JP4268284B2 - Photocurable resin composition, liquid crystal inlet sealing agent and liquid crystal display cell - Google Patents
Photocurable resin composition, liquid crystal inlet sealing agent and liquid crystal display cell Download PDFInfo
- Publication number
- JP4268284B2 JP4268284B2 JP26602999A JP26602999A JP4268284B2 JP 4268284 B2 JP4268284 B2 JP 4268284B2 JP 26602999 A JP26602999 A JP 26602999A JP 26602999 A JP26602999 A JP 26602999A JP 4268284 B2 JP4268284 B2 JP 4268284B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- resin composition
- photocurable resin
- sealing agent
- inlet 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.)
- Expired - Lifetime
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 101
- 238000007789 sealing Methods 0.000 title claims description 55
- 239000003795 chemical substances by application Substances 0.000 title claims description 44
- 239000011342 resin composition Substances 0.000 title claims description 43
- 238000007259 addition reaction Methods 0.000 claims description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 30
- 239000007795 chemical reaction product Substances 0.000 claims description 25
- -1 polyene compound Chemical class 0.000 claims description 25
- 229920006295 polythiol Polymers 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 19
- 125000000524 functional group Chemical group 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 238000002347 injection Methods 0.000 description 15
- 239000007924 injection Substances 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 150000004808 allyl alcohols Chemical class 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 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 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- RBKHNGHPZZZJCI-UHFFFAOYSA-N (4-aminophenyl)-phenylmethanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC=C1 RBKHNGHPZZZJCI-UHFFFAOYSA-N 0.000 description 1
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- LOZWAPSEEHRYPG-UHFFFAOYSA-N 1,4-dithiane Chemical group C1CSCCS1 LOZWAPSEEHRYPG-UHFFFAOYSA-N 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-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
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- NVZUUSWURIHBAK-UHFFFAOYSA-N C1(=CC=C(C=C1)N=[N+]=[N-])N=[N+]=[N-].N(=[N+]=[N-])C1=CC=C(C=C1)C=CC1=CC=C(C=C1)N=[N+]=[N-] Chemical compound C1(=CC=C(C=C1)N=[N+]=[N-])N=[N+]=[N-].N(=[N+]=[N-])C1=CC=C(C=C1)C=CC1=CC=C(C=C1)N=[N+]=[N-] NVZUUSWURIHBAK-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 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
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 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
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 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 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 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
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- FPODCVUTIPDRTE-UHFFFAOYSA-N bis(prop-2-enyl) hexanedioate Chemical compound C=CCOC(=O)CCCCC(=O)OCC=C FPODCVUTIPDRTE-UHFFFAOYSA-N 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- UOQACRNTVQWTFF-UHFFFAOYSA-N decane-1,10-dithiol Chemical compound SCCCCCCCCCCS UOQACRNTVQWTFF-UHFFFAOYSA-N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 239000001294 propane Substances 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- HEKQWIORQJRILW-UHFFFAOYSA-N tetrakis(prop-2-enyl) benzene-1,2,4,5-tetracarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=C(C(=O)OCC=C)C=C1C(=O)OCC=C HEKQWIORQJRILW-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-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
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、光硬化性樹脂組成物、その光硬化性樹脂組成物からなる液晶注入口封止剤、及び、その液晶注入口封止剤が用いられた液晶表示セルに関する。
【０００２】
【従来の技術】
液晶表示セルは、２枚の電極付き透明基板を所定の間隔をおいて対向させ、その周囲を適当なシール体で封着してセルを形成し、その一部に設けられた液晶注入口からセル内に液晶を注入し、この液晶注入口を液晶注入口封止剤を用いて封止することにより製造される。
【０００３】
従来、液晶注入口封止剤としては、１液型または２液型の硬化性エポキシ樹脂液や光硬化型のアクリル系樹脂液が広く用いられてきた。しかし、１液型の硬化性エポキシ樹脂液は、一般的に高温で長時間の加熱を要するため生産性に劣り、２液型の硬化性エポキシ樹脂液は、主剤と硬化剤とを混合するのに手間がかかり、しかも混合後は可使時間（ポットライフ）内に使用しなければならないため、特に作業性に劣るものであった。また、光硬化型のアクリル系樹脂液は、作業性や生産性には優れているものの、液晶との相互作用が強いため液晶を汚染して色むらを生じたり、表面の硬化性が悪いため硬化表面に粘着性が残り、埃や汚れを付着し易いものであった。
【０００４】
このような問題点に対応するため種々の検討が行われており、例えば、特開平６−１４８６５６号公報では、「１分子中に２個以上のチオール基を有するポリチオール化合物と、１分子中に２個以上の炭素−炭素二重結合を有するポリエン化合物と、光重合開始剤とからなる液晶注入口封止剤」が開示されており、また、特公昭５７−４２６４９号公報では、「特定のポリエン化合物、特定のポリチオール化合物及び有機ケイ素化合物の各特定量と光増感剤の各成分を含有する光硬化性組成物（液晶注入口封止剤）」が開示されている。
【０００５】
しかし、上記開示にあるような液晶注入口封止剤は、液晶注入口封止剤として必要な接着力（封止力）が未だ十分ではないという問題点や、液晶中に有機ケイ素化合物が溶出して液晶の配向不良を来すという問題点があり、十分に満足のいくものではなかった。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、上記従来の問題点に鑑み、優れた接着力（封止力）を発揮すると共に、液晶中に溶出せず、従って液晶の配向不良を来すことのない高性能の液晶注入口封止剤を得るに適する光硬化性樹脂組成物、及び、その光硬化性樹脂組成物からなる液晶注入口封止剤、並びに、その液晶注入口封止剤を用いた液晶表示セルを提供することにある。
【０００７】
【課題を解決するための手段】
請求項１に記載の光硬化性樹脂組成物は、ポリチオール化合物またはポリエン化合物とシランカップリング剤との付加反応物及び光重合開始剤が含有されてなることを特徴とする。
【０００８】
請求項２に記載の光硬化性樹脂組成物は、１分子中に２個以上の官能基を有するモノマーまたはオリゴマーとシランカップリング剤との付加反応物及び光重合開始剤が含有されてなることを特徴とする。
【０００９】
また、請求項３に記載の液晶注入口封止剤は、上記請求項１または請求項２のいずれかに記載の光硬化性樹脂組成物からなることを特徴とする。
【００１０】
さらに、請求項４に記載の液晶表示セルは、液晶が注入されたセルの液晶注入口が上記請求項３に記載の液晶注入口封止剤により封止されてなることを特徴とする。
【００１１】
本発明において、シランカップリング剤との付加反応物を生成させるために用いられるポリチオール化合物としては、１分子中に２個以上のチオール基を有するポリチオール化合物が好ましく、例えば、エタンジチオール、プロパンジチオール、ヘキサメチレンジチオール、デカメチレンジチオール、トリレン−２，４−ジチオール等の脂肪族ポリチオール；キシレンジチオール等の芳香族ポリチオール；ジグリコールジメルカプタン、トリグリコールジメルカプタン、テトラグリコールジメルカプタン、チオジグリコールジメルカプタン、チオトリグリコールジメルカプタン、チオテトラグリコールジメルカプタン、トリメチロールプロパントリス−β−メルカプトプロピオネート、１，４−ジチアン環含有ポリチオール化合物等の環状スルフィド化合物等が挙げられる。これらのポリチオール化合物は、単独で用いられても良いし、２種類以上が併用されても良い。
【００１２】
また、本発明において、シランカップリング剤との付加反応物を生成させるために用いられるポリエン化合物としては、１分子中に２個以上の炭素−炭素二重結合を有するポリエン化合物が好ましく、例えば、アリルアルコール誘導体、アクリル酸もしくはメタクリル酸と多価アルコールとのエステル類、ウレタンアクリレート、ジビニルベンゼン等が挙げられる。これらのポリエン化合物は、単独で用いられても良いし、２種類以上が併用されても良い。
【００１３】
アリルアルコール誘導体の具体例としては、例えば、トリアリルシアヌレート、トリアリルイソシアヌレート、ジアリルマレエート、ジアリルアジペート、ジアリルフタレート、トリアリルトリメリテート、テトラアリルピロメリテート、グリセリンジアリルエーテル、トリメチロールプロパンジアリルエーテル、ペンタエリスリトール、ジアリルエーテル等が挙げられる。これらのアリルアルコール誘導体は、単独で用いられても良いし、２種類以上が併用されても良い。
【００１４】
また、アクリル酸もしくはメタクリル酸と多価アルコールとのエステル類に用いられる多価アルコールとしては、例えば、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール等が挙げられる。これらの多価アルコールは、単独で用いられても良いし、２種類以上が併用されても良い。
【００１５】
上記各種ポリエン化合物の内、アリルアルコール誘導体が好適に用いられ、なかでもトリアリルシアヌレートやトリアリルイソシアヌレート等がより好適に用いられる。
【００１６】
本発明においては、前記ポリチオール化合物と上記ポリエン化合物は、それぞれ単独で用いられても良いが、両者が併用される方がより好ましい。また、両者が併用される場合、両者の内の少なくとも一方がシランカップリング剤との付加反応物を生成しておれば良い。
【００１７】
本発明において、シランカップリング剤との付加反応物を生成させるために用いられる１分子中に２個以上の官能基を有するモノマーとしては、例えば、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ビスフェノールＡジエトキシジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）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、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、トリス（メタアクリロキシエチル）イソシアヌレート等が挙げられる。これらのモノマーは、単独で用いられても良いし、２種類以上が併用されても良い。
【００１８】
また、本発明において、シランカップリング剤との付加反応物を生成させるために用いられる１分子中に２個以上の官能基を有するオリゴマーとしては、例えば、ウレタンアクリレート、エポキシアクリレート、ポリエステルアクリレート等が挙げられる。これらのオリゴマーは、単独で用いられても良いし、２種類以上が併用されても良い。
【００１９】
尚、上記１分子中に２個以上の官能基を有するモノマーとオリゴマーは、それぞれ単独で用いられても良いし、両者が併用されても良い。
【００２０】
本発明において、上述したポリチオール化合物またはポリエン化合物、または、１分子中に２個以上の官能基を有するモノマーまたはオリゴマーとの付加反応物を生成させるために用いられるシランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン等の不飽和基含有シランカップリング剤；γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン等のグリシジル基含有シランカップリング剤；γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン等のアミノ基含有シランカップリング剤；γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン等のメルカプト基含有シランカップリング剤等が挙げられる。これらのシランカップリング剤は、単独で用いられても良いし、２種類以上が併用されても良い。
【００２１】
前記ポリチオール化合物またはポリエン化合物、または、１分子中に２個以上の官能基を有するモノマーまたはオリゴマーと上記シランカップリング剤との付加反応方法は、特別なものではなく、溶媒の存在下もしくは非存在下で、また、常圧下もしくは減圧下で、例えばベンゾイルパーオキサイド等を反応触媒として、４０〜１２０℃程度の反応温度で常法により付加反応を行うことにより、所望の付加反応物を得ることが出来る。
【００２２】
本発明の光硬化性樹脂組成物には、上記付加反応物が必須成分として含有されるが、上記付加反応物と共に、シランカップリング剤との付加反応が行われていない前記ポリチオール化合物またはポリエン化合物、または、１分子中に２個以上の官能基を有するモノマーまたはオリゴマーの１種もしくは２種以上が併用される形で含有されていても良い。
【００２３】
本発明の光硬化性樹脂組成物には、光硬化反応を惹起及び促進するために、光重合開始剤が含有される。
【００２４】
上記光重合開始剤としては、例えば、ベンゾフェノン、ｐ−アミノベンゾフェノン、ｐ，ｐ’−ジメチルアミノベンゾフェノン、オルソベンゾイル安息香酸メチル、４−ベンゾイル−４’−メチルジフェニルサルファイド等のベンゾフェノン系光重合開始剤；アセトフェノン、ベンズアルデヒド、ベンジルジメチルケタール、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モルホリノプロパン−１、オリゴ〔２−ヒドロキシ−２−メチル−１−｛４−（１−メチルビニル）フェニル｝プロパノン〕等のアセトフェノン系光重合開始剤；ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾインエーテル系光重合開始剤；２，２’−アゾビスイソブチロニトリル等のアゾ系光重合開始剤；ジアゾアミノベンゼン等のジアゾ系光重合開始剤化合物、４，４’−ジアジドスチルベン−ｐ−フェニレンビスアジド、イソプロピルチオキサントン、ジエチルチオキサントン、アシルホスフィンオキサイド、ベンジル、カンファーキノン、アントラキノン、ミヒラーケトン等が挙げられる。これらの光重合開始剤は、単独で用いられても良いし、２種類以上が併用されても良い。
【００２５】
本発明の光硬化性樹脂組成物において、上記光重合開始剤の使用量は、特に限定されるものではないが、前記付加反応物１００重量部に対し、もしくは、前記付加反応物とシランカップリング剤との付加反応が行われていないポリチオール化合物またはポリエン化合物、または、１分子中に２個以上の官能基を有するモノマーまたはオリゴマーとの合計量１００重量部に対し、光重合開始剤０．０００１〜１０重量部であることが好ましく、より好ましくは０．０５〜５重量部である。
【００２６】
本発明の光硬化性樹脂組成物には、必須成分である前記付加反応物及び上記光重合開始剤以外に、本発明の課題達成を阻害しない範囲で必要に応じて、ウレタン系オリゴマー、アクリル系オリゴマー、エポキシ系オリゴマー、ポリエステル系オリゴマー、ゴム系オリゴマー等の各種オリゴマーの１種もしくは２種以上が含有されていても良い。
【００２７】
また、本発明の光硬化性樹脂組成物には、必須成分である前記付加反応物及び上記光重合開始剤以外に、本発明の課題達成を阻害しない範囲で必要に応じて、接着性向上剤、酸化防止剤、熱安定剤、重合禁止剤、充填剤、着色剤、揺変性付与剤、硬化促進剤、可塑剤、界面活性剤等の各種添加剤の１種もしくは２種以上が含有されていても良い。
【００２８】
次に、本発明の液晶注入口封止剤は、上述した本発明の光硬化性樹脂組成物からなる。本発明の光硬化性樹脂組成物を液晶注入口封止剤として使用するには、先ず、ＩＴＯ薄膜等の透明電極付きの２枚の透明板を、適当なスペーサを介して間隔をおいて対向させ、その周囲を液晶の注入口を残して適当なシール体でシールしてセルを形成する。上記シール体としては、例えば、エポキシ樹脂、ポリイミド樹脂等が挙げられる。
【００２９】
次いで、液晶注入口からセル内に液晶を注入した後、液晶注入口を液晶注入口封止剤で塞ぎ、これに活性光線を照射して液晶注入口封止剤（光硬化性樹脂組成物）を硬化させる。このような方法を用いることにより液晶注入口を支障なく効果的に封止することが出来る。
【００３０】
上記液晶としては、例えば、ネマチック液晶、コレステリック液晶、スメチック液晶等の一般的に用いられている各種液晶が挙げられ、好適に用いられる。
【００３１】
また、液晶注入口封止剤（光硬化性樹脂組成物）を硬化させるための活性光線としては、例えば、超高圧の水銀灯、高圧の水銀灯、低圧の水銀灯、メタルハライドランプなどを光源とする紫外線等の各種活性光線が挙げられ、好適に用いられる。
【００３２】
上記活性光線の照射により、本発明の光硬化性樹脂組成物からなる液晶注入口封止剤は、従来の例えばポリエン・ポリチオール系光硬化性樹脂組成物からなる液晶注入口封止剤と同様に、数秒から数分の短時間で硬化し、液晶注入口を支障なく効果的に封止することが出来る。
【００３３】
従って、上記の工程を経ることにより、本発明の液晶表示セルを作製することが出来る。
【００３４】
【作用】
本発明の光硬化性樹脂組成物は、ポリチオール化合物またはポリエン化合物とシランカップリング剤との付加反応物、または、１分子中に２個以上の官能基を有するモノマーまたはオリゴマーとシランカップリング剤との付加反応物を含有するので、優れた接着力（封止力）を発揮する。また、上記付加反応物は分子量が高いので、液晶中に溶出せず、従って液晶の配向不良を来すことがない。
【００３５】
また、本発明の液晶注入口封止剤は、上記光硬化性樹脂組成物からなるので、優れた接着力（封止力）を発揮すると共に、液晶中に溶出せず、従って液晶の配向不良を来すことのない高性能のものである。
【００３６】
さらに、本発明の液晶表示セルは、上記液晶注入口封止剤により液晶注入口が封止されているので、長期安定的に優れた封止性を有し、且つ、液晶の配向不良を来すことのない高性能のものである。
【００３７】
【発明の実施の形態】
本発明をさらに詳しく説明するため以下に実施例を挙げるが、本発明はこれら実施例のみに限定されるものではない。尚、実施例中の「部」は「重量部」を意味する。
【００３８】
（実施例１）
【００３９】
（１）光硬化性樹脂組成物（液晶注入口封止剤）の作製
トリレンジイソシアネート１７４部をセパラブルビーカーに仕込み、５０℃に加熱した後、この中に２−ヒドロキシプロピルアクリレート１３０部を約１時間かけて滴下し、反応させ、さらにｎ−ブタノール７４部を約３０分かけて滴下し、反応させて、ウレタンオリゴマーを合成した。
【００４０】
ポリチオール化合物としてトリメチロールプロパントリス−β−メルカプトプロピオネート３０部に対し、シランカップリング剤としてγ−メタクリロキシプロピルトリメトキシシラン４部及び反応触媒としてベンゾイルパーオキサイド（ＢＰＯ）０．０３部を添加混合し、８０℃で反応させて、ポリチオール化合物とシランカップリング剤との付加反応物を合成した。
【００４１】
上記で得られた付加反応物３４部に対し、前記で合成したウレタンオリゴマー４４部、ポリエン化合物としてトリアリルイソシアヌレート２０部及び光重合開始剤としてベンジルジメチルケタール２部を添加し、均一に加熱混合して、光硬化性樹脂組成物（液晶注入口封止剤）を作製した。
【００４２】
（実施例２）
ポリエン化合物としてトリアリルイソシアヌレート２０部に対し、シランカップリング剤としてγ−メルカプトプロピルトリメトキシシラン４部及び反応触媒としてＢＰＯ０．０３部を添加混合し、８０℃で反応させて、ポリエン化合物とシランカップリング剤との付加反応物を合成した。
【００４３】
上記で得られた付加反応物２４部に対し、実施例１で合成したウレタンオリゴマー４４部、ポリチオール化合物としてトリメチロールプロパントリス−β−メルカプトプロピオネート３０部及び光重合開始剤としてベンジルジメチルケタール２部を添加し、均一に加熱混合して、光硬化性樹脂組成物（液晶注入口封止剤）を作製した。
【００４４】
（実施例３）
１分子中に２個以上の官能基を有するモノマーとしてペンタエリスリトールテトラアクリレート５０部に対し、シランカップリング剤としてγ−メルカプトプロピルトリメトキシシラン４部及び反応触媒としてＢＰＯ０．０３部を添加混合し、８０℃で反応させて、１分子中に２個以上の官能基を有するモノマーとシランカップリング剤との付加反応物を合成した。
【００４５】
上記で得られた付加反応物５４部に対し、実施例１で合成したウレタンオリゴマー４４部及び光重合開始剤としてベンジルジメチルケタール２部を添加し、均一に加熱混合して、光硬化性樹脂組成物（液晶注入口封止剤）を作製した。
【００４６】
（比較例１）
光硬化性樹脂組成物（液晶注入口封止剤）の作製において、ポリチオール化合物（トリメチロールプロパントリス−β−メルカプトプロピオネート）３０部とシランカップリング剤（γ−メタクリロキシプロピルトリメトキシシラン）４部を付加反応させることなく、単に添加混合したこと以外は実施例１の場合と同様にして、光硬化性樹脂組成物（液晶注入口封止剤）を作製した。
【００４７】
（比較例２）
光硬化性樹脂組成物（液晶注入口封止剤）の作製において、シランカップリング剤（γ−メタクリロキシプロピルトリメトキシシラン）を添加しなかったこと以外は実施例１の場合と同様にして、光硬化性樹脂組成物（液晶注入口封止剤）を作製した。
【００４８】
（比較例３）
光硬化性樹脂組成物（液晶注入口封止剤）の作製において、１分子中に２個以上の官能基を有するモノマー（ペンタエリスリトールテトラアクリレート）５０部とシランカップリング剤（γ−メルカプトプロピルトリメトキシシラン）４部を付加反応させることなく、単に添加混合したこと以外は実施例３の場合と同様にして、光硬化性樹脂組成物（液晶注入口封止剤）を作製した。
【００４９】
実施例１〜３及び比較例１〜３で得られた光硬化性樹脂組成物（液晶注入口封止剤）の性能（▲１▼引張接着力、▲２▼液晶配向乱れ）を以下の方法で評価した。その結果は表１に示すとおりであった。
【００５０】
▲１▼引張接着力：２０ｍｍ×６０ｍｍ×８ｍｍの一方のガラス板に光硬化性樹脂組成物（液晶注入口封止剤）を約１ｍｇ塗布し、同一サイズの他方のガラス板を十文字に重ねた後、３０００ｍｊ／ｃｍ2 の光強度の紫外線を照射して接着した。次いで、この接着物を平面引張試験機にセットし、５ｍｍ／分の引張速度で平面引張試験を行って、引張接着力を測定した。尚、測定は３回行い、その平均値をもって引張接着力（ｋｇ／ｃｍ2 ）とした。
【００５１】
▲２▼液晶配向乱れ：配向処理｛配向膜：商品名「８０３４」（ジェイエスアール社製）を塗布後、ラビング｝が施された５０ｍｍ×５０ｍｍの一方の基板の中央に光硬化性樹脂組成物（液晶注入口封止剤）１滴と液晶｛商品名「ＪＣ−５００４ＬＡ」（チッソ社製）｝１滴とを滴下し、同一サイズの他方の基板を角度９０度の方向に重ねてオープンセルを作製した。次いで、光硬化性樹脂組成物（液晶注入口封止剤）と液晶との界面を偏光顕微鏡で観察し、液晶の配向が乱れている領域の幅（ｍｍ）を測定した。
【００５２】
【表１】
表１から明らかなように、本発明による実施例１〜３の光硬化性樹脂組成物（液晶注入口封止剤）は、いずれも接着力（封止力）に優れ、且つ、液晶の配向乱れも小さかった。
【００５４】
これに対し、ポリチオール化合物とシランカップリング剤を付加反応させることなく、単に添加した比較例１の光硬化性樹脂組成物（液晶注入口封止剤）は、接着力は良好であったものの、液晶の配向乱れが大きかった。
【００５５】
また、シランカップリング剤を添加しなかった比較例２の光硬化性樹脂組成物（液晶注入口封止剤）は、液晶の配向乱れは小さかったものの、接着力が極端に低かった。
【００５６】
さらに、１分子中に２個以上の官能基を有するモノマーとシランカップリング剤を付加反応させることなく、単に添加した比較例３の光硬化性樹脂組成物（液晶注入口封止剤）は、液晶の配向乱れが極端に大きく、接着力も低かった。
【００５７】
【発明の効果】
以上述べたように、本発明による光硬化性樹脂組成物は、優れた接着力（封止力）を発揮すると共に、液晶中に溶出せず、従って液晶の配向不良を来すことのない高性能の液晶注入口封止剤を得るに適する。
【００５８】
また、本発明による液晶注入口封止剤は、上記光硬化性樹脂組成物からなるので、優れた接着力（封止力）を発揮すると共に、液晶中に溶出せず、従って液晶の配向不良を来すことのない高性能のものであり、液晶表示セルの注入口封止用として好適に用いられる。
【００５９】
さらに、本発明による液晶表示セルは、上記液晶注入口封止剤により液晶注入口が封止されているので、長期安定的に優れた封止性を有し、且つ、液晶の配向不良を来すことのない高性能のものである。従って、液晶表示セルが用いられる各種用途むけ液晶表示セルとして好適に用いられる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photocurable resin composition, a liquid crystal inlet sealing agent comprising the photocurable resin composition, and a liquid crystal display cell using the liquid crystal inlet sealing agent.
[0002]
[Prior art]
The liquid crystal display cell has two transparent substrates with electrodes facing each other at a predetermined interval, and the periphery is sealed with an appropriate sealing body to form a cell. From a liquid crystal injection port provided in a part of the cell It is manufactured by injecting liquid crystal into the cell and sealing the liquid crystal inlet with a liquid crystal inlet sealing agent.
[0003]
Conventionally, as a liquid crystal inlet sealing agent, a one-component or two-component curable epoxy resin solution or a photocurable acrylic resin solution has been widely used. However, a one-component curable epoxy resin solution is generally inferior in productivity because it requires heating at a high temperature for a long time, and a two-component curable epoxy resin solution is a mixture of a main agent and a curing agent. In addition, after mixing, it must be used within the pot life (pot life), so that the workability is particularly poor. In addition, although photo-curable acrylic resin liquid is excellent in workability and productivity, it has strong interaction with the liquid crystal, so it contaminates the liquid crystal and causes uneven color, and the surface has poor curability. Stickiness remained on the cured surface, and dust and dirt were likely to adhere.
[0004]
Various studies have been made to deal with such problems. For example, in JP-A-6-148656, “a polythiol compound having two or more thiol groups in one molecule and a molecule in one molecule” is disclosed. A liquid crystal injection port sealing agent comprising a polyene compound having two or more carbon-carbon double bonds and a photopolymerization initiator ”is disclosed, and Japanese Patent Publication No. 57-42649 discloses a“ specific product ”. A photocurable composition (liquid crystal inlet sealing agent) containing each specific amount of a polyene compound, a specific polythiol compound and an organosilicon compound and each component of a photosensitizer is disclosed.
[0005]
However, the liquid crystal inlet sealing agent as disclosed above has a problem that the adhesive force (sealing power) necessary for the liquid crystal inlet sealing agent is not yet sufficient, and the organosilicon compound is eluted in the liquid crystal. As a result, there is a problem that the alignment of the liquid crystal is poor, which is not satisfactory.
[0006]
[Problems to be solved by the invention]
In view of the above-mentioned conventional problems, the object of the present invention is to provide a high-performance liquid crystal that exhibits excellent adhesive force (sealing power) and does not elute into the liquid crystal, and therefore does not cause poor alignment of the liquid crystal. A photocurable resin composition suitable for obtaining an inlet sealant, a liquid crystal inlet sealing agent comprising the photocurable resin composition, and a liquid crystal display cell using the liquid crystal inlet sealing agent It is to provide.
[0007]
[Means for Solving the Problems]
The photocurable resin composition according to claim 1 contains an addition reaction product of a polythiol compound or polyene compound and a silane coupling agent and a photopolymerization initiator.
[0008]
The photocurable resin composition according to claim 2 contains an addition reaction product of a monomer or oligomer having two or more functional groups in one molecule and a silane coupling agent and a photopolymerization initiator. It is characterized by.
[0009]
Moreover, the liquid-crystal inlet sealing agent of Claim 3 consists of the photocurable resin composition in any one of the said Claim 1 or Claim 2, It is characterized by the above-mentioned.
[0010]
Furthermore, the liquid crystal display cell according to claim 4 is characterized in that the liquid crystal inlet of the cell into which the liquid crystal is injected is sealed with the liquid crystal inlet sealing agent according to claim 3.
[0011]
In the present invention, the polythiol compound used for generating an addition reaction product with a silane coupling agent is preferably a polythiol compound having two or more thiol groups in one molecule, such as ethanedithiol, propanedithiol, Aliphatic polythiols such as hexamethylene dithiol, decamethylene dithiol, tolylene-2,4-dithiol; aromatic polythiols such as xylene dithiol; diglycol dimercaptan, triglycol dimercaptan, tetraglycol dimercaptan, thiodiglycol dimercaptan, Cyclic rings such as thiotriglycol dimercaptan, thiotetraglycol dimercaptan, trimethylolpropane tris-β-mercaptopropionate, 1,4-dithiane ring-containing polythiol compound Fido compounds. These polythiol compounds may be used alone or in combination of two or more.
[0012]
In the present invention, the polyene compound used for generating an addition reaction product with a silane coupling agent is preferably a polyene compound having two or more carbon-carbon double bonds in one molecule. Examples include allyl alcohol derivatives, esters of acrylic acid or methacrylic acid and polyhydric alcohols, urethane acrylates, divinylbenzene, and the like. These polyene compounds may be used alone or in combination of two or more.
[0013]
Specific examples of allyl alcohol derivatives include, for example, triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl adipate, diallyl phthalate, triallyl trimellitate, tetraallyl pyromellitate, glyceryl diallyl ether, trimethylolpropane Examples include diallyl ether, pentaerythritol, diallyl ether and the like. These allyl alcohol derivatives may be used alone or in combination of two or more.
[0014]
Examples of the polyhydric alcohol used in esters of acrylic acid or methacrylic acid and polyhydric alcohol include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylol. Examples include propane, pentaerythritol, sorbitol and the like. These polyhydric alcohols may be used alone or in combination of two or more.
[0015]
Of the various polyene compounds, allyl alcohol derivatives are preferably used, and among them, triallyl cyanurate and triallyl isocyanurate are more preferably used.
[0016]
In the present invention, the polythiol compound and the polyene compound may be used alone, but it is more preferable that both are used in combination. Moreover, when both are used together, at least one of both should just produce | generate the addition reaction product with a silane coupling agent.
[0017]
In the present invention, as a monomer having two or more functional groups in one molecule used for generating an addition reaction product with a silane coupling agent, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, bisphenol A diethoxydi (meth) ) Acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaene Sri Tall hexa (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate. These monomers may be used independently and 2 or more types may be used together.
[0018]
Moreover, in this invention, as an oligomer which has a 2 or more functional group in 1 molecule used in order to produce | generate an addition reaction product with a silane coupling agent, urethane acrylate, epoxy acrylate, polyester acrylate etc. are mentioned, for example. Can be mentioned. These oligomers may be used alone or in combination of two or more.
[0019]
The monomer and oligomer having two or more functional groups in one molecule may be used alone or in combination.
[0020]
In the present invention, as the above-mentioned polythiol compound or polyene compound, or a silane coupling agent used for generating an addition reaction product with a monomer or oligomer having two or more functional groups in one molecule, for example, Unsaturated group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ- Glycidyl group-containing silane coupling agents such as glycidoxypropyltriethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl ) .Gamma.-amino group-containing silane coupling agents such as aminopropyltriethoxysilane; .gamma.-mercaptopropyltrimethoxysilane, a mercapto group-containing silane coupling agents such as .gamma.-mercaptopropyl triethoxy silane. These silane coupling agents may be used alone or in combination of two or more.
[0021]
The addition reaction method of the polythiol compound or polyene compound, or a monomer or oligomer having two or more functional groups in one molecule and the silane coupling agent is not special, and in the presence or absence of a solvent. The desired addition reaction product can be obtained by performing an addition reaction at a reaction temperature of about 40 to 120 ° C. at a reaction temperature of about 40 to 120 ° C. under normal pressure or under reduced pressure, for example, using benzoyl peroxide as a reaction catalyst. I can do it.
[0022]
The photocurable resin composition of the present invention contains the addition reaction product as an essential component, but the addition reaction product and the polythiol compound or polyene compound are not subjected to addition reaction with a silane coupling agent. Alternatively, one or two or more monomers or oligomers having two or more functional groups in one molecule may be contained.
[0023]
The photocurable resin composition of the present invention contains a photopolymerization initiator in order to induce and accelerate the photocuring reaction.
[0024]
Examples of the photopolymerization initiator include benzophenone photopolymerization initiators such as benzophenone, p-aminobenzophenone, p, p'-dimethylaminobenzophenone, methyl orthobenzoylbenzoate and 4-benzoyl-4'-methyldiphenyl sulfide. Acetophenone, benzaldehyde, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, oligo [ Acetophenone photopolymerization initiators such as 2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone]; benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether Ether photopolymerization initiators; azo photopolymerization initiators such as 2,2′-azobisisobutyronitrile; diazo photopolymerization initiator compounds such as diazoaminobenzene, 4,4′-diazidostilbene-p -Phenylenebisazide, isopropylthioxanthone, diethylthioxanthone, acylphosphine oxide, benzyl, camphorquinone, anthraquinone, Michler's ketone and the like. These photoinitiators may be used independently and 2 or more types may be used together.
[0025]
In the photocurable resin composition of the present invention, the amount of the photopolymerization initiator used is not particularly limited, but is 100 parts by weight of the addition reaction product or the addition reaction product and silane coupling. The photopolymerization initiator is 0.0001 per 100 parts by weight of the total amount of the polythiol compound or polyene compound not subjected to addition reaction with the agent, or the monomer or oligomer having two or more functional groups in one molecule. It is preferable that it is -10 weight part, More preferably, it is 0.05-5 weight part.
[0026]
In the photocurable resin composition of the present invention, in addition to the addition reaction product and the photopolymerization initiator, which are essential components, a urethane-based oligomer and an acrylic-based material are necessary as long as they do not hinder achievement of the present invention. One or more of various oligomers such as an oligomer, an epoxy-based oligomer, a polyester-based oligomer, and a rubber-based oligomer may be contained.
[0027]
In addition to the addition reaction product and the photopolymerization initiator, which are essential components, the photocurable resin composition of the present invention has an adhesion improver as necessary within a range that does not hinder the achievement of the present invention. 1 type, or 2 or more types of various additives, such as an antioxidant, a heat stabilizer, a polymerization inhibitor, a filler, a coloring agent, a thixotropic agent, a hardening accelerator, a plasticizer, and a surfactant, are contained. May be.
[0028]
Next, the liquid crystal inlet sealing agent of the present invention is composed of the above-described photocurable resin composition of the present invention. In order to use the photocurable resin composition of the present invention as a liquid crystal inlet sealing agent, first, two transparent plates with transparent electrodes such as an ITO thin film are opposed to each other with an appropriate spacer therebetween. Then, the periphery is sealed with an appropriate sealing body leaving a liquid crystal injection port, thereby forming a cell. As said sealing body, an epoxy resin, a polyimide resin, etc. are mentioned, for example.
[0029]
Next, after injecting liquid crystal into the cell from the liquid crystal injection port, the liquid crystal injection port is closed with a liquid crystal injection port sealing agent, and this is irradiated with actinic rays to seal the liquid crystal injection port (photocurable resin composition). Is cured. By using such a method, the liquid crystal injection port can be effectively sealed without hindrance.
[0030]
Examples of the liquid crystal include various commonly used liquid crystals such as nematic liquid crystal, cholesteric liquid crystal, and smectic liquid crystal, and are preferably used.
[0031]
In addition, examples of the active light for curing the liquid crystal injection port sealant (photo-curable resin composition) include, for example, ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, and ultraviolet light using a metal halide lamp as a light source. And various actinic rays are preferably used.
[0032]
By irradiation with the actinic ray, the liquid crystal inlet sealing agent made of the photocurable resin composition of the present invention is similar to the liquid crystal inlet sealing agent made of a conventional polyene / polythiol-based photocurable resin composition, for example. It can be cured in a short time from several seconds to several minutes, and the liquid crystal injection port can be effectively sealed without hindrance.
[0033]
Therefore, the liquid crystal display cell of the present invention can be manufactured through the above steps.
[0034]
[Action]
The photocurable resin composition of the present invention includes an addition reaction product of a polythiol compound or a polyene compound and a silane coupling agent, or a monomer or oligomer having two or more functional groups in one molecule and a silane coupling agent. Therefore, it exhibits excellent adhesion (sealing force). Further, since the addition reaction product has a high molecular weight, it does not elute into the liquid crystal, and therefore does not cause alignment failure of the liquid crystal.
[0035]
In addition, since the liquid crystal inlet sealing agent of the present invention is composed of the above-mentioned photocurable resin composition, it exhibits excellent adhesive force (sealing power) and does not elute into the liquid crystal, and therefore the liquid crystal is poorly aligned. It is a high performance thing that does not come.
[0036]
Furthermore, the liquid crystal display cell of the present invention has a liquid crystal inlet sealed with the above-mentioned liquid crystal inlet sealing agent, so that it has an excellent sealing property for a long period of time and causes poor alignment of the liquid crystal. High performance without anything
[0037]
DETAILED DESCRIPTION OF THE INVENTION
In order to describe the present invention in more detail, examples are given below, but the present invention is not limited to these examples. In the examples, “part” means “part by weight”.
[0038]
Example 1
[0039]
(1) Preparation of photocurable resin composition (liquid crystal inlet sealing agent) 174 parts of tolylene diisocyanate were charged in a separable beaker and heated to 50 ° C., and then 130 parts of 2-hydroxypropyl acrylate was added therein. It dripped over 1 hour and made it react, Furthermore, 74 parts of n-butanol was dripped over about 30 minutes, and it was made to react, and the urethane oligomer was synthesize | combined.
[0040]
To 30 parts of trimethylolpropane tris-β-mercaptopropionate as a polythiol compound, 4 parts of γ-methacryloxypropyltrimethoxysilane as a silane coupling agent and 0.03 part of benzoyl peroxide (BPO) as a reaction catalyst are added. The mixture was mixed and reacted at 80 ° C. to synthesize an addition reaction product of a polythiol compound and a silane coupling agent.
[0041]
To 34 parts of the addition reaction product obtained above, 44 parts of the urethane oligomer synthesized above, 20 parts of triallyl isocyanurate as a polyene compound and 2 parts of benzyl dimethyl ketal as a photopolymerization initiator are added and mixed uniformly. Then, a photocurable resin composition (liquid crystal injection port sealing agent) was produced.
[0042]
(Example 2)
To 20 parts of triallyl isocyanurate as a polyene compound, 4 parts of γ-mercaptopropyltrimethoxysilane as a silane coupling agent and 0.03 part of BPO as a reaction catalyst are mixed and reacted at 80 ° C. An addition reaction product with a coupling agent was synthesized.
[0043]
44 parts of the urethane oligomer synthesized in Example 1 with respect to 24 parts of the addition reaction product obtained above, 30 parts of trimethylolpropane tris-β-mercaptopropionate as a polythiol compound, and benzyldimethyl ketal 2 as a photopolymerization initiator Part was added and uniformly heated and mixed to prepare a photocurable resin composition (liquid crystal injection port sealing agent).
[0044]
(Example 3)
To 50 parts of pentaerythritol tetraacrylate as a monomer having two or more functional groups in one molecule, 4 parts of γ-mercaptopropyltrimethoxysilane as a silane coupling agent and 0.03 part of BPO as a reaction catalyst are added and mixed. By reacting at 80 ° C., an addition reaction product of a monomer having two or more functional groups in one molecule and a silane coupling agent was synthesized.
[0045]
44 parts of the urethane oligomer synthesized in Example 1 and 2 parts of benzyl dimethyl ketal as a photopolymerization initiator were added to 54 parts of the addition reaction product obtained above, and the mixture was uniformly heated and mixed to obtain a photocurable resin composition. A product (liquid crystal inlet sealing agent) was prepared.
[0046]
(Comparative Example 1)
In preparation of a photocurable resin composition (liquid crystal inlet sealing agent), 30 parts of a polythiol compound (trimethylolpropane tris-β-mercaptopropionate) and a silane coupling agent (γ-methacryloxypropyltrimethoxysilane) A photocurable resin composition (liquid crystal inlet sealing agent) was produced in the same manner as in Example 1 except that 4 parts were not added and simply added and mixed.
[0047]
(Comparative Example 2)
In the production of the photocurable resin composition (liquid crystal inlet sealing agent), the same as in Example 1 except that no silane coupling agent (γ-methacryloxypropyltrimethoxysilane) was added, A photocurable resin composition (liquid crystal inlet sealing agent) was produced.
[0048]
(Comparative Example 3)
In the preparation of a photocurable resin composition (liquid crystal inlet sealing agent), 50 parts of a monomer (pentaerythritol tetraacrylate) having two or more functional groups in one molecule and a silane coupling agent (γ-mercaptopropyltri) A photocurable resin composition (liquid crystal inlet sealing agent) was prepared in the same manner as in Example 3 except that 4 parts of methoxysilane) were not added and mixed, but simply added and mixed.
[0049]
The performance ((1) tensile adhesive force, (2) liquid crystal alignment disorder) of the photocurable resin compositions (liquid crystal inlet sealing agent) obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was measured as follows. It was evaluated with. The results are shown in Table 1.
[0050]
(1) Tensile adhesive force: About 1 mg of a photocurable resin composition (liquid crystal inlet sealing agent) was applied to one glass plate of 20 mm × 60 mm × 8 mm, and the other glass plate of the same size was overlapped in a cross Thereafter, the film was adhered by being irradiated with ultraviolet rays having a light intensity of 3000 mj / cm 2 . Next, this adhesive was set on a flat tensile tester, and a flat tensile test was performed at a tensile speed of 5 mm / min to measure the tensile adhesive force. The measurement was performed three times, and the average value was taken as the tensile adhesive force (kg / cm 2 ).
[0051]
(2) Disturbance of alignment of liquid crystal: alignment treatment {alignment film: product name “8034” (manufactured by JSR), then rubbing} is applied to the center of one 50 mm × 50 mm substrate. (Liquid crystal inlet sealant) 1 drop and 1 drop of liquid crystal {trade name “JC-5004LA” (manufactured by Chisso)} are dropped on the other substrate of the same size in the direction of 90 degrees open cell Was made. Next, the interface between the photocurable resin composition (liquid crystal inlet sealing agent) and the liquid crystal was observed with a polarizing microscope, and the width (mm) of the region where the alignment of the liquid crystal was disturbed was measured.
[0052]
[Table 1]
As is apparent from Table 1, the photocurable resin compositions (liquid crystal inlet sealing agents) of Examples 1 to 3 according to the present invention are all excellent in adhesive force (sealing force) and aligned with liquid crystal. The disturbance was small.
[0054]
On the other hand, the photocurable resin composition of Comparative Example 1 (liquid crystal inlet sealing agent) simply added without causing an addition reaction between the polythiol compound and the silane coupling agent had good adhesive strength, The alignment disorder of the liquid crystal was large.
[0055]
Further, the photocurable resin composition of Comparative Example 2 (liquid crystal injection port sealing agent) to which no silane coupling agent was added had extremely low adhesive force, although the liquid crystal alignment disorder was small.
[0056]
Furthermore, the photocurable resin composition of Comparative Example 3 (liquid crystal inlet sealing agent) simply added without causing an addition reaction between a monomer having two or more functional groups in one molecule and a silane coupling agent is: The alignment disorder of the liquid crystal was extremely large and the adhesive strength was low.
[0057]
【The invention's effect】
As described above, the photocurable resin composition according to the present invention exhibits an excellent adhesive force (sealing force) and does not elute into the liquid crystal, and therefore does not cause poor alignment of the liquid crystal. Suitable for obtaining performance liquid crystal inlet sealant.
[0058]
In addition, since the liquid crystal inlet sealing agent according to the present invention is composed of the above-mentioned photocurable resin composition, it exhibits excellent adhesive force (sealing force) and does not elute into the liquid crystal, and therefore the liquid crystal is poorly aligned. The liquid crystal display cell is suitably used for sealing the inlet of a liquid crystal display cell.
[0059]
Furthermore, the liquid crystal display cell according to the present invention has a liquid crystal injection port sealed with the liquid crystal injection port sealing agent, so that it has an excellent sealing property for a long period of time and causes poor alignment of the liquid crystal. High performance without anything Therefore, it is suitably used as a liquid crystal display cell for various applications in which the liquid crystal display cell is used.
Claims (4)
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| Application Number | Priority Date | Filing Date | Title |
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| JP26602999A JP4268284B2 (en) | 1999-09-20 | 1999-09-20 | Photocurable resin composition, liquid crystal inlet sealing agent and liquid crystal display cell |
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| Application Number | Priority Date | Filing Date | Title |
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| JP26602999A JP4268284B2 (en) | 1999-09-20 | 1999-09-20 | Photocurable resin composition, liquid crystal inlet sealing agent and liquid crystal display cell |
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| JP2001089568A JP2001089568A (en) | 2001-04-03 |
| JP4268284B2 true JP4268284B2 (en) | 2009-05-27 |
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