CN113661438A - Liquid crystal sealing agent, liquid crystal display panel using same, and method for manufacturing same - Google Patents
Liquid crystal sealing agent, liquid crystal display panel using same, and method for manufacturing same Download PDFInfo
- Publication number
- CN113661438A CN113661438A CN202080027583.0A CN202080027583A CN113661438A CN 113661438 A CN113661438 A CN 113661438A CN 202080027583 A CN202080027583 A CN 202080027583A CN 113661438 A CN113661438 A CN 113661438A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- sealing agent
- resin
- seal pattern
- crystal sealing
- 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.)
- Granted
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 209
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 185
- 238000007789 sealing Methods 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000758 substrate Substances 0.000 claims abstract description 93
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 51
- 238000013007 heat curing Methods 0.000 claims abstract description 35
- 238000002844 melting Methods 0.000 claims abstract description 35
- 230000008018 melting Effects 0.000 claims abstract description 35
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 33
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 32
- 239000003999 initiator Substances 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims description 63
- 229920000647 polyepoxide Polymers 0.000 claims description 63
- 238000001723 curing Methods 0.000 claims description 39
- -1 thioxanthone compound Chemical class 0.000 claims description 24
- 230000009477 glass transition Effects 0.000 claims description 18
- 239000011146 organic particle Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000010954 inorganic particle Substances 0.000 claims description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000565 sealant Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 description 27
- 229920001187 thermosetting polymer Polymers 0.000 description 24
- 238000000016 photochemical curing Methods 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 19
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 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 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229930185605 Bisphenol Natural products 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000001029 thermal curing Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 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 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- APAJFZPFBHMFQR-UHFFFAOYSA-N anthraflavic acid Chemical compound OC1=CC=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1 APAJFZPFBHMFQR-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 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 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 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 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JYKHAJGLEVKEAA-UHFFFAOYSA-N 2-(hydroxymethyl)anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CO)=CC=C3C(=O)C2=C1 JYKHAJGLEVKEAA-UHFFFAOYSA-N 0.000 description 2
- GCDBEYOJCZLKMC-UHFFFAOYSA-N 2-hydroxyanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(O)=CC=C3C(=O)C2=C1 GCDBEYOJCZLKMC-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZGFPUTOTEJOSAY-UHFFFAOYSA-N FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 Chemical compound FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 ZGFPUTOTEJOSAY-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
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 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
- 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 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
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- 229910021642 ultra pure water Inorganic materials 0.000 description 2
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- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- HSGPYLOMHMYWBJ-UHFFFAOYSA-N 1-chloro-4-ethoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCC)=CC=C2Cl HSGPYLOMHMYWBJ-UHFFFAOYSA-N 0.000 description 1
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
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- 229910000278 bentonite Inorganic materials 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 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
- 238000006073 displacement reaction Methods 0.000 description 1
- GRGBENNNGZARRZ-UHFFFAOYSA-N dodecanedihydrazide Chemical compound NNC(=O)CCCCCCCCCCC(=O)NN GRGBENNNGZARRZ-UHFFFAOYSA-N 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 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 1
- 238000007561 laser diffraction method 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
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 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
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000006839 xylylene group Chemical group 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention provides a liquid crystal sealing agent which can be used in a liquid crystal dropping process, is not easy to cause relative position deviation of a pair of substrates when a liquid crystal display panel is manufactured, and has high adhesive force. The liquid crystal sealing agent for solving the above problems comprises: a (meth) acrylic resin (A); a resin (B) having an epoxy group and a (meth) acrylic group in 1 molecule; a heat-curing agent (C) containing a heat-curing agent having a melting point of 90 ℃ or lower and/or a heat-curing agent having a melting point of 170 ℃ or higher; and a photopolymerization initiator (D). At a rate of 3000mJ/cm2The liquid crystal sealing agent is irradiated with 365nm light to form a cured filmAn elastic modulus at 120 ℃ of 30MPa or more and 100MPa or less.
Description
Technical Field
The present invention relates to a liquid crystal sealing agent, a liquid crystal display panel using the same, and a method for manufacturing the same.
Background
The liquid crystal display panel generally includes a pair of substrates, a frame-shaped sealing member disposed between the substrates, and liquid crystal filled in a region surrounded by the pair of substrates and the sealing agent. As a filling method of liquid crystal, a liquid crystal dropping process is mostly adopted. In the liquid crystal dropping process, a frame-shaped seal pattern is formed on one of the pair of substrates using a liquid crystal sealant. Then, liquid crystal is dropped into the seal pattern without curing the seal pattern. Thereafter, it is a common process to laminate 2 substrates with a seal pattern interposed therebetween, and cure the seal pattern by irradiating the seal pattern with light or heating the seal pattern (for example, patent documents 1 and 2). The cured seal pattern (hereinafter also referred to as a "seal member") not only prevents leakage of the liquid crystal but also serves a function of bonding the pair of substrates.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5584801
Patent document 2: japanese patent laid-open publication No. 2017-90931
Disclosure of Invention
Problems to be solved by the invention
Here, the liquid crystal sealing agent (seal pattern) applied to the substrate is cured to some extent by photo-curing. Then, the cured product is further heated to be sufficiently cured, and thereby, sufficient strength and hardness are exhibited. However, when the seal pattern is heated after photocuring, the seal pattern is temporarily softened by heat. Here, the seal pattern is often heated while moving on a conveyor device in which a plurality of rollers are arranged in parallel. However, when the seal pattern is softened during the movement, the substrates may be bent between the rollers or the relative positions of the pair of substrates may be shifted due to vibration during the conveyance. Also, as the seal pattern is cured by further heating, the substrates will be kept in a state of being shifted from each other. On the other hand, if the seal pattern after photocuring is hardened so that the seal pattern is not deformed by heat, the adhesive strength is liable to be lowered. As a result, the substrate and the sealing member may be peeled off, and liquid crystal leakage may occur.
Accordingly, the present invention provides a liquid crystal sealing agent which is usable even in a liquid crystal dropping process, and which is less likely to cause relative positional displacement between a pair of substrates in the production of a liquid crystal display panel and has a high adhesive force.
Means for solving the problems
The present invention provides the following liquid crystal sealing agent.
[1]A liquid crystal sealant comprising: a (meth) acrylic resin (A); a resin (B) having an epoxy group and a (meth) acrylic group in 1 molecule; a heat-curing agent (C) containing a heat-curing agent having a melting point of 90 ℃ or lower and/or a heat-curing agent having a melting point of 170 ℃ or higher; and a photopolymerization initiator (D) at 3000mJ/cm for the liquid crystal sealant2The cured film obtained by irradiating a light having a wavelength of 365nm has an elastic modulus of 30MPa or more and 100MPa or less at 120 ℃.
[2]Such as [1]]The liquid crystal sealing agent is prepared at a concentration of 3000mJ/cm2The glass transition temperature of the cured product is 120 ℃ or lower when the cured product is cured at 120 ℃ for 1 hour after being irradiated with 365nm light.
[3] The liquid crystal sealing agent according to [1] or [2], wherein the heat-curing agent (C) is at least one heat-curing agent selected from the group consisting of dihydrazide-based heat-latent curing agents, imidazole-based heat-latent curing agents, amine adduct-based heat-latent curing agents, and polyamine-based heat-latent curing agents.
[4] The liquid crystal sealing agent according to any one of [1] to [3], wherein the photopolymerization initiator (D) contains at least one of a thioxanthone compound and an oxime ester compound.
[5] The liquid crystal sealing agent according to any one of [1] to [4], further comprising an epoxy resin (E) which is liquid at ordinary temperature (excluding the resin (B)).
[6] The liquid crystal sealing agent according to any one of [1] to [5], further comprising inorganic particles (F) and/or organic particles (G).
The present invention also provides a method of manufacturing the liquid crystal display panel described below.
[7] A method of manufacturing a liquid crystal display panel having a pair of substrates, a frame-shaped sealing member disposed between the pair of substrates, and liquid crystal filled between the pair of substrates and inside the frame-shaped sealing member, the method comprising: a seal pattern forming step of applying the liquid crystal sealing agent according to any one of [1] to [6] onto one of the pair of substrates to form a frame-shaped seal pattern; a liquid crystal dropping step of dropping a liquid crystal into a region which is located on the one substrate and surrounded by the seal pattern, or a region which is located on the other substrate and surrounded by the seal pattern when the other substrate is opposed to the one substrate; an overlapping step of overlapping the one substrate and the other substrate with the seal pattern interposed therebetween; and a curing step of curing the seal pattern.
[8] The method for manufacturing a liquid crystal display panel according to [7], wherein the curing step irradiates the seal pattern with light.
[9] The method of manufacturing a liquid crystal display panel according to [8], wherein the curing step further includes heating after the irradiation of the light.
The present invention also provides the following liquid crystal display panel.
[10] A liquid crystal display panel having: a pair of substrates; a frame-shaped sealing member disposed between the pair of substrates; and a liquid crystal filled between the pair of substrates and inside the frame-shaped sealing member, wherein the sealing member is a cured product of the liquid crystal sealing agent according to any one of [1] to [6 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the liquid crystal sealing agent of the present invention, when a liquid crystal display panel is manufactured by a liquid crystal dropping process, a relative positional shift between a pair of substrates is less likely to occur. In addition, the substrates can be firmly bonded to each other. Therefore, a high-quality liquid crystal display panel can be manufactured.
Drawings
FIG. 1 is a schematic view for explaining a method of carrying out an offset test in examples.
Detailed Description
1. Liquid crystal sealing agent
The liquid crystal sealing agent of the present invention is preferably used for a liquid crystal sealing agent for a liquid crystal dropping process, which is mostly cured by both light and heat, but may be applied to other methods. The liquid crystal sealing agent comprises (meth) acrylic resin (A), resin (B) having an epoxy group and a (meth) acrylic group in 1 molecule, thermal curing agent (C), and photopolymerization initiator (D). The liquid crystal sealing agent may contain epoxy resin (E), inorganic particles (F), organic particles (G), various additives, and the like as necessary.
As described above, when a liquid crystal display panel is produced using a conventional liquid crystal sealing agent, the seal pattern is temporarily softened by heating after photocuring, and the relative positions of the pair of substrates are likely to be shifted (hereinafter, also referred to as "positional shift of substrates"). On the other hand, if the seal pattern after photocuring is hardened in order to suppress deformation of the seal pattern, the adhesive strength is insufficient, and the seal member and the substrate may be peeled off.
The heating temperature of the seal pattern is generally 100 to 150 ℃. The heat-curing agent (latent heat-curing agent) contained in the conventional liquid crystal sealing agent is solid at room temperature, and has a melting point of about 100 to 150 ℃. The latent curing agent is melted by heating and reacts with a thermosetting resin (e.g., epoxy resin, etc.). However, as a result of intensive studies by the inventors of the present application, it was found that when the heating temperature of the seal pattern is close to the melting point of the thermosetting agent, not only the thermosetting resin is softened by heat at the time of curing, but also the thermosetting agent before reacting with the thermosetting resin or the like melts, thereby also causing a decrease in the viscosity of the seal pattern. If the viscosity of the seal pattern is reduced, the substrate is likely to be displaced.
In contrast, the liquid crystal sealing agent of the present invention contains a thermosetting agent having a melting point of 90 ℃ or lower, or a thermosetting agent having a melting point of 170 ℃ or higher as the thermosetting agent (C). When the melting point of the thermosetting agent (C) is 90 ℃ or lower, the thermosetting agent is smoothly melted at a low temperature. Further, since the thermosetting resin is cured by the thermosetting agent (C) before the thermosetting resin is softened by heat, the above-described positional deviation of the substrate is less likely to occur. On the other hand, when the heat-curing agent (C) is a heat-curing agent having a melting point of 170 ℃ or higher, the curing agent is gradually melted, so that the viscosity of the liquid crystal sealing agent after photocuring is not likely to be excessively lowered, and the substrate is not likely to be displaced.
The liquid crystal sealing agent of the present invention is described in detail, but the elastic modulus of the cured film after photocuring (before heat curing) is within a certain range. If the elastic modulus of the cured film after photocuring is too high, the adhesive strength tends to be low, and if the elastic modulus is too low, the above-described positional deviation tends to occur. On the other hand, if the modulus of elasticity of the cured film is within a certain range, good adhesion strength and prevention of positional deviation of the substrate can be achieved at the same time. Hereinafter, each component of the liquid crystal sealing agent of the present invention will be described.
1-1. (meth) acrylic resin (A)
The (meth) acrylic resin (a) may contain 1 or more (meth) acrylic groups in one molecule. However, in the present specification, the resin (B) containing a (meth) acrylic group and an epoxy group in 1 molecule is not included in the (meth) acrylic resin (a). In the present specification, the term (meth) acrylic refers to methacrylic acid, acrylic acid, or both, and the resin includes not only polymers but also monomers and oligomers.
Here, examples of the (meth) acrylic resin (a) include: di (meth) acrylates of polyethylene glycol, propylene glycol, polypropylene glycol, and the like; di (meth) acrylate ester of tris (2-hydroxyethyl) isocyanurate; di (meth) acrylate of diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol; di (meth) acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol a; di-or tri (meth) acrylate of triol obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane; di (meth) acrylate of diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of bisphenol a; tri (meth) acrylate esters of tris (2-hydroxyethyl) isocyanurate; tri (meth) acrylate of trimethylolpropane, or an oligomer thereof; tri (meth) acrylate of pentaerythritol, or an oligomer thereof; poly (meth) acrylates of dipentaerythritol; tris (acryloyloxyethyl) isocyanurate; caprolactone-modified tris (acryloyloxyethyl) isocyanurate; caprolactone-modified tris (methacryloyloxyethyl) isocyanurate; poly (meth) acrylates of alkyl-modified dipentaerythritol; caprolactone-modified poly (meth) acrylates of dipentaerythritol; di (meth) acrylate of hydroxypivalic acid neopentyl glycol; di (meth) acrylate of caprolactone-modified hydroxypivalic acid neopentyl glycol; ethylene oxide-modified phosphoric acid (meth) acrylate; (meth) acrylic acid esters of ethylene oxide-modified alkylated phosphoric acids; oligomeric (meth) acrylates of neopentyl glycol, trimethylolpropane, pentaerythritol; and so on.
Among these, from the viewpoint of easily bringing the elastic modulus of the film after photocuring of the liquid crystal sealing agent into a desired range, a resin having a glass transition temperature of 25 ℃ or more and less than 200 ℃ is preferable. The glass transition temperature is more preferably 40 to 200 ℃, and still more preferably 50 to 150 ℃. The glass transition temperature can be measured by a viscoelasticity measuring apparatus (DMS).
In addition, it is particularly preferable that the (meth) acrylic resin (a) contains a hydrogen-bonding functional group such as a hydroxyl group, a urethane bond, an amide group, or a carboxyl group. The hydrogen-bonding functional group also includes a hydroxyl group, a urethane bond, a carboxyl group, an amide group, and the like contained in the raw material of the (meth) acrylic resin (a).
When the (meth) acrylic resin (a) contains a hydrogen-bonding functional group, the compatibility with a liquid crystal which is usually hydrophobic is low. As a result, the liquid crystal sealing agent is not easily dissolved in the liquid crystal, and is suitable for the liquid crystal dropping process.
The hydrogen-bonding functional group equivalent of the (meth) acrylic resin (a) contained in the liquid crystal sealing agent is preferably 1.0 × 10-4～5×10-3mol/g, more preferably 2.0X 10-3～4.5×10-3mol/g. If the hydrogen-bonding functional group equivalent is less than 1.0X 10-4When the amount of the hydrogen-bonding functional group is small in mol/g, the amount of the hydrogen-bonding functional group in the molecule of the (meth) acrylic resin (A)1 is small, and the inhibition of the hydrogen-bonding in the liquid crystal is not easily obtainedThe effect of dissolution in (1). If the hydrogen-bonding functional group equivalent of the (meth) acrylic resin (A) is more than 5X 10-3The mol/g tends to lower the moisture resistance of the cured product of the liquid crystal sealing agent.
The hydrogen-bonding functional group equivalent (mol/g) of the (meth) acrylic resin (a) can be determined from "(the number of hydrogen-bonding functional groups contained in a molecule of the (meth) acrylic resin (a) 1"/"(the weight average molecular weight (Mw) of the (meth) acrylic resin (a)"). Here, the hydrogen bonding functional group equivalent of the (meth) acrylic resin (a) can be adjusted by the number of hydrogen bonding functional groups contained in the (meth) acrylic resin.
The weight average molecular weight of the (meth) acrylic resin (A) is preferably 310 to 1000, more preferably 400 to 900. The weight average molecular weight Mw of the (meth) acrylic resin (a) can be measured (in terms of polystyrene) by, for example, Gel Permeation Chromatography (GPC).
The amount of the (meth) acrylic resin (a) contained in the liquid crystal sealing agent depends on the desired curability of the liquid crystal sealing agent, but is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, and still more preferably 3 to 10 parts by mass, based on 100 parts by mass of the liquid crystal sealing agent. When the amount of the (meth) acrylic resin (a) is within the above range, the elastic modulus of the liquid crystal sealing agent after photocuring tends to be good.
1-2. resin (B)
The resin (B) is a resin having an epoxy group and a (meth) acrylic group in 1 molecule, and examples thereof include a (meth) acrylic acid-modified epoxy resin obtained by reacting an epoxy resin with (meth) acrylic acid in the presence of a basic catalyst.
The resin (B) has an epoxy group and a (meth) acrylic group in the molecule, and thus has both photocurability and thermosetting properties. Here, the amorphous epoxy resin is highly soluble in liquid crystal, and therefore, it is generally preferable not to be contained in a liquid crystal sealing agent used in a liquid crystal dropping process. However, in the case where the epoxy resin has a (meth) acrylic group as in the resin (B) of the present invention, the solubility in liquid crystal is lowered. Therefore, the resin (B) may be a resin obtained by introducing a (meth) acrylic group into an amorphous epoxy resin.
The epoxy resin used as a raw material of the resin (B) may be a 2-or more-functional epoxy resin having 2 or more epoxy groups in the molecule, and includes bisphenol type epoxy resins such as bisphenol a type, bisphenol F type, 2' -diallylbisphenol a type, bisphenol AD type, and hydrogenated bisphenol type epoxy resins; novolac type epoxy resins such as phenol Novolac type, cresol Novolac type, biphenyl Novolac type, and trisphenol Novolac type; biphenyl type epoxy resin; naphthalene type epoxy resins, and the like. The (meth) acrylic-modified epoxy resin obtained by (meth) acrylic-modifying a 3-functional, 4-functional or other polyfunctional epoxy resin has a high crosslinking density, and the adhesive strength between the sealing member and the substrate is likely to decrease when the liquid crystal display panel is manufactured. Therefore, a (meth) acrylic-modified epoxy resin obtained by (meth) acrylic-modifying a 2-functional epoxy resin is preferable.
The 2-functional epoxy resin is preferably a biphenyl type epoxy resin, a naphthalene type epoxy resin, or a bisphenol type epoxy resin, and bisphenol type epoxy resins such as bisphenol a type and bisphenol F type are more preferable from the viewpoint of coating efficiency of the liquid crystal sealing agent. Bisphenol epoxy resins have advantages such as superior coatability compared with epoxy resins such as biphenyl ether resins.
Here, the epoxy resin to be a raw material of the resin (B) may be one kind, or two or more kinds. The epoxy resin used as a raw material is preferably purified by a molecular distillation method, a cleaning method, or the like.
Here, the resin (B) also preferably contains a hydrogen-bonding functional group such as a hydroxyl group, a urethane bond, an amide group, and a carboxyl group. Examples of the hydrogen-bonding functional group also include a hydroxyl group formed by reacting an epoxy group of an epoxy resin with (meth) acrylic acid. Examples of the hydrogen-bonding functional group also include (meth) acrylic acid as a raw material of the resin (B), a hydroxyl group, a urethane bond, a carboxyl group, an amide group, and the like contained in an epoxy resin.
If the resin (B) contains a hydrogen-bonding functional group, the compatibility of the resin (B) with the hydrophobic liquid crystal becomes low. As a result, the liquid crystal sealing agent is not easily dissolved in the liquid crystal, and is suitable for the liquid crystal dropping process.
The hydrogen-bonding functional group equivalent of the resin (B) is preferably 1.0X 10-4～5×10-3mol/g, more preferably 2.0X 10-3～4.5×10-3mol/g. If the hydrogen-bonding functional group equivalent is less than 1.0X 10-4When the amount is mol/g, the number of hydrogen-bonding functional groups in the resin (B) is small, and the effect of suppressing dissolution in the liquid crystal is not easily obtained. If the hydrogen-bonding functional group equivalent of the resin (B) is more than 5X 10-3The mol/g tends to lower the moisture resistance of the cured product of the liquid crystal sealing agent.
The hydrogen-bonding functional group equivalent (mol/g) of the resin (B) can be determined from "the number of hydrogen-bonding functional groups contained in one molecule of the resin (B"/"the weight average molecular weight (Mw) of the resin (B)". For example, when the hydrogen-bonding functional group of the resin (B) is only a hydroxyl group generated by the reaction of (meth) acrylic acid and an epoxy resin, the hydrogen-bonding functional group can be determined by dividing the number of moles of (meth) acrylic acid subjected to the reaction by the weight average molecular weight (Mw) of the resin (B).
Here, the hydrogen-bonding functional group equivalent of the resin (B) can be controlled by adjusting the number of moles of (meth) acrylic acid reacted with the epoxy resin as a raw material, or adjusting the amount of hydrogen-bonding functional groups contained in the (meth) acrylic acid and the epoxy resin as raw materials. The hydroxyl value equivalent of the resin (B) is particularly preferably 2.0X 10-3～5×10-3mol/g。
The weight average molecular weight of the resin (B) is, for example, preferably 310 to 1000, more preferably 350 to 900. The weight average molecular weight Mw of the resin (B) can be measured (in terms of polystyrene) by Gel Permeation Chromatography (GPC), for example.
The amount of the resin (B) contained in the liquid crystal sealing agent is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 40 to 70 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. When the amount of the resin (B) is within this range, the liquid crystal sealing agent is easily cured with good heat.
1-3 thermal curing agent (C)
The heat-curing agent (C) contains either or both of a heat-curing agent having a melting point of 90 ℃ or lower and a heat-curing agent having a melting point of 170 ℃ or higher. More preferably, the heat-curing agent (C) contains at least a heat-curing agent having a melting point of 90 ℃ or lower.
The melting point of the thermosetting agent having a melting point of 90 ℃ or lower is preferably 60 to 90 ℃, and more preferably 70 to 90 ℃. When the melting point of the thermosetting agent is 90 ℃ or lower, the substrate is less likely to be displaced when the liquid crystal display panel is produced as described above. On the other hand, when the melting point of the thermosetting agent is 60 ℃ or higher, the storage stability of the liquid crystal sealing agent tends to be good.
The melting point of the thermosetting agent having a melting point of 170 ℃ or higher is preferably 170 to 300 ℃, more preferably 170 to 230 ℃. When the melting point of the thermosetting agent is 170 ℃ or higher, the seal pattern is less likely to be softened excessively and the substrate is less likely to be displaced when the liquid crystal display panel is manufactured as described above. On the other hand, when the melting point of the thermosetting agent is 230 ℃ or lower, it is easy to sufficiently heat-cure the liquid crystal sealing agent without excessively raising the temperature at the time of curing.
The heat curing agent (C) is not particularly limited as long as it has the melting point and can cure the resin (B) by heating, but is preferably at least one heat curing agent selected from the group consisting of dihydrazide-based heat latent curing agents, imidazole-based heat latent curing agents, amine adduct-based heat latent curing agents, and polyamine-based heat latent curing agents. The heat-curing agent (C) may contain only one of them, or may contain two or more of them.
Examples of dihydrazide-based heat latent curing agents include adipic acid dihydrazide (melting point 181 ℃ C.), dodecanedioic acid dihydrazide (melting point 190 ℃ C.), and sebacic acid dihydrazide (melting point 189 ℃ C.).
Examples of the imidazole-based heat latent curing agent include 2, 4-diamino-6- [2 '-ethylimidazolyl- (1') ] -ethyltriazine (melting point 215 to 225 ℃).
The amine adduct-based heat latent curing agent is a heat latent curing agent formed of an adduct compound obtained by reacting an amine compound having catalytic activity with an arbitrary compound.
The polyamine-based heat latent curing agent is a heat latent curing agent having a polymer structure obtained by reacting an amine with an epoxide, and examples thereof include Adeka Harden EH4357S (softening point 73 to 83 ℃) manufactured by ADEKA, and Adeka Harden EH5057P (melting point 75 to 85 ℃) manufactured by ADEKA.
The amount of the heat-curing agent (C) is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, and still more preferably 5 to 13 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. When the amount of the thermosetting agent (C) is within this range, the liquid crystal sealing agent can be easily cured sufficiently by heating.
1-4 photo polymerization initiator (D)
The photopolymerization initiator (D) may be a compound that can generate an active species by irradiation with light, and may be a self-cleavage type photopolymerization initiator or a hydrogen abstraction type photopolymerization initiator. The liquid crystal sealing agent may contain only one kind of photopolymerization initiator (D), or may contain two or more kinds.
Examples of the self-cleavage type photopolymerization initiator include: alkylphenone-based compounds (e.g., benzildimethyl ketal such as 2, 2-dimethoxy-1, 2-diphenylethane-1-one (IRGACURE 651 manufactured by BASF Co., Ltd.), α -aminoalkylphenone such as 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1-one (IRGACURE 907 manufactured by BASF Co., Ltd.), α -hydroxyalkylphenone such as 1-hydroxycyclohexylphenylketone (IRGACURE 184 manufactured by BASF Co., Ltd.), acylphosphine oxide-based compounds (e.g., 2,4, 6-trimethylbenzoin diphenylphosphine oxide), titanocene-based compounds (e.g., bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, etc.), (e.g., bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium), Acetophenone-based compounds (e.g., diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzildimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) one, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-mercaptomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, etc.), benzoyl formate-based compounds (e.g., methyl phenylglyoxylate (methyl phenylglyoylester), etc.), Benzoin ether compounds (e.g., benzoin methyl ether, benzoin isopropyl ether, etc.), and oxime ester compounds (e.g., 1, 2-octanedione-1- [4- (phenylsulfanyl) -2- (O-benzoyl oxime) ] (IRGACURE OXE01, BASF Co., Ltd.), ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (0-acetyl oxime) (IRGACURE OXE02, BASF Co., Ltd.).
Examples of the hydrogen abstraction-type photopolymerization initiator include: benzophenone-based compounds (e.g., benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4 ' -dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4 ' -methyl-diphenylsulfide, acrylated benzophenone, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3 ' -dimethyl-4-methoxybenzophenone, etc.), thioxanthone-based compounds (e.g., thioxanthone, 2-chlorothioxanthone (manufactured by Tokyo chemical industries), 1-chloro-4-propoxythioxanthone, 1-chloro-4-ethoxythioxanthone (manufactured by Lambson Limited Speedcure CPTX), 2-isopropylxanthone (manufactured by Lambson Limited, Speedcure ITX), 4-isopropylthioxanthone, 2, 4-dimethylthioxanthone, 2, 4-Diethylthioxanthone (DETX) (Speedcure DETX manufactured by Lambson Limited), 2, 4-dichlorothioxanthone, anthraquinone-based compounds (e.g., 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertbutylanthraquinone, 1-chloroanthraquinone, 2-Hydroxyanthraquinone (2-Hydroxyanthone manufactured by Tokyo chemical Co., Ltd.), 2, 6-dihydroxyanthraquinone (Anthraflavic Acid manufactured by Tokyo chemical Co., Ltd.), 2-hydroxymethylanthraquinone (2- (Hydroxymethyl) anthaquinone manufactured by pure chemical Co., Ltd.), and benzyl-based compounds.
Among the above, the thioxanthone-based compounds, anthraquinone-based compounds, and oxime ester-based compounds are preferable, and the thioxanthone-based compounds and oxime ester-based compounds are particularly preferable.
The molecular weight of the photopolymerization initiator (D) is preferably 200 or more and 5000 or less. When the molecular weight is 200 or more, the polymer is not easily eluted into the liquid crystal. When the molecular weight is 5000 or less, the compatibility with the (meth) acrylic resin (a) is improved, and sufficient curability is easily obtained. The molecular weight of the photopolymerization initiator (D) is more preferably 230 to 3000 inclusive, and still more preferably 230 to 1500 inclusive.
The content of the photopolymerization initiator (D) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. When the amount of the photopolymerization initiator (D) is within this range, the (meth) acrylic resin (a) and the resin (B) can be easily photocured sufficiently.
1-5. epoxy resin (E)
The liquid crystal sealing agent may further contain an epoxy resin (E) which is liquid at ordinary temperature. When the liquid crystal sealing agent contains the epoxy resin (E), the display characteristics of the resulting liquid crystal panel become good, and the moisture resistance of the cured product of the liquid crystal sealing agent is improved.
Examples of such epoxy resins (E) include epoxy resins having a weight average molecular weight of 500 to 10000, and more preferably aromatic epoxy resins having a weight average molecular weight of 1000 to 5000. The weight average molecular weight of the epoxy resin can be measured (in terms of polystyrene) by, for example, Gel Permeation Chromatography (GPC).
Examples of such aromatic epoxy resins include: aromatic polyglycidyl ether compounds obtained by reacting aromatic diols represented by bisphenol a, bisphenol S, bisphenol F, bisphenol AD, and the like, diols obtained by modifying these with ethylene glycol, propylene glycol, or alkylene glycol, and epichlorohydrin; a Novolac-type polyglycidyl ether compound obtained by the reaction of a polyphenol represented by a Novolac resin derived from phenol or cresol and formaldehyde, a polyallyphenol, a copolymer thereof, or the like, with epichlorohydrin; glycidyl ether compounds of xylylene phenol resins, and the like.
Among them, the aromatic epoxy resin is preferably cresol Novolac type epoxy resin, phenol Novolac type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, trisphenol ethane type epoxy resin, trisphenol type epoxy resin, dicyclopentadiene type epoxy resin, diphenyl ether type epoxy resin, biphenyl type epoxy resin. The liquid crystal sealing agent may contain only one of them, or may contain two or more of them.
The content of the liquid epoxy resin (E) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 1 to 10 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. When the amount of the liquid epoxy resin (E) is within this range, the moisture resistance of a cured product of the liquid crystal sealing agent is easily improved.
1-6 inorganic particles (F) and organic particles (G)
The liquid crystal sealing agent may further contain inorganic particles (F) and organic particles (G) as needed. The liquid crystal sealing agent may contain either or both of the inorganic particles (F) and the organic particles (G). When the liquid crystal sealing agent contains the inorganic particles (F), the viscosity of the liquid crystal sealing agent, the strength of the cured product, and the linear expansibility of the cured product can be easily adjusted. On the other hand, when the liquid crystal sealing agent contains the organic particles (G), the elastic modulus and the like of the liquid crystal sealing agent after photocuring can be easily adjusted.
Examples of the inorganic particles (F) include inorganic fillers such as calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silica (silica), potassium titanate, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride and the like, and preferably include silica and talc. Among these, silica (silica) or talc is preferable. The liquid crystal sealing agent may contain only one kind of inorganic particles (F), or may contain two or more kinds.
The shape of the inorganic particles (F) is not particularly limited, and may be a fixed shape such as a sphere, a plate, or a needle, or an indefinite shape. The inorganic particles (F) preferably have an average primary particle diameter of 1.5 μm or less and a specific surface area of 0.5m or less2/g～20m2(ii) in terms of/g. The average primary particle diameter of the inorganic particles (F) can be measured by a laser diffraction method described in JIS Z8825-1. The specific surface area can be measured by the BET method described in JIS Z8830.
The content of the inorganic particles (F) is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, and still more preferably 5 to 20 parts by mass, based on 100 parts by mass of the liquid crystal sealing agent. When the amount of the inorganic particles (F) is within this range, the viscosity of the liquid crystal sealing agent and the like can be easily brought within a desired range.
On the other hand, examples of the organic particles (G) include silicone particles, acrylic particles, styrene particles such as styrene-divinylbenzene copolymer, and polyolefin particles. The liquid crystal sealing agent may contain only one kind of organic particles (G), or may contain two or more kinds. The organic particles (G) preferably have an average primary particle diameter of 0.05 to 13 μm, more preferably 0.1 to 10 μm, and still more preferably 0.1 to 8 μm.
The shape of the organic particles (G) is not particularly limited, but is preferably spherical, and more preferably spherical. The spherical shape means that the ratio b/a of the minimum value (b) to the maximum value (a) of the diameters of the particles is 0.9 to 1.0. The average primary particle diameter of the organic particles (G) can be measured by image analysis using a microscope, specifically, an electron microscope. In addition, the surface of the organic particles (G) is preferably smooth. When the surface is smooth, the specific surface area decreases, and the amount of the organic particles (G) that can be added to the liquid crystal sealing agent increases.
The content of the organic particles (G) is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and still more preferably 0.3 to 15 parts by mass, per 100 parts by mass of the liquid crystal sealing agent. When the amount of the organic particles (G) is within this range, the elastic modulus of the liquid crystal sealing agent after photocuring can be easily brought within a desired range.
1-7 physical Properties of other additives and liquid Crystal sealing agent
The liquid crystal sealing agent may further contain a coupling agent such as a silane coupling agent, an ion capturing agent, an ion exchanger, a leveling agent, a pigment, a dye, a plasticizer, an antifoaming agent, and the like as required. In addition, spacers (spacers) and the like may be further included to adjust the gap of the liquid crystal display panel.
The viscosity of the liquid crystal sealing agent at 25 ℃ and 2.5rpm is preferably 200 to 450 pas, more preferably 300 to 400 pas. When the viscosity is within the above range, the liquid crystal sealing agent (seal pattern) is likely to deform to fill the gap when the pair of substrates are laminated with the liquid crystal sealing agent interposed therebetween. Therefore, the gap width between the pair of substrates of the liquid crystal display panel can be appropriately controlled.
In addition, from the viewpoint of coatability of the liquid crystal sealing agent, the thixotropic index (TI value) of the liquid crystal sealing agent of the present invention is preferably 1.0 to 1.5, and more preferably 1.1 to 1.3. The TI values are the following: the viscosity η 1 of the liquid crystal sealant at room temperature (25 ℃), at 0.5rpm, and the viscosity η 2 of the liquid crystal sealant at 5rpm were measured using an E-type viscometer, and the measured values were applied to the values obtained by the following formula (1).
TI value (. eta.1 (25 ℃) at 0.5 rpm)/(. eta.2 (25 ℃) at 5 rpm) · (1)
At a rate of 3000mJ/cm2The cured film obtained by irradiating the liquid crystal sealing agent with 365nm light has an elastic modulus at 120 ℃ of 30MPa to 100MPa, more preferably 32 to 90MPa, and still more preferably 34 to 88 MPa. The elastic modulus of the film cured under the above conditions substantially corresponds to the elastic modulus of the liquid crystal sealing agent after photocuring and before heat curing. If the elastic modulus is 30MPa or more, the seal pattern is not excessively deformed and the substrate is less likely to be displaced when the liquid crystal display panel is manufactured. On the other hand, if the elastic modulus is 100MPa or less, the bonding strength between the sealing member and the substrate is sufficiently improved when the liquid crystal display panel is manufactured. The elastic modulus can be adjusted by the structure of the (meth) acrylic resin (a), the structure of the resin (B) having an epoxy group and a (meth) acrylic group in 1 molecule, the reactive functional group equivalent, and the like.
The elastic modulus is a storage elastic modulus measured as follows. First, a liquid crystal sealing agent was applied to a thickness of 100 μm using an applicator or the like, and the applied liquid crystal sealing agent was heated to 3000mJ/cm in a nitrogen atmosphere2The light having a wavelength of 365nm was irradiated to carry out photocuring. The obtained cured film was cut into a rectangular shape, and the temperature was raised from room temperature at 5 ℃ per minute to 180 ℃ using a viscoelasticity measuring apparatus DMS, and the storage elastic modulus at 120 ℃ was determined.
On the other hand, at 3000mJ/cm2The glass transition temperature of the liquid crystal sealing agent when cured at 120 ℃ for 1 hour after irradiation with 365nm light is preferably 120 ℃ or lower, more preferably 80 to 120 ℃, and still more preferably 80 to 110 ℃. The glass transition temperature of the cured product under the above conditions substantially corresponds to the glass transition temperature of the liquid crystal sealing agent after photocuring and heat curing. When the glass transition temperature is 120 ℃ or lower, the adhesion strength between the sealing member and the substrate is likely to be improved. The glass transition temperature can be controlled by (A)Group) glass transition temperature of the acrylic resin (a).
The glass transition temperature of a cured product of the liquid crystal sealing agent can be measured as follows. The liquid crystal sealing agent was applied to a thickness of 100 μm using an applicator, and the thickness was 3000mJ/cm in a nitrogen atmosphere2The light having a wavelength of 365nm was irradiated to carry out photocuring. Thereafter, heat curing was carried out in an oven at 120 ℃ for one hour to obtain a cured film having a thickness of 100. mu.m. Then, the obtained cured film was cut into a rectangular shape, and the temperature was raised from room temperature at 5 ℃/min to 180 ℃ using a viscoelasticity measuring apparatus DMS, and the point at which the ratio of the storage elastic modulus (E ') to the loss elastic modulus (E') was the largest was defined as the glass transition temperature.
2. Liquid crystal display panel
The liquid crystal display panel of the present invention includes a pair of substrates, a frame-shaped sealing member disposed between the substrates, and a liquid crystal filled between the pair of substrates and inside the frame-shaped sealing member. In the liquid crystal display panel, the sealing member is a cured product of the liquid crystal sealing agent. As described above, since the elastic modulus of the liquid crystal sealing member after photocuring is in an appropriate range, the substrate is less likely to be displaced when the liquid crystal panel is manufactured. Further, since the sealing member has high adhesion strength to the substrate, liquid crystal leakage or the like is less likely to occur.
The pair of substrates (also referred to as a "display substrate and a counter substrate") are both transparent substrates. Examples of the material of the transparent substrate include glass, polycarbonate, polyethylene terephthalate, polyether sulfone, PMMA, and the like.
A matrix of TFTs, color filters, black matrices, and the like may be disposed on the surface of the display substrate or the counter substrate. An alignment film may be further formed on the surface of the display substrate or the counter substrate. The alignment film contains known organic alignment agents, inorganic alignment agents, and the like. In addition, known liquid crystals can be used as the liquid crystal.
The method for manufacturing the liquid crystal display panel generally includes a liquid crystal dropping process and a liquid crystal injecting process, but the method for manufacturing the liquid crystal display panel of the present invention is preferably the liquid crystal dropping process.
The manufacturing method of the liquid crystal display panel based on the liquid crystal dropping process comprises the following steps: 1) a seal pattern forming step of forming a frame-shaped seal pattern by applying the liquid crystal sealing agent on one substrate; 2) a liquid crystal dropping step of dropping a liquid crystal into a region surrounded by the seal pattern on the one substrate or a region surrounded by the seal pattern on the other substrate when the other substrate is opposed to the one substrate in a state where the seal pattern is not cured; 3) an overlapping step of overlapping one substrate and the other substrate with a seal pattern therebetween; and 4) a curing process of curing the seal pattern.
1) In the seal pattern forming step, the liquid crystal sealing agent is applied to one substrate. The method of applying the liquid crystal sealing agent is not particularly limited as long as it is a method capable of forming a seal pattern with a desired thickness and width, such as screen printing or dispenser application, and is the same as the known method of applying the liquid crystal sealing agent.
The shape of the seal pattern to be formed may be appropriately selected according to the application of the liquid crystal display panel, and may be a shape that prevents liquid crystal from leaking. For example, a rectangular frame shape may be used, but the shape is not limited to this. The line width of the seal pattern is preferably 0.2 to 1.0mm, and more preferably 0.2 to 0.7 mm.
2) In the liquid crystal dropping step, the pair of substrates are opposed to each other with the seal pattern uncured. Here, the uncured state of the seal pattern means a state in which the curing reaction of the liquid crystal sealing agent does not proceed to the gelation point. Before the liquid crystal dropping step, the seal pattern may be semi-cured by light irradiation or heating in order to suppress dissolution of the liquid crystal sealing agent in the liquid crystal. In addition, in the same manner as the known liquid crystal dropping method, the liquid crystal may be dropped on the substrate on which the seal pattern is formed, or may be dropped on the substrate (the other substrate) on which the seal pattern is not formed.
3) In the laminating step, one substrate and the other substrate are laminated so as to face each other with the seal pattern interposed therebetween. In this case, the gap between the substrates is controlled to be within a desired range.
4) In the curing step, the seal pattern is cured. The curing method of the seal pattern is not particularly limited, but it is preferable that the temporary curing is performed by irradiation with light of a predetermined wavelength and then the main curing is performed by heating. By the light irradiation, the seal pattern can be cured instantaneously, and the dissolution of the component in the liquid crystal sealant into the liquid crystal can be suppressed.
The wavelength of the light to be irradiated may be appropriately selected according to the kind of the photopolymerization initiator, and is preferably ultraviolet light. The light irradiation time depends on the composition of the liquid crystal sealing agent, but is, for example, about 10 minutes. The amount of energy irradiated at this time may be an amount of energy of such a degree that the (meth) acrylic resin (a), the resin (B), and the like can be cured.
On the other hand, the heating temperature depends on the composition of the liquid crystal sealing agent, but is, for example, 100 to 150 ℃ and the heating time is preferably about 2 hours.
Examples
The present invention will be described in detail based on examples, but the present invention is not limited to these examples.
[ Material ]
In examples and comparative examples, the following materials were used.
[ meth (acrylic) resin (A) > ]
(meth) acrylic resin (A-1): ebecryl3700 (manufactured by Daicel Allnex Ltd., bisphenol A type epoxy acrylate (completely esterified product), glass transition temperature 65 ℃ C.)
(meth) acrylic resin (A-2): A-BPE-10 (ethoxylated bisphenol A diacrylate, manufactured by Xinzhongcun chemical industries, glass transition temperature: -12 ℃ C.)
(meth) acrylic resin (A-3): A-TMPT (trimethylolpropane triacrylate, glass transition temperature: 250 ℃ or higher, manufactured by Ningzhongcun chemical industries Co., Ltd.)
< resin (B) >)
Resin (B-1): synthesis of methacrylic-modified bisphenol F type epoxy resin (75% partial methacrylate) obtained in Synthesis example 1 described below
Resin (B-2): acrylic-modified bisphenol A epoxy resin (75% partially acrylated) obtained in synthetic example 2 described below
< thermosetting agent (C) >)
Thermal curing agent (C-1): adeka Harden EH5057P (polyamine latent heat-curing agent, manufactured by ADEKA corporation, melting point 75-85 ℃ C.)
Thermal curing agent (C-2): ADH (adipic acid dihydrazide, melting Point 177-184 ℃ manufactured by Nippon Kasei Co., Ltd.)
Thermal curing agent (C-3): MDH (manufactured by Japan Finechem Inc., malonic acid dihydrazide, melting point 152 ℃ C.)
< photopolymerization initiator (D) >)
Photopolymerization initiator (D-1): IRGACURE OXE01 (manufactured by BASF corporation)
< epoxy resin (E) >)
Epoxy resin (E-1): epikote 1004AF (manufactured by Mitsubishi Chemical Corporation, epoxy resin, softening point 97 ℃ C.)
Epoxy resin (E-2): YL983U (epoxy resin, model bis F, liquid at ambient temperature, manufactured by Mitsubishi Chemical Corporation)
< inorganic particles (F) and organic particles (G) >)
Inorganic particles (F-1): s-100 (silica particles, manufactured by Nippon catalytic chemical Co., Ltd.)
Organic particles (G-1): fine particle Polymer F351(Aica Kogyo Co., Ltd.)
< Others >
Silane coupling agent (H-1): KBM-403 (manufactured by Xinyue chemical industry Co., Ltd.)
< Synthesis example 1 >
Liquid bisphenol F-type epoxy resin (Epotohto YDF-8170C, manufactured by Tokyo chemical Co., Ltd., epoxy equivalent of 160g/eq)160g, a polymerization inhibitor (p-methoxyphenol) 0.1g, a catalyst (triethanolamine) 0.2g, and methacrylic acid 61.3g were charged into a flask, and reacted for 5 hours while refluxing and stirring at 90 ℃ by feeding dry air. The obtained compound was washed with ultrapure water 20 times to obtain a methacrylic acid-modified bisphenol F type epoxy resin (B-1)).
< Synthesis example 2 >
A liquid bisphenol A type epoxy resin (JER 828, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190g/eq), 190g of a polymerization inhibitor (p-methoxyphenol) 0.1g, a catalyst triethanolamine (0.2g), and 54.0g of acrylic acid were charged into a flask, and reacted for 5 hours while refluxing and stirring at 90 ℃ by feeding dry air. The obtained compound was washed 20 times with ultrapure water to obtain an acrylic-modified bisphenol A type epoxy resin (photocurable resin (B-2)).
[ examples and comparative examples ]
The raw materials described in table 1 were mixed at the ratios described in table 1, and sufficiently mixed to form a uniform liquid using three rolls, to obtain each liquid crystal sealing agent.
[ evaluation method ]
The liquid crystal sealing materials obtained in the examples and comparative examples were evaluated as follows. The results are shown in Table 1.
< evaluation of elastic modulus >
The liquid crystal sealing materials obtained in examples and comparative examples were applied to a thickness of 100 μm using an applicator, and the thickness was 3000mJ/cm in a nitrogen atmosphere2Curing is carried out by irradiating with 365nm light. The obtained cured film was cut into a rectangular shape, and the temperature was raised from room temperature at 5 ℃ per minute to 180 ℃ using a viscoelasticity measuring apparatus DMS, and the storage elastic modulus (E') at 120 ℃ was determined.
< evaluation of glass transition temperature >
The liquid crystal sealing materials obtained in examples and comparative examples were applied to a thickness of 100 μm using an applicator, and the thickness was 3000mJ/cm in a nitrogen atmosphere2The light having a wavelength of 365nm was irradiated to carry out photocuring. Thereafter, heat curing was carried out in an oven at 120 ℃ for one hour to obtain a cured film having a thickness of 100. mu.m. The obtained cured film was cut into a rectangular shape, and the temperature was raised from room temperature at 5 ℃/min to 180 ℃ using a viscoelasticity measuring apparatus DMS, and the point at which the ratio of the storage elastic modulus (E ') to the loss elastic modulus (E') obtained was the largest was defined as the glass transition temperature.
< offset test >
Using a screen printing plate, a liquid crystal sealing agent was printed at a width of 25mm X a length of 45mApproximately in the center of the glass substrate, m.times.5 mm thick alkali-free glass. The seal pattern was set in a circular shape with a diameter of 1 mm. Then, the pair of alkali-free glasses was placed on the seal pattern so as to be slightly shifted in the longitudinal direction, and fixed by a jig. The test piece was fixed by a jig using an ultraviolet irradiation apparatus (manufactured by USHIO INC.) at 500mW/cm2Irradiating 365nm light to cure the liquid crystal sealing agent. In this case, the ultraviolet light was set to an illuminance energy of 3000mJ/cm2. Next, as shown in FIG. 1, the end of one glass 10a of the test piece is held by a jig 20 and hung vertically. Then, a 500g weight 21 was hung from the lower end of the other glass 10 b. As described above, the cured product 11 of the liquid crystal sealing agent is disposed between the pair of glasses 10a and 10 b. The test piece with the weight 21 suspended thereon was put into an oven at 120 ℃, and the time until the other substrate 10b fell was measured and evaluated as follows.
Good: does not fall for more than 10 minutes
X: fall in less than 10 minutes
< evaluation of Photocurability (adhesive Strength) >)
The liquid crystal sealant was printed on alkali-free glass of 25mm × 45mm × 5mm thickness using a screen printing plate. The seal pattern was set in a circular shape with a diameter of 1 mm. Then, the pair of alkali-free glasses was placed on the seal pattern and fixed by a jig.
The test piece was fixed by a jig using an ultraviolet irradiation apparatus (manufactured by USHIO INC.) at 500mW/cm2The liquid crystal sealing agent was cured by irradiating light having a wavelength of 365 nm. In this case, the ultraviolet light was set to an illuminance energy of 3000mJ/cm2. The test piece obtained by photocuring the liquid crystal sealing agent with ultraviolet rays was subjected to a heat treatment at 120 ℃ for 60 minutes in an oven to prepare a sample for measuring the adhesive strength.
The cured liquid crystal sealant was peeled off in a direction parallel to the glass surface at a tensile rate of 2 mm/min using a tensile tester (manufactured by INTESCO Co., Ltd.), thereby measuring the in-plane tensile strength. Here, the adhesive strength was evaluated in accordance with the magnitude of the plane tensile strength as follows.
Good: tensile strength of 15MPa or more, and no problem in practical use
And (delta): the tensile strength is 10MPa or more and less than 15MPa, and the method has no problem in practical use
X: tensile strength of less than 10MPa, and the product cannot be used
[ Table 1]
As shown in table 1, according to the liquid crystal sealing agent containing the (meth) acrylic resin (a), the resin (B), the thermosetting agent (C) having a melting point of 90 ℃ or less or 170 ℃ or more, and the photopolymerization initiator (D) and having the cured film photocured under a certain condition, the cured film had an elastic modulus at 120 ℃ of 30MPa or more and 100MPa or less, the results of the offset test were good, and the results of the adhesion strength test were good (examples 1 to 7).
On the other hand, when the elastic modulus at 120 ℃ is too low, the evaluation results of the offset test are poor (comparative examples 1 and 3). It can be said that if the elastic modulus after photocuring (before heat curing) is low, the substrate is likely to be displaced when the liquid crystal display panel is manufactured. On the other hand, when the elastic modulus at 120 ℃ after photocuring (before heat curing) is too high, the adhesion strength between the sealing member and the substrate is low (comparative example 2).
Even if the 120 ℃ elastic modulus after photocuring (before thermal curing) is 30MPa or more and 100MPa or less, the results of the offset test are poor when the melting point of the thermosetting agent (C) is in the range of higher than 90 ℃ and lower than 170 ℃ (comparative example 4). It is presumed that the liquid crystal sealing agent after photo-curing is temporarily softened until it is cured by heating and thus has a shift due to a high melting point of the thermal polymerization initiator.
The present application claims priority based on japanese patent application No. 2019-089857 filed on 5/10 in 2019. The contents described in the specification and drawings are all incorporated in the specification of the present application.
Industrial applicability
According to the liquid crystal sealing agent of the present invention, substrates can be firmly bonded to each other without causing positional deviation of the substrates by a liquid crystal dropping process. Therefore, it is very useful for manufacturing a high-quality liquid crystal display panel.
Description of the reference numerals
10a substrate
10b another substrate
11 cured product of liquid crystal sealing agent
20 clamping apparatus
21 weight
Claims (10)
1. A liquid crystal sealant comprising:
a (meth) acrylic resin (A);
a resin (B) having an epoxy group and a (meth) acrylic group in 1 molecule;
a heat-curing agent (C) containing a heat-curing agent having a melting point of 90 ℃ or lower and/or a heat-curing agent having a melting point of 170 ℃ or higher; and
a photopolymerization initiator (D),
for the liquid crystal sealant, 3000mJ/cm2The cured film obtained by irradiating a light having a wavelength of 365nm has an elastic modulus of 30MPa or more and 100MPa or less at 120 ℃.
2. The liquid crystal sealing agent according to claim 1, wherein the sealing agent is used at a concentration of 3000mJ/cm2The glass transition temperature of the cured product is 120 ℃ or lower when the cured product is cured at 120 ℃ for 1 hour after being irradiated with 365nm light.
3. The liquid crystal sealing agent according to claim 1 or 2, wherein the heat curing agent (C) is at least one heat curing agent selected from the group consisting of dihydrazide-based heat latent curing agents, imidazole-based heat latent curing agents, amine adduct-based heat latent curing agents, and polyamine-based heat latent curing agents.
4. A liquid crystal sealing agent according to any one of claims 1 to 3, wherein the photopolymerization initiator (D) comprises at least one of a thioxanthone compound and an oxime ester compound.
5. A liquid crystal sealing agent according to any one of claims 1 to 4, further comprising an epoxy resin (E) which is liquid at ordinary temperature (excluding the resin (B)).
6. A liquid crystal sealing agent according to any one of claims 1 to 5, further comprising inorganic particles (F) and/or organic particles (G).
7. A method of manufacturing a liquid crystal display panel having a pair of substrates, a frame-shaped sealing member disposed between the pair of substrates, and liquid crystal filled between the pair of substrates and inside the frame-shaped sealing member, the method comprising:
a seal pattern forming step of forming a frame-shaped seal pattern by applying the liquid crystal sealing agent according to any one of claims 1 to 6 to one of the pair of substrates;
a liquid crystal dropping step of dropping a liquid crystal into a region which is located on the one substrate and surrounded by the seal pattern, or a region which is located on the other substrate and surrounded by the seal pattern when the other substrate is opposed to the one substrate;
a laminating step of laminating the one substrate and the other substrate with the seal pattern interposed therebetween; and
and a curing step of curing the seal pattern.
8. The method of manufacturing a liquid crystal display panel according to claim 7, wherein in the curing step, the seal pattern is irradiated with light.
9. The method of manufacturing a liquid crystal display panel according to claim 8, wherein the curing step further comprises heating after the irradiation of light.
10. A liquid crystal display panel having:
a pair of substrates;
a frame-shaped sealing member disposed between the pair of substrates; and
a liquid crystal filled between the pair of substrates and inside the frame-shaped sealing member,
the sealing member is a cured product of the liquid crystal sealing agent according to any one of claims 1 to 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-089857 | 2019-05-10 | ||
| JP2019089857 | 2019-05-10 | ||
| PCT/JP2020/018466 WO2020230678A1 (en) | 2019-05-10 | 2020-05-01 | Liquid crystal sealant, liquid crystal display panel using same, and production method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113661438A true CN113661438A (en) | 2021-11-16 |
| CN113661438B CN113661438B (en) | 2024-06-28 |
Family
ID=
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Also Published As
| Publication number | Publication date |
|---|---|
| JP7238112B2 (en) | 2023-03-13 |
| JPWO2020230678A1 (en) | 2021-12-09 |
| TW202106737A (en) | 2021-02-16 |
| WO2020230678A1 (en) | 2020-11-19 |
| KR20210148294A (en) | 2021-12-07 |
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