.5rpmの粘度が50〜450Pa・sであることが好ましく、より好ましくは2.5rpmの粘度が150〜450Pa・sの範囲にある。その範囲の初期粘度特性を保持させることで、塗布ムラのない塗布作業性を発揮出来るため、好ましい。特に25℃においてE型粘度計による2.5rpmの粘度が50Pa・s以上の初期粘度であれば塗布後のシール形状保持性が優れることから好ましく、150Pa・s以上の初期粘度であればより好ましい。また450Pa・s以下の初期粘度であれば、ノズル径が0.15〜0.5mm径のディスペンス塗布性が確保でき好ましい。 The liquid crystal dropping method sealing agent composition of the present invention preferably has a viscosity at 2.5 rpm of 50 to 450 Pa · s by an E-type viscometer at 25 ° C., and more preferably has a viscosity of 2.5 rpm of 150 to 450 Pa.・ It is in the range of s. By maintaining the initial viscosity characteristics within that range, it is preferable because application workability without application unevenness can be exhibited. In particular, if the viscosity at 2.5 rpm by an E-type viscometer at 25 ° C. is an initial viscosity of 50 Pa · s or more, it is preferable because the seal shape retention after coating is excellent, and an initial viscosity of 150 Pa · s or more is more preferable. . Further, an initial viscosity of 450 Pa · s or less is preferable because it can ensure the dispense applicability with a nozzle diameter of 0.15 to 0.5 mm.
<液晶表示パネルおよびその製造方法>
本発明の液晶表示パネルは、前述のようにして得られた液晶滴下工法用シール剤組成物を用いて、液晶滴下工法により製造される。製造方法の一例を以下に説明する。
予め設定したギャップ幅のスペーサーを本発明の液晶滴下工法用シール剤組成物に混合し、脱泡しておく。さらに一対の液晶セル用ガラス基板を用い、一方の液晶セル用ガラス基板上に該液晶シール剤組成物をディスペンサーにて枠型に塗布する。次いで、対となるガラス基板の貼り合わせ後のパネル内部容量に相当する液晶材料をその枠内に精密に滴下する。その後、他方のガラスを対向させ、紫外線を500〜18000mJ/cm2の量を照射してガラス基板を貼り合わせる。さらにその後、100℃〜140℃の温度でおよそ30分〜1時間加熱して充分に硬化させ液晶表示パネルを形成する。
用いられる液晶セル用基板としては、例えば、ガラス基板、プラスチック基板が挙げられる。なお、前記した基板群では当然のこととして酸化インジウムに代表される透明電極やポリイミド等に代表される配向膜、その他無機質イオン遮蔽膜等が必要部に施工されてなる、いわゆる液晶セル構成用ガラス基板又は同プラスチック基板が用いられる。
液晶セル用基板に液晶滴下工法用シール剤組成物を塗布する方法には特に限定はなく、例えば、スクリーン印刷塗布方法又はディスペンサー塗布方法などで行って良い。
<Liquid crystal display panel and manufacturing method thereof>
The liquid crystal display panel of the present invention is manufactured by a liquid crystal dropping method using the liquid crystal dropping method sealing agent composition obtained as described above. An example of the manufacturing method will be described below.
A spacer having a preset gap width is mixed with the sealing composition for a liquid crystal dropping method of the present invention and defoamed. Further, a pair of glass substrates for liquid crystal cells is used, and the liquid crystal sealing agent composition is applied to a frame shape with a dispenser on one glass substrate for liquid crystal cells. Next, a liquid crystal material corresponding to the internal capacity of the panel after the glass substrates forming a pair are bonded is precisely dropped into the frame. Then, the other glass is made to oppose and the glass substrate is bonded together by irradiating ultraviolet rays in an amount of 500 to 18000 mJ / cm 2 . Further, after that, it is heated for about 30 minutes to 1 hour at a temperature of 100 ° C. to 140 ° C. and sufficiently cured to form a liquid crystal display panel.
Examples of the liquid crystal cell substrate used include a glass substrate and a plastic substrate. In the substrate group described above, naturally, a transparent electrode represented by indium oxide, an alignment film represented by polyimide, etc., and other so-called glass for constituting a liquid crystal cell, in which an inorganic ion shielding film is applied to a necessary part. A substrate or the same plastic substrate is used.
There is no particular limitation on the method for applying the liquid crystal dropping method sealing agent composition to the liquid crystal cell substrate. For example, the screen printing application method or the dispenser application method may be used.
<分析手法>
1)エポキシ量は、樹脂を塩酸−ジオキサン溶液に溶解させた後、エポキシ基によって消費された塩酸量を滴定する方法により算出した。
2)オキシラン酸素濃度は、臭化水素滴定を行い算出した。
3)酸価は、樹脂をジエチルエーテル・エタノール溶液に溶解させ、フェノールフタレインエタノール溶液を添加し、溶液が無色になるまで滴下したエタノール性0.1NのKOHの消費量から算出した。
4)合成した(メタ)アクリル樹脂の数平均分子量の測定には、多角度光散乱装置つきゲルパーミエーションクロマトグラフィー(GPC−MALLS)を用いた。測定条件は以下の通りである。
本体:昭和電工(株)製、システム21
溶離液:テトラヒドロフラン
流速:1.0ml/分
カラム:Shodex製 GPC KF−802.5
検出器:ワイアットテクノロジー社の多角度光散乱検出器DAWN
<硬化性樹脂の超純水洗浄>
本発明における硬化性樹脂の洗浄方法について説明する。断りのない限り、硬化性樹脂の洗浄とは本方法を意味する。硬化性樹脂を同重量のトルエンに溶解し、0.7μS/cm以下の超純水を加え、攪拌機を備え付けた分液ロートで攪拌混合し、トルエン層とその半重量加えた水層が分離するまで静置した。その後、水層のみ排出した。この際、硬化性樹脂の酸価相当以上の水酸化ナトリウムを超純水に溶かしておいた。更に、超純水を加え、攪拌混合、静置、分離を行い、最終の超純水の電気伝導度が1μS/cmとなるまで超純水洗浄を繰り返した。
<Analysis method>
1) The amount of epoxy was calculated by a method of titrating the amount of hydrochloric acid consumed by the epoxy group after dissolving the resin in a hydrochloric acid-dioxane solution.
2) The oxirane oxygen concentration was calculated by performing hydrogen bromide titration.
3) The acid value was calculated from the consumption of ethanolic 0.1N KOH added dropwise by dissolving the resin in diethyl ether / ethanol solution, adding phenolphthalein ethanol solution, and the solution became colorless.
4) For the measurement of the number average molecular weight of the synthesized (meth) acrylic resin, gel permeation chromatography (GPC-MALLS) with a multi-angle light scattering device was used. The measurement conditions are as follows.
Body: Showa Denko KK, System 21
Eluent: Tetrahydrofuran Flow rate: 1.0 ml / min Column: GPC KF-802.5 manufactured by Shodex
Detector: Multi-angle light scattering detector DAWN from Wyatt Technology
<Cleaning of curable resin with ultra pure water>
The cleaning method of the curable resin in the present invention will be described. Unless otherwise noted, washing of the curable resin means this method. Dissolve the curable resin in the same weight of toluene, add 0.7μS / cm or less of ultrapure water, and stir and mix in a separatory funnel equipped with a stirrer, separating the toluene layer and the half-weighted water layer. Left to stand. Thereafter, only the water layer was discharged. At this time, sodium hydroxide equivalent to or higher than the acid value of the curable resin was dissolved in ultrapure water. Furthermore, ultrapure water was added, stirring, mixing, standing and separation were performed, and ultrapure water washing was repeated until the final ultrapure water had an electric conductivity of 1 μS / cm.
<硬化性樹脂のカラム精製>
本発明における硬化性樹脂のカラム精製方法について説明する。断りのない限り、硬化性樹脂のカラム精製とは本方法を意味する。硬化性樹脂をトルエンに溶解し、充填剤としてシリカゲルを用い、溶離液としてヘキサン、トルエン、テトラヒドロフラン、酢酸エチル、クロロホルムから1種あるいは2種類以上を混合して用いた。カラム精製は、必要に応じて回数を増やし、1回以上行なっている。断りのない限り、脱溶剤は減圧下70℃で行い、溶剤を除去した。
<Column purification of curable resin>
The column purification method of the curable resin in the present invention will be described. Unless otherwise noted, column purification of a curable resin means this method. A curable resin was dissolved in toluene, silica gel was used as a filler, and one or more of hexane, toluene, tetrahydrofuran, ethyl acetate, and chloroform were mixed and used as an eluent. Column purification is performed one or more times, increasing the number as necessary. Unless otherwise noted, solvent removal was performed at 70 ° C. under reduced pressure to remove the solvent.
以下、代表的な実施例により本発明を詳細に説明する。
(合成例1)
無水フタル酸296.2g(2モル)、2−ヒドロキシエチルアクリレートの6−ヘキサノリド付加物(プラクセルFA3、分子量:459g/mol、ダイセル化学製)917.0g(2モル)、トリエチルアミン4g、ヒドロキノン0.9gを110℃で加熱攪拌し、酸価が48mgKOH/gとなってから、更に90℃でビスフェノールFジグリシジルエーテル312.4g(1モル)、テトラブチルアンモニウムブロマイド6.4gを添加後、酸価が2mgKOH/gとなるまで加熱攪拌を続けた。
さらに、次のように精製操作を実施した。得られたアクリル樹脂200gを同量のトルエンに溶かし、シリカゲルを使ってカラム精製操作を行い、2−ヒドロキシエチルアクリレートの6−ヘキサノリド付加物、無水フタル酸と−ビスフェノールFジグリシジルエーテルの反応化合物の溶液を得た。さらに減圧下70℃で溶媒を除去した後、得られた樹脂100gをトルエン100gに溶解し、水酸化ナトリウム溶液を加えた超純水100gを使い、攪拌洗浄、静置後洗浄水分離操作を行い、2回目以降は超純水100gのみで攪拌洗浄、静置後洗浄水分離操作を行い、最終の超純水の電気伝導度を1μS/cmとなるまで超純水洗浄を繰り返した。得られた25℃で液状のアクリル樹脂(A−1)の水素結合性官能基量を算出したところ、1.3×10−3mol/gであった。得られたアクリル樹脂(A−1)のGPC−MALLSによる数平均分子量は1526g/molであり、単一ピークであった。
Hereinafter, the present invention will be described in detail by way of representative examples.
(Synthesis Example 1)
296.2 g (2 mol) of phthalic anhydride, 6-hexanolide adduct of 2-hydroxyethyl acrylate (Placcel FA3, molecular weight: 459 g / mol, manufactured by Daicel Chemical Industries) 917.0 g (2 mol), 4 g of triethylamine, 0. 9 g was heated and stirred at 110 ° C., and after the acid value reached 48 mg KOH / g, after adding 312.4 g (1 mol) of bisphenol F diglycidyl ether and 6.4 g of tetrabutylammonium bromide at 90 ° C., the acid value was Was continued with heating and stirring until 2 mgKOH / g.
Further, purification operation was performed as follows. 200 g of the obtained acrylic resin is dissolved in the same amount of toluene, and column purification operation is performed using silica gel, and a reaction product of 6-hexanolide adduct of 2-hydroxyethyl acrylate, phthalic anhydride and -bisphenol F diglycidyl ether. A solution was obtained. Further, after removing the solvent at 70 ° C. under reduced pressure, 100 g of the obtained resin was dissolved in 100 g of toluene, and 100 g of ultrapure water to which a sodium hydroxide solution was added was used for stirring and washing, followed by washing water separation operation. From the second time onward, washing with stirring was carried out with 100 g of ultrapure water only, and after standing, washing water was separated, and washing with ultrapure water was repeated until the final ultrapure water had an electric conductivity of 1 μS / cm. It was 1.3 * 10 < -3 > mol / g when the amount of hydrogen bondable functional groups of liquid acrylic resin (A-1) obtained at 25 degreeC was computed. The number average molecular weight by GPC-MALLS of the obtained acrylic resin (A-1) was 1526 g / mol, and it was a single peak.
[実施例1]
合成例1で得られた(メタ)アクリル樹脂(A−1)、エピクロン850CRP(b−1)(ビスフェノールA型エポキシ樹脂:大日本インキ化学工業製)、アミキュアVDH(c)(味の素ファインケミカル製)、イルガキュア184(d-1)(1−ヒドロキシシクロヘキシルフエニルケトン:チバ・スペシャルティー・ケミカルズ製)、SO-E1(e−1)(超高純度シリカ:アドマテックス製)、KBM−403(シランカップリング剤:信越化学工業製)を表1に記した配合量にてダルトンミキサーで3本ロールを用いて充分に混練し、E型粘度計(2.5rpm)による25℃における粘度が350Pa・sの液晶滴下工法用シール剤組成物(S−1)を得た。このS−1に、5μmのスペーサーを添加して以下の液晶滴下工法用シール剤としての評価を実施した。
[Example 1]
(Meth) acrylic resin (A-1), Epicron 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals), Amicure VDH (c) (manufactured by Ajinomoto Fine Chemical) obtained in Synthesis Example 1 , Irgacure 184 (d-1) (1-hydroxycyclohexyl phenyl ketone: manufactured by Ciba Specialty Chemicals), SO-E1 (e-1) (ultra high purity silica: manufactured by Admatechs), KBM-403 (silane) Coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) was sufficiently kneaded with a Dalton mixer using three rolls in the blending amounts shown in Table 1, and the viscosity at 25 ° C. by an E-type viscometer (2.5 rpm) was 350 Pa · The sealing compound composition (S-1) for liquid crystal dropping method of s was obtained. A 5 μm spacer was added to S-1 and evaluation as a sealing agent for the following liquid crystal dropping method was performed.
1.粘度安定性
液晶滴下工法用シール剤(S−1)の25℃の粘度を測定してその値を基準とする。液晶滴下工法用シール剤(S−1)をポリエチレン製容器中に入れ、密閉し、23℃一定条件にて保管する。7日経過後、同じ条件で粘度を測定してその増加率により、次のように判定した。
○:20%未満
△:20%以上50%未満
×:50%以上
2.塗布適性
液晶滴下工法用シール剤(S−1)を10ccのシリンジに充填した後、脱泡を行なった。ディスペンサー(ショットマスター:武蔵エンジニアリング製)にて描画を行なった。塗布は、毎秒4cmのスピードで行なった。以下の判定基準で優劣を判断した。
○:染み出しおよび糸曳きが無く、直線性も良好であった
△:染み出しおよび糸曳きは無いが、直線性が不良であった。
×:染み出しおよび糸曳きが発生して塗布適性が著しく劣る。
3.接着強度
液晶滴下工法用シール剤(S−1)を25mm×45mm厚さ4mmの無アルカリガラス上に直径1mmの円状にスクリーン印刷し、対となる同様のガラスを十字に貼り合わせて、2000mJ/cm2の紫外線照射し、続いて120℃で1時間の加熱を行なった。25℃湿度50%の恒温槽にて24時間保管後、得られた試験片を引張り試験装置(インテスコ製)を使用し、引張り速度2mm/分で平面引張り強度を測定した。
4.高温高湿加速試験後の接着強度
液晶滴下工法用シール剤(S−1)を25mm×45mm厚さ4mmの無アルカリガラス上に直径1mmの円状にスクリーン印刷し、対となる同様のガラスを十字に貼り合わせた後、2000mJ/cm2の紫外線照射し、続いて120℃で1時間の加熱を行なった。さらに、温度121℃、湿度100%、圧力2.1気圧の高温高湿加速試験機(楠本化成社製 ETAC PLAMOUNT PM422)に20時間保管し、さらに25℃湿度50%の恒温槽にて24時間保管後、得られた試験片を引張り試験装置(インテスコ製)を使用し、引張り速度2mm/分で平面引張り強度を測定した。
5.液晶パネルの電気特性評価
透明電極及び配向膜を付した40mm×45mmガラス基板(EHC社製、RT−DM88−PIN)上に、液晶滴下工法用シール剤(S−1)を、ディスペンサー(ショットマスター:武蔵エンジニアリング製)にて、線幅0.5mm、厚み50μmで35mm×40mmの型枠に描画し、続いて、貼り合せ後のパネル内容量に相当する液晶材料(MLC−11900−000:メルク社製)を、ディスペンサーを用いて精密に滴下し、更に対になるガラス基板を減圧下で貼り合せ、紫外線を2000mJ/cm2照射した。続いて、120℃で1時間の加熱を行ない、さらに60℃、湿度95%の条件下で1000時間の高温・高湿動作試験を行い、試験後の電圧保持率を測定した。
電圧保持率が98%以上を○、95%以上98未満を△、95%未満を×として判定した。
6.液晶表示パネルの表示特性評価
紫外線を1000mJ/cm2照射した以外は、上記と同様に液晶パネルを作成し、た。得られた液晶表示パネルを、65℃、95%RH、1000時間放置前後に、シール部周辺の液晶に生じる色むらを目視で観察した。
この液晶パネルを、直流電源装置を用いて5Vの印加電圧で駆動させ、液晶シール剤近傍の液晶表示機能が駆動初期から正常に機能するか否かでパネル表示特性の評価判定を行った。該判定方法は、シール際まで液晶表示機能が発揮出来ている場合を表示特性が良好であるとして記号○とし、シール際の近傍0.3mm未満で表示機能の異常を見た場合を表示特性が劣るとして記号△、またシール際の近傍0.3mmを超えて表示機能の異常を見た場合を表示特性が著しく劣るとして記号×と表示した。
評価結果を表2に示した。
1. The viscosity at 25 ° C. of the viscosity-stable liquid crystal dropping method sealing agent (S-1) is measured, and the value is used as a reference. A sealing agent for liquid crystal dropping method (S-1) is placed in a polyethylene container, sealed, and stored under constant conditions at 23 ° C. After the elapse of 7 days, the viscosity was measured under the same conditions, and the increase rate was determined as follows.
○: Less than 20% Δ: 20% or more and less than 50% ×: 50% or more
2. Application suitability After filling a 10 cc syringe with a sealing agent for liquid crystal dropping method (S-1), defoaming was performed. Drawing was performed with a dispenser (Shot Master: manufactured by Musashi Engineering). The application was performed at a speed of 4 cm per second. Superiority or inferiority was judged according to the following criteria.
◯: There was no seepage and stringing, and the linearity was good. Δ: There was no seepage and stringing, but the linearity was poor.
X: Exudation and stringing occur and applicability is extremely poor.
3. Adhesive strength A liquid crystal dropping method sealant (S-1) was screen-printed in a circular shape with a diameter of 1 mm on an alkali-free glass with a thickness of 25 mm × 45 mm and a thickness of 4 mm, and a pair of similar glasses were bonded together in a cross shape. , 2000 mJ / cm 2 of UV irradiation, followed by heating at 120 ° C. for 1 hour. After storage for 24 hours in a constant temperature bath at 25 ° C. and 50% humidity, the obtained test piece was measured for flat tensile strength at a pulling speed of 2 mm / min using a tensile tester (manufactured by Intesco).
4). Adhesive strength after high-temperature and high-humidity accelerated test Screen-printed sealing agent for liquid crystal dropping method (S-1) on non-alkali glass of 25 mm × 45 mm thickness 4 mm in a 1 mm diameter circle, and a pair of similar glasses After being bonded to a cross, ultraviolet irradiation of 2000 mJ / cm 2 was performed, followed by heating at 120 ° C. for 1 hour. Furthermore, it is stored for 20 hours in a high-temperature and high-humidity acceleration tester (ETAC PLAMOUNT PM422 manufactured by Enomoto Kasei Co., Ltd.) having a temperature of 121 ° C., a humidity of 100% and a pressure of 2.1 atm. After storage, the tensile strength of the obtained test piece was measured using a tensile test apparatus (manufactured by Intesco) at a pulling speed of 2 mm / min.
5. Evaluation of electrical properties of liquid crystal panel On a 40 mm × 45 mm glass substrate (RT-DM88-PIN, manufactured by EHC) with a transparent electrode and an alignment film, a sealant for liquid crystal dropping method (S-1) was dispensed (shot master). : Made by Musashi Engineering Co., Ltd., drawn on a 35mm x 40mm formwork with a line width of 0.5mm and a thickness of 50µm, and then a liquid crystal material (MLC-11900-000: Merck) corresponding to the panel capacity after bonding (Manufactured by Kogyo Co., Ltd.) was precisely dropped using a dispenser, and a pair of glass substrates were bonded together under reduced pressure, and ultraviolet rays were irradiated at 2000 mJ / cm 2 . Subsequently, heating was performed at 120 ° C. for 1 hour, and a high-temperature and high-humidity operation test was performed for 1000 hours under the conditions of 60 ° C. and 95% humidity, and the voltage holding ratio after the test was measured.
A voltage holding ratio of 98% or more was judged as ◯, 95% or more and less than 98 as Δ, and less than 95% as x.
6). Except that the irradiation 1000 mJ / cm 2 display characterization ultraviolet of the liquid crystal display panel, in the same manner as described above to create a liquid crystal panel was. The obtained liquid crystal display panel was visually observed for color unevenness generated in the liquid crystal around the seal portion before and after being left at 65 ° C. and 95% RH for 1000 hours.
This liquid crystal panel was driven with a DC power supply device at an applied voltage of 5 V, and the panel display characteristics were evaluated and judged depending on whether or not the liquid crystal display function in the vicinity of the liquid crystal sealant functions normally from the beginning of driving. In this judgment method, the symbol “◯” indicates that the liquid crystal display function can be exhibited until the sealing, and the display characteristics are good. The symbol Δ was shown as being inferior, and the symbol X was shown as being markedly inferior in the display characteristics when an abnormality in the display function was observed beyond 0.3 mm in the vicinity of the seal.
The evaluation results are shown in Table 2.
(合成例2)
合成例1で得られたアクリル樹脂(A−1)140.6g(0.1モル)と、トルエン250g、トリエチルアミン2.0gを混合し、メタクリル酸クロリド10.45g(0.1モル)を滴下した後、90℃で5時間加熱攪拌を行なった。得られた溶液200gをトルエン100gに溶解し、水酸化ナトリウム溶液を加えた超純水100gを使い、攪拌洗浄、静置後洗浄水分離操作を行い、2回目以降は超純水100gのみで攪拌洗浄、静置後洗浄水分離操作を行い、最終の超純水の電気伝導度を1μS/cmとなるまで超純水洗浄を繰り返した。続いて得られたアクリル樹脂溶液を、シリカゲルを使ってカラム精製操作を行い、合成例1と同様の精製操作を行い、2−ヒドロキシエチルアクリレートの6−ヘキサノリド付加物、無水フタル酸とビスフェノールFジグリシジルエーテルの反応化合物のメタリル化物を得た。得られたメタクリル樹脂(A−2)の水素結合性官能基量を算出したところ、6.3×10−4mol/gであった。得られたアクリル樹脂(A−2)のGPC−MALLSによる数平均分子量は1594g/molであり、単一ピークであった。
(合成例3)
超純水洗浄およびカラム精製した2−ヒドロキシエチルメタクリレートの6−ヘキサノリド付加物(プラクセルFM1D、分子量:244.3g/mol、ダイセル化学製)488.6g(2モル)、ビスフェノールFジグリシジルエーテル312.3g(1モル)、トリエタノールアミン2g、メチルハイドロキノン1gを混合し、乾燥空気バブリング下に、90℃で加熱攪拌し、酸価が2mgKOH/gとなるまで加熱攪拌を続けた。このメタクリル樹脂を合成例1と同様に洗浄し、エポキシ基の100%がメタクリル化されたメタクリル樹脂を得た。得られた液状のメタクリル樹脂(a−1)の水素結合性官能基量を算出したところ、2.5×10−3mol/gであった。得られたメタクリル樹脂(a−1)のGPC−MALLSによる数平均分子量は801g/molであり、単一ピークであった。
(Synthesis Example 2)
140.6 g (0.1 mol) of the acrylic resin (A-1) obtained in Synthesis Example 1 is mixed with 250 g of toluene and 2.0 g of triethylamine, and 10.45 g (0.1 mol) of methacrylic acid chloride is added dropwise. After that, the mixture was stirred with heating at 90 ° C. for 5 hours. 200 g of the obtained solution was dissolved in 100 g of toluene, and 100 g of ultrapure water to which a sodium hydroxide solution was added was used for stirring and washing, followed by washing water separation operation. After the second time, stirring with only 100 g of ultrapure water was performed. Washing and standing were followed by washing water separation, and washing with ultrapure water was repeated until the final ultrapure water had an electric conductivity of 1 μS / cm. Subsequently, the obtained acrylic resin solution was subjected to a column purification operation using silica gel, the same purification operation as in Synthesis Example 1, and a 6-hexanolide adduct of 2-hydroxyethyl acrylate, phthalic anhydride and bisphenol F di-dioxide. A methallylated product of a reaction compound of glycidyl ether was obtained. It was 6.3 * 10 < -4 > mol / g when the amount of hydrogen bondable functional groups of the obtained methacrylic resin (A-2) was computed. The number average molecular weight by GPC-MALLS of the obtained acrylic resin (A-2) was 1594 g / mol, and it was a single peak.
(Synthesis Example 3)
2-Hydroxyethyl methacrylate 6-hexanolide adduct (Placcel FM1D, molecular weight: 244.3 g / mol, manufactured by Daicel Chemical Industries) 488.6 g (2 mol), bisphenol F diglycidyl ether 312. 3 g (1 mol), 2 g of triethanolamine, and 1 g of methylhydroquinone were mixed and heated and stirred at 90 ° C. under dry air bubbling, and the stirring was continued until the acid value reached 2 mgKOH / g. This methacrylic resin was washed in the same manner as in Synthesis Example 1 to obtain a methacrylic resin in which 100% of the epoxy groups were methacrylated. It was 2.5 * 10 < -3 > mol / g when the amount of hydrogen bondable functional groups of the obtained liquid methacrylic resin (a-1) was computed. The number average molecular weight by GPC-MALLS of the obtained methacrylic resin (a-1) was 801 g / mol, which was a single peak.
[実施例2]
合成例2で得られた(メタ)アクリル樹脂(A−2)、合成例3で得られた(メタ)アクリル樹脂(a−1)、エピクロン850CRP(b−1)(ビスフェノールA型エポキシ樹脂:大日本インキ化学工業製)、アミキュアVDH(c)(味の素ファインケミカル製)、イルガキュア184(d-1)(1−ヒドロキシシクロヘキシルフエニルケトン:チバ・スペシャルティー・ケミカルズ製)、SO-E1(e−1)(超高純度シリカ:アドマテックス製)、KBM−403(シランカップリング剤:信越化学工業製)を表1に記した配合量にてダルトンミキサーで3本ロールを用いて充分に混練し、E型粘度計(2.5rpm)による25℃における粘度が150Pa・sの液晶滴下工法用シール剤組成物(S−2)を得た。このS−2を使用して、液晶滴下工法用シール剤としての評価を実施した結果を表2に示した。
(合成例4)
無水フタル酸296.2g(2モル)、超純水洗浄およびカラム精製した2−ヒドロキシエチルメタクリレートの6−ヘキサノリド付加物(プラクセルFM3、分子量:472.6g/mol、ダイセル化学製)945.2g(2モル)、トリエチルアミン4g、ヒドロキノン0.9gを110℃で加熱攪拌し、酸価が47mgKOH/gとなってから、更に90℃でビスフェノールFジグリシジルエーテル312.4g(1モル)、テトラブチルアンモニウムブロマイド6.4gを添加後、酸価が2mgKOH/gとなるまで加熱攪拌を続けた。さらに、得られたメタクリル樹脂溶液を超純水洗浄した。得られたメタクリル樹脂のGPC−MALLSによる数平均分子量は933g/molであり、単一ピークであった。次に、この得られたメタクリル樹脂93.3g(0.1モル)と、トルエン250g、トリエチルアミン2.0gを混合し、90℃で加熱攪拌しながらアクリル酸クロリド9.1g(0.1モル)を滴下した後、さらに90℃で加熱攪拌を5時間行なった。続いて、得られたメタクリル樹脂をカラム精製し、超純水洗浄を行なった。得られた液状のメタクリル樹脂(A−3)の水素結合性官能基量を算出したところ、6.2×10−4mol/gであった。得られたアクリル樹脂(A−3)のGPC−MALLSによる数平均分子量は1608g/molであり、単一ピークであった。
[Example 2]
(Meth) acrylic resin (A-2) obtained in Synthesis Example 2, (Meth) acrylic resin (a-1) obtained in Synthesis Example 3, and Epicron 850CRP (b-1) (bisphenol A type epoxy resin: Dainippon Ink and Chemicals), Amicure VDH (c) (Ajinomoto Fine Chemicals), Irgacure 184 (d-1) (1-hydroxycyclohexyl phenyl ketone: Ciba Specialty Chemicals), SO-E1 (e- 1) (Ultra-high-purity silica: manufactured by Admatechs) and KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) were sufficiently kneaded with a Dalton mixer using three rolls in the compounding amounts shown in Table 1. A sealing agent composition for liquid crystal dropping method (S-2) having a viscosity of 150 Pa · s at 25 ° C. by an E-type viscometer (2.5 rpm) was obtained. Table 2 shows the results of evaluation using this S-2 as a sealing agent for liquid crystal dropping method.
(Synthesis Example 4)
296.2 g (2 mol) of phthalic anhydride, ultra-pure water washed and column purified 2-hydroxyethyl methacrylate 6-hexanolide adduct (PLAXEL FM3, molecular weight: 472.6 g / mol, manufactured by Daicel Chemical Industries) 945.2 g ( 2 mol), 4 g of triethylamine and 0.9 g of hydroquinone were heated and stirred at 110 ° C., and after an acid value of 47 mg KOH / g, bisphenol F diglycidyl ether 312.4 g (1 mol), tetrabutylammonium at 90 ° C. After adding 6.4 g of bromide, heating and stirring were continued until the acid value reached 2 mgKOH / g. Furthermore, the obtained methacrylic resin solution was washed with ultrapure water. The number average molecular weight by GPC-MALLS of the obtained methacrylic resin was 933 g / mol, and it was a single peak. Next, 93.3 g (0.1 mol) of the obtained methacrylic resin, 250 g of toluene, and 2.0 g of triethylamine were mixed, and 9.1 g (0.1 mol) of acrylic acid chloride was heated and stirred at 90 ° C. Then, the mixture was further heated and stirred at 90 ° C. for 5 hours. Subsequently, the obtained methacrylic resin was purified through a column and washed with ultrapure water. It was 6.2 * 10 < -4 > mol / g when the amount of hydrogen bondable functional groups of the obtained liquid methacrylic resin (A-3) was computed. The number average molecular weight by GPC-MALLS of the obtained acrylic resin (A-3) was 1608 g / mol, which was a single peak.
[実施例3]
合成例4で得られた(メタ)アクリル樹脂(A−3)、合成例3で得られた(メタ)アクリル樹脂(a−1)、エピクロン850CRP(b−1)(ビスフェノールA型エポキシ樹脂:大日本インキ化学工業製)、アミキュアVDH(c)(味の素ファインケミカル製)、イルガキュア184(d-1)(1−ヒドロキシシクロヘキシルフエニルケトン:チバ・スペシャルティー・ケミカルズ製)、SG−2000(e−2)(タルク:日本タルク製)、KBM−403(シランカップリング剤:信越化学工業製)を表1に記した配合量にてダルトンミキサーで3本ロールを用いて充分に混練し、E型粘度計(2.5rpm)による25℃における粘度が450Pa・sの液晶滴下工法用シール剤組成物(S−3)を得た。このS−3を使用して、液晶滴下工法用シール剤としての評価を実施した結果を表2に示した。
[Example 3]
(Meth) acrylic resin (A-3) obtained in Synthesis Example 4, (Meth) acrylic resin (a-1) obtained in Synthesis Example 3, and Epicron 850CRP (b-1) (bisphenol A type epoxy resin: Dainippon Ink & Chemicals, Inc., Amicure VDH (c) (Ajinomoto Fine Chemical), Irgacure 184 (d-1) (1-hydroxycyclohexyl phenyl ketone: Ciba Specialty Chemicals), SG-2000 (e- 2) (Talc: manufactured by Nihon Talc) and KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed thoroughly in a Dalton mixer using three rolls in the blending amounts shown in Table 1, and the E type A sealant composition for liquid crystal dropping method (S-3) having a viscosity at 25 ° C. by a viscometer (2.5 rpm) of 450 Pa · s was obtained. Table 2 shows the results of evaluation using this S-3 as a sealing agent for the liquid crystal dropping method.
[比較例1]
合成例3で得られた(メタ)アクリル樹脂(a−1)、光開始剤イルガキュア651(d−2)(2,2−ジメトキシ−1,2−ジフェニルエタン−1−オン;チバ・スペシャルティー・ケミカルズ製)、バイカロックスCR−10(e−3)(アルミナ;バイコウスキー製)、KBM−403(シランカップリング剤:信越化学工業製)を表1に記した配合量にてダルトンミキサーで混合後、3本ロールを用いて充分に混練し、E型粘度計(2.5rpm)による25℃における粘度が300Pa・sの液晶滴下工法用シール剤組成物(C−1)を得た。このC−1を使用して、液晶滴下工法用シール剤としての評価を実施した結果を表2に示した。
(合成例5)
フェノールノボラック型エポキシ樹脂N−770(大日本インキ製)190gをトルエン500mLに溶解し、これにトリフェニルホスフィン0.1gを加えて、均一な溶液とし、さらにアクリル酸35gを還流撹拌下2時間かけて滴下した後、続けて還流撹拌を6時間行った。さらに超純水洗浄およびカラム精製を行なった。得られた樹脂を塩酸−ジオキサン溶液に溶解させた後、エポキシ当量を測定したところ、エポキシ基の50%がアクリル酸で変性されたフェノールノボラック型エポキシ樹脂(b−2)を得た。得られたエポキシ樹脂(b−2)の水素結合性官能基量を算出したところ、2.5×10−3mol/gであった。
(合成例6)
ポリオキシアルキレンビスフェノールAジグリシジルエーテルEP4000S(エポキシ当量260g/eq:アデカ製)520g、p−メトキシフェノール0.75g、トリエチルアミン0.75g、アクリル酸72gを空気を送り込みながら、90℃で還流攪拌しながら5時間反応させた。得られた樹脂を、超純水洗浄およびカラム精製をすることにより、50%部分アクリル化プロピレンオキサイドビスフェノールAエポキシ樹脂(b−3)を得た。得られたエポキシ樹脂(b−3)の水素結合性官能基量を算出したところ、1.9×10−3mol/gであった。
[Comparative Example 1]
(Meth) acrylic resin (a-1) obtained in Synthesis Example 3, photoinitiator Irgacure 651 (d-2) (2,2-dimethoxy-1,2-diphenylethane-1-one; Ciba Specialty・ Dalton mixer with chemicals), Baikalox CR-10 (e-3) (alumina; Baikowski), KBM-403 (silane coupling agent: Shin-Etsu Chemical Co., Ltd.) After mixing, the mixture was sufficiently kneaded using three rolls to obtain a liquid crystal dropping method sealing agent composition (C-1) having a viscosity of 300 Pa · s at 25 ° C. using an E-type viscometer (2.5 rpm). . Table 2 shows the results of evaluation as a sealing agent for liquid crystal dropping method using this C-1.
(Synthesis Example 5)
Dissolve 190 g of phenol novolac epoxy resin N-770 (Dainippon Ink) in 500 mL of toluene, add 0.1 g of triphenylphosphine to make a uniform solution, and then add 35 g of acrylic acid over 2 hours under reflux and stirring. Then, the mixture was stirred under reflux for 6 hours. Further, ultrapure water washing and column purification were performed. The obtained resin was dissolved in a hydrochloric acid-dioxane solution, and then the epoxy equivalent was measured to obtain a phenol novolac type epoxy resin (b-2) in which 50% of the epoxy groups were modified with acrylic acid. It was 2.5 * 10 < -3 > mol / g when the amount of hydrogen bondable functional groups of the obtained epoxy resin (b-2) was computed.
(Synthesis Example 6)
520 g of polyoxyalkylene bisphenol A diglycidyl ether EP4000S (epoxy equivalent 260 g / eq: manufactured by ADEKA), 0.75 g of p-methoxyphenol, 0.75 g of triethylamine, and 72 g of acrylic acid were stirred at 90 ° C. while refluxing. The reaction was allowed for 5 hours. The obtained resin was washed with ultrapure water and subjected to column purification to obtain 50% partially acrylated propylene oxide bisphenol A epoxy resin (b-3). It was 1.9 * 10 < -3 > mol / g when the amount of hydrogen bonding functional groups of the obtained epoxy resin (b-3) was computed.
[比較例2]
合成例5で得られたエポキシ樹脂(b−2)、合成例6で得られたエポキシ樹脂(b−3)、アミキュアVDH(c)(味の素ファインケミカル製)、2,2−ジエトキシアセトフエノン(d−3)、SO-E1(e−1)(超高純度シリカ:アドマテックス製)、KBM−403(シランカップリング剤:信越化学工業製)を表1に記した配合量にてダルトンミキサーで混合後、3本ロールを用いて充分に混練し、E型粘度計(2.5rpm)による25℃における粘度が40Pa・sの液晶滴下工法用シール剤組成物(C−2)を得た。このC−2を使用して、液晶滴下工法用シール剤としての評価を実施した結果を表2に示した。
(合成例7)
エピクロン850CRP(b−1)(ビスフェノールA型エポキシ樹脂:大日本インキ化学工業製)を200g、メタクリル酸100g、トルエン900g、トリエチルアミン0.4g、パラメトキシフエノール0.4gを混合し、90℃で8時間加熱攪拌した。さらに、超純水洗浄およびカラム精製をすることにより、エポキシ基の100%がメタクリル化された25℃で固形のメタクリル樹脂を得た。得られたメタクリル樹脂(a−2)の水素結合性官能基量を算出したところ、3.9×10−3mol/gであった。得られたメタクリル樹脂(a−2)のGPC−MALLSによる数平均分子量は513g/molであり、単一ピークであった。
(合成例8)
エピクロン850CRP(b−1)(ビスフェノールA型エポキシ樹脂:大日本インキ化学工業製)を200g、メタクリル酸50g、トルエン180g、トリエチルアミン0.4g、パラメトキシフエノール0.4gを混合し、90℃で8時間加熱攪拌した。さらに、超純水洗浄およびカラム精製をすることにより、エポキシ基の50%がメタクリル化されたエポキシ樹脂を得た。得られたエポキシ樹脂(b−4)のGPC−MALLSによる数平均分子量は427g/molであり、単一ピークであった。
[Comparative Example 2]
Epoxy resin (b-2) obtained in Synthesis Example 5, epoxy resin (b-3) obtained in Synthesis Example 6, Amicure VDH (c) (manufactured by Ajinomoto Fine Chemicals), 2,2-diethoxyacetophenone (D-3), SO-E1 (e-1) (ultra-high-purity silica: manufactured by Admatechs), KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) at the blending amounts shown in Table 1, Dalton After mixing with a mixer, the mixture is sufficiently kneaded using three rolls, and a liquid crystal dropping method sealing agent composition (C-2) having a viscosity of 40 Pa · s at 25 ° C. by an E-type viscometer (2.5 rpm) is obtained. It was. Table 2 shows the results of evaluation using this C-2 as a sealing agent for liquid crystal dropping method.
(Synthesis Example 7)
200 g of Epicron 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink & Chemicals), 100 g of methacrylic acid, 900 g of toluene, 0.4 g of triethylamine, and 0.4 g of paramethoxyphenol were mixed at 8 ° C. Stir with heating for hours. Furthermore, by performing ultrapure water washing and column purification, a solid methacrylic resin was obtained at 25 ° C. in which 100% of the epoxy groups were methacrylated. The amount of the hydrogen bonding functional group of the obtained methacrylic resin (a-2) was calculated to be 3.9 × 10 −3 mol / g. The number average molecular weight by GPC-MALLS of the obtained methacrylic resin (a-2) was 513 g / mol, and it was a single peak.
(Synthesis Example 8)
200 g of Epicron 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals), 50 g of methacrylic acid, 180 g of toluene, 0.4 g of triethylamine and 0.4 g of paramethoxyphenol were mixed at 8 ° C. Stir with heating for hours. Furthermore, by washing with ultrapure water and column purification, an epoxy resin in which 50% of the epoxy groups were methacrylated was obtained. The number average molecular weight by GPC-MALLS of the obtained epoxy resin (b-4) was 427 g / mol, which was a single peak.
[比較例3]
合成例7でアクリル樹脂(a−2)、エピクロン850CRP(b−1)(ビスフェノールA型エポキシ樹脂:大日本インキ化学工業製)、合成例8で得られたエポキシ樹脂(b−4)、アミキュアVDH(c)(味の素ファインケミカル製)、イルガキュア184(d-1)(1−ヒドロキシシクロヘキシルフエニルケトン:チバ・スペシャルティー・ケミカルズ製)、SO-E1(e−1)(超高純度シリカ:アドマテックス製)、KBM−403(シランカップリング剤:信越化学工業製)を表1に記した配合量にてダルトンミキサーで混合後、3本ロールを用いて充分に混練し、E型粘度計(2.5rpm)による25℃における粘度が100Pa・sの液晶滴下工法用シール剤組成物(C−3)を得た。このC−3を使用して、液晶滴下工法用シール剤としての評価を実施した結果を表2に示した。
(合成例9)
エピクロン850CRP(b−1)(ビスフェノールA型エポキシ樹脂:大日本インキ化学工業製)680g、p−メトキシフェノール1g、トリエチルアミン1g、アクリル酸288gを、空気を送り込みながら110℃で還流攪拌して、5時間反応させた。得られた樹脂を、カラム精製した後、超純水洗浄し、25℃で固形のアクリル樹脂(a−3)を得た。得られたアクリル樹脂のGPC−MALLSによる数平均分子量は484g/molであり、単一ピークであった。この水素結合性官能基量を算出したところ、4.1×10−3mol/gであった。
[Comparative Example 3]
Acrylic resin (a-2) in synthesis example 7, epiclone 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals), epoxy resin (b-4) obtained in synthesis example 8, and amicure VDH (c) (manufactured by Ajinomoto Fine Chemical), Irgacure 184 (d-1) (1-hydroxycyclohexyl phenyl ketone: manufactured by Ciba Specialty Chemicals), SO-E1 (e-1) (ultra high purity silica: AD Mattex) and KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) at the blending amounts shown in Table 1 and then kneaded thoroughly using a three roll, E-type viscometer ( The sealing agent composition for liquid crystal dropping method (C-3) having a viscosity of 100 Pa · s at 25 ° C. by 2.5 rpm) was obtained. Table 2 shows the results of evaluation using this C-3 as a sealing agent for liquid crystal dropping method.
(Synthesis Example 9)
Epiclone 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals) 680 g, p-methoxyphenol 1 g, triethylamine 1 g, and acrylic acid 288 g were refluxed and stirred at 110 ° C. while feeding air. Reacted for hours. The obtained resin was subjected to column purification and then washed with ultrapure water to obtain a solid acrylic resin (a-3) at 25 ° C. The number average molecular weight by GPC-MALLS of the obtained acrylic resin was 484 g / mol, and it was a single peak. The amount of the hydrogen bonding functional group was calculated to be 4.1 × 10 −3 mol / g.
[比較例4]
合成例9で得られたアクリル樹脂(a−3)、アミキュアVDH(c)(味の素ファインケミカル製)、2,2−ジエトキシアセトフェノン(d−3)、SO-E1(e−1)(超高純度シリカ:アドマテックス製)、KBM−403(シランカップリング剤:信越化学工業製)を表1に記した配合量にてダルトンミキサーで混合後、3本ロールを用いて充分に混練し、E型粘度計(2.5rpm)による25℃における粘度が350Pa・sの液晶滴下工法用シール剤組成物(C−4)を得た。このC−4を使用して、液晶滴下工法用シール剤としての評価を実施した結果を表2に示した。
[Comparative Example 4]
Acrylic resin (a-3) obtained in Synthesis Example 9, Amicure VDH (c) (manufactured by Ajinomoto Fine Chemical), 2,2-diethoxyacetophenone (d-3), SO-E1 (e-1) (super high Purified silica (manufactured by Admatechs) and KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with a Dalton mixer in the blending amounts shown in Table 1, and then sufficiently kneaded using three rolls. A sealant composition for liquid crystal dropping method (C-4) having a viscosity of 350 Pa · s at 25 ° C. with a mold viscometer (2.5 rpm) was obtained. Table 2 shows the results of evaluation using this C-4 as a sealing agent for liquid crystal dropping method.
[比較例5]
超純水洗浄したエポキシ樹脂ビス(3,5−ビス−ヒドロキシメチル−4−グリシジルオキシフェニル)メタン(b−5)、アミキュアVDH(c)(味の素ファインテクノ社製)、SO-E1(e−1)(超高純度シリカ:アドマテックス製)、KBM−403(シランカップリング剤:信越化学工業製)を表1に記した配合量にてダルトンミキサーで混合後、3本ロールを用いて充分に混練し、E型粘度計(2.5rpm)による25℃における粘度が500Pa・sの液晶滴下工法用シール剤組成物(C−5)を得た。このC−5を使用して、液晶滴下工法用シール剤としての評価を実施した結果を表2に示した。
(合成例10)
2−ヒドロキシエチルアクリレート232g(2モル)、無水ピロメリット酸218g(1モル)、トリフェニルホスフィン1.8g及びヒドロキノン0.45gを仕込み、110℃に加温して反応させ、酸価が251mgKOH/gとなってから、4−ヒドロキシブチルアクリレートグリシジル400g(2モル)を加え、酸価が2mgKOH/g以下で、かつ、オキシラン酸素濃度が0.25重量部以下となるまで反応を行い、続いて得られたアクリル樹脂溶液を、カラム精製した後、さらに超純水洗浄を行い、25℃で液状のアクリル樹脂(a−4)を得た。得られたアクリル樹脂のGPC−MALLSによる数平均分子量は851g/molであり、単一ピークであった。この水素結合性官能基量を算出したところ、2.4×10−3g/molであった。
[Comparative Example 5]
Epoxy resin bis (3,5-bis-hydroxymethyl-4-glycidyloxyphenyl) methane (b-5), Amicure VDH (c) (manufactured by Ajinomoto Fine Techno Co.), SO-E1 (e- 1) (Ultra high-purity silica: manufactured by Admatechs), KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed with a Dalton mixer in the blending amounts shown in Table 1, and sufficient using three rolls. To obtain a sealant composition for liquid crystal dropping method (C-5) having a viscosity of 500 Pa · s at 25 ° C. measured by an E-type viscometer (2.5 rpm). Table 2 shows the results of evaluation using this C-5 as a sealing agent for liquid crystal dropping method.
(Synthesis Example 10)
232 g (2 mol) of 2-hydroxyethyl acrylate, 218 g (1 mol) of pyromellitic anhydride, 1.8 g of triphenylphosphine and 0.45 g of hydroquinone were added and reacted by heating to 110 ° C. to give an acid value of 251 mgKOH / Then, 400 g (2 mol) of 4-hydroxybutyl acrylate glycidyl was added, and the reaction was continued until the acid value was 2 mg KOH / g or less and the oxirane oxygen concentration was 0.25 parts by weight or less. The obtained acrylic resin solution was subjected to column purification and then washed with ultrapure water to obtain a liquid acrylic resin (a-4) at 25 ° C. The number average molecular weight by GPC-MALLS of the obtained acrylic resin was 851 g / mol, and it was a single peak. The amount of the hydrogen bonding functional group was calculated to be 2.4 × 10 −3 g / mol.
[比較例6]
合成例10で得られたアクリル樹脂(a−4)、エピクロン850CRP(b−1)(ビスフェノールA型エポキシ樹脂:大日本インキ化学工業製)、アミキュアVDH(c)(味の素ファインケミカル製)、2,2−ジエトキシアセトフエノン(d−3)、SO-E1(e−1)(超高純度シリカ:アドマテックス製)、KBM−403(シランカップリング剤:信越化学工業製)を表1に記した配合量にてダルトンミキサーで混合後、3本ロールを用いて充分に混練し、E型粘度計(2.5rpm)による25℃における粘度が350Pa・sの液晶滴下工法用シール剤組成物(C−6)を得た。このC−6を使用して、液晶滴下工法用シール剤としての評価を実施した結果を表2に示した。
[Comparative Example 6]
Acrylic resin (a-4) obtained in Synthesis Example 10, Epicron 850CRP (b-1) (bisphenol A type epoxy resin: manufactured by Dainippon Ink and Chemicals), Amicure VDH (c) (manufactured by Ajinomoto Fine Chemical), 2, Table 2 shows 2-diethoxyacetophenone (d-3), SO-E1 (e-1) (ultra high purity silica: manufactured by Admatechs), KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.). After mixing with a Dalton mixer at the indicated blending amount, the mixture is sufficiently kneaded using three rolls, and a sealing agent composition for a liquid crystal dropping method having a viscosity of 350 Pa · s at 25 ° C. by an E-type viscometer (2.5 rpm). (C-6) was obtained. Table 2 shows the results of evaluation using this C-6 as a sealing agent for liquid crystal dropping method.
Claims (5)
水素結合性官能基量が1.5×10−3mol/g以上である(メタ)アクリル樹脂(a)0〜30重量部と、
エポキシ樹脂(b)1〜60重量部と、
潜在性エポキシ硬化剤(c)1〜30重量部と、
光開始剤(d)0.5〜10重量部と、
フィラー(e) 1〜40重量部とを含有する、液晶滴下工法用シール剤組成物。 100 parts by weight of (meth) acrylic resin (A) having a hydrogen bonding functional group amount of more than 0 mol / g and less than 1.5 × 10 −3 mol / g ;
(Meth) acrylic resin (a) having a hydrogen bonding functional group amount of 1.5 × 10 −3 mol / g or more, 0 to 30 parts by weight ;
1 to 60 parts by weight of epoxy resin (b) ,
1-30 parts by weight of latent epoxy curing agent (c) ,
0.5-10 parts by weight of photoinitiator (d) ,
Filler (e) 1 to 40 containing a part by weight liquid crystal dropping process sealant composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006243056A JP4875441B2 (en) | 2006-09-07 | 2006-09-07 | Sealant composition for liquid crystal dropping method and method for producing liquid crystal display panel using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006243056A JP4875441B2 (en) | 2006-09-07 | 2006-09-07 | Sealant composition for liquid crystal dropping method and method for producing liquid crystal display panel using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2008065065A JP2008065065A (en) | 2008-03-21 |
JP4875441B2 true JP4875441B2 (en) | 2012-02-15 |
Family
ID=39287838
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2006243056A Active JP4875441B2 (en) | 2006-09-07 | 2006-09-07 | Sealant composition for liquid crystal dropping method and method for producing liquid crystal display panel using the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4875441B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101804108B1 (en) | 2015-09-02 | 2017-12-01 | 세키스이가가쿠 고교가부시키가이샤 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1405888A1 (en) * | 2001-05-16 | 2004-04-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
JP3825742B2 (en) * | 2002-11-14 | 2006-09-27 | 積水化学工業株式会社 | Curable resin, curable resin composition, display element sealing agent, display element sealing agent, and display element |
JP2006176576A (en) * | 2004-12-21 | 2006-07-06 | Dainippon Ink & Chem Inc | Photocurable composition for liquid crystal panel sealing and liquid crystal panel |
-
2006
- 2006-09-07 JP JP2006243056A patent/JP4875441B2/en active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101804108B1 (en) | 2015-09-02 | 2017-12-01 | 세키스이가가쿠 고교가부시키가이샤 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
Also Published As
Publication number | Publication date |
---|---|
JP2008065065A (en) | 2008-03-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4531566B2 (en) | Liquid crystal sealant composition and method for producing liquid crystal display panel using the same | |
JP5257941B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
JP5172321B2 (en) | Liquid crystal sealant | |
JP5571436B2 (en) | Liquid crystal sealant, liquid crystal display panel manufacturing method using the same, and liquid crystal display panel | |
JP4948317B2 (en) | Liquid crystal sealant, liquid crystal display panel manufacturing method using the same, and liquid crystal display panel | |
KR20130073610A (en) | Black sealing agent composition for liquid crystal display materials | |
JPWO2011118192A1 (en) | Liquid crystal sealant, liquid crystal display panel manufacturing method using the same, and liquid crystal display panel | |
TWI422932B (en) | A liquid crystal sealant and a liquid crystal display unit using the same | |
JP2005222037A (en) | Sealing agent composition for liquid crystal display element | |
KR20100118518A (en) | Sealant for liquid crystal, and liquid crystal displaycell made with the same | |
JP5645765B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
JP4875440B2 (en) | Sealant composition for liquid crystal dropping method and method for producing liquid crystal display panel using the same | |
JP2007219039A (en) | Sealant composition for liquid crystal display cell | |
JP2003119249A (en) | Liquid crystal sealing resin composition | |
JP4875441B2 (en) | Sealant composition for liquid crystal dropping method and method for producing liquid crystal display panel using the same | |
JP5153123B2 (en) | SEALING AGENT FOR LIQUID CRYSTAL DROPING METHOD, LIQUID CRYSTAL DISPLAY PANEL MANUFACTURING METHOD USING SAME, AND LIQUID CRYSTAL DISPLAY PANEL | |
JP4845667B2 (en) | Liquid crystal sealant, liquid crystal display panel manufacturing method using the same, and liquid crystal display panel | |
JP5032340B2 (en) | Liquid crystal sealing agent and liquid crystal panel manufacturing method using the same | |
JP5748273B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
KR20100028556A (en) | Sealing material for liquid crystal and liquid-crystal display cell made with the same | |
JP2007178473A (en) | Sealing agent for liquid crystal dropping method and method for producing liquid crystal display panel using same | |
JP4302381B2 (en) | Liquid crystal sealant composition, method for producing liquid crystal display cell, and liquid crystal display element | |
JP2003119248A (en) | Liquid crystal sealing resin composition | |
JP2004339341A (en) | Sealing agent composition | |
JP2005195978A (en) | Curing resin composition for liquid crystal display element, sealant for liquid crystal display element, and vertical conduction material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080708 |
|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20090216 |
|
RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20090216 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110518 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110712 |
|
RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20110713 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110907 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111108 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111125 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141202 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4875441 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |