JP7472792B2 - Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element - Google Patents
Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- JP7472792B2 JP7472792B2 JP2020539573A JP2020539573A JP7472792B2 JP 7472792 B2 JP7472792 B2 JP 7472792B2 JP 2020539573 A JP2020539573 A JP 2020539573A JP 2020539573 A JP2020539573 A JP 2020539573A JP 7472792 B2 JP7472792 B2 JP 7472792B2
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- liquid crystal
- irradiation
- crystal alignment
- carbon atoms
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 177
- 238000000034 method Methods 0.000 title claims description 55
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- 239000000758 substrate Substances 0.000 claims description 63
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 17
- 125000002723 alicyclic group Chemical group 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
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- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 9
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- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229940094941 isoamyl butyrate Drugs 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IPLONMMJNGTUAI-UHFFFAOYSA-M lithium;bromide;hydrate Chemical compound [Li+].O.[Br-] IPLONMMJNGTUAI-UHFFFAOYSA-M 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- VNRDAMBPFDPXSM-UHFFFAOYSA-N n'-[2-(3-triethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCNCCN VNRDAMBPFDPXSM-UHFFFAOYSA-N 0.000 description 1
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- OKRNLSUTBJUVKA-UHFFFAOYSA-N n,n,n',n'-Tetrakis(2-hydroxyethyl)adipamide Chemical compound OCCN(CCO)C(=O)CCCCC(=O)N(CCO)CCO OKRNLSUTBJUVKA-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- ICWPRFNZEBFLPT-UHFFFAOYSA-N n-(2-hydroxyphenyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=CC=C1O ICWPRFNZEBFLPT-UHFFFAOYSA-N 0.000 description 1
- KIQBVKPQYARZTK-UHFFFAOYSA-N n-(2-hydroxyphenyl)prop-2-enamide Chemical compound OC1=CC=CC=C1NC(=O)C=C KIQBVKPQYARZTK-UHFFFAOYSA-N 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- YGRMNBNGHHDGCX-UHFFFAOYSA-N n-(ethoxymethyl)-2-methylprop-2-enamide Chemical compound CCOCNC(=O)C(C)=C YGRMNBNGHHDGCX-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 1
- ILRLVKWBBFWKTN-UHFFFAOYSA-N n-benzyl-3-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCC1=CC=CC=C1 ILRLVKWBBFWKTN-UHFFFAOYSA-N 0.000 description 1
- CLYWMXVFAMGARU-UHFFFAOYSA-N n-benzyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC1=CC=CC=C1 CLYWMXVFAMGARU-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OHPZPBNDOVQJMH-UHFFFAOYSA-N n-ethyl-4-methylbenzenesulfonamide Chemical compound CCNS(=O)(=O)C1=CC=C(C)C=C1 OHPZPBNDOVQJMH-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- HVYCQBKSRWZZGX-UHFFFAOYSA-N naphthalen-1-yl 2-methylprop-2-enoate Chemical compound C1=CC=C2C(OC(=O)C(=C)C)=CC=CC2=C1 HVYCQBKSRWZZGX-UHFFFAOYSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 125000002971 oxazolyl group Chemical group 0.000 description 1
- ZADZUSCZHASNAH-UHFFFAOYSA-N oxetan-3-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1COC1 ZADZUSCZHASNAH-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- JCMFJIHDWDKYIL-UHFFFAOYSA-N propyl 3-methoxypropanoate Chemical compound CCCOC(=O)CCOC JCMFJIHDWDKYIL-UHFFFAOYSA-N 0.000 description 1
- JTTWNTXHFYNETH-UHFFFAOYSA-N propyl 4-methylbenzenesulfonate Chemical compound CCCOS(=O)(=O)C1=CC=C(C)C=C1 JTTWNTXHFYNETH-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical group C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 125000002345 steroid group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ONXYYBNZRHGVOC-UHFFFAOYSA-N thiiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CS1 ONXYYBNZRHGVOC-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- KYWIYKKSMDLRDC-UHFFFAOYSA-N undecan-2-one Chemical compound CCCCCCCCCC(C)=O KYWIYKKSMDLRDC-UHFFFAOYSA-N 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本発明は、液晶配向剤を用いる液晶配向膜の製造方法、これにより得られる液晶配向膜、及び得られた液晶配向膜を具備する液晶表示素子に関する。さらに詳しくは、特定の液晶配向剤を用いることにより得られる、焼成温度が低く、焼成時間が短い場合においても、液晶配向性が良好であり、プレチルト角発現能にも優れ、且つ高い信頼性が得られるとともに、プレチルト角の上書きが可能である液晶配向膜、および特定の液晶配向剤を用いる、表示品位に優れるマルチドメイン液晶配向膜の製造方法、マルチドメイン液晶配向膜及び液晶表示素子に関する。The present invention relates to a method for producing a liquid crystal alignment film using a liquid crystal aligning agent, a liquid crystal alignment film obtained by the method, and a liquid crystal display element having the liquid crystal alignment film obtained. More specifically, the present invention relates to a liquid crystal alignment film obtained by using a specific liquid crystal aligning agent, which has good liquid crystal alignment properties even when the baking temperature is low and the baking time is short, has excellent pretilt angle expression ability, and is highly reliable and allows the pretilt angle to be overwritten, and to a method for producing a multi-domain liquid crystal alignment film using a specific liquid crystal aligning agent and has excellent display quality, a multi-domain liquid crystal alignment film, and a liquid crystal display element.
液晶表示素子において、液晶配向膜は液晶を一定の方向に配向させるという役割を担っている。現在、工業的に使用されている主な液晶配向膜は、ポリイミド前駆体であるポリアミド酸(ポリアミック酸ともいわれる)、ポリアミック酸エステルや、ポリイミドの溶液からなるポリイミド系の液晶配向剤を、基板に塗布し成膜することで作製される。
また、基板面に対して液晶を平行配向又は傾斜配向させる場合は、成膜した後、更にラビングによる表面延伸処理が行われている。
In liquid crystal display elements, the role of the liquid crystal alignment film is to align the liquid crystal in a certain direction. Currently, the main liquid crystal alignment films used industrially are produced by coating a substrate with a polyimide-based liquid crystal alignment agent made of a polyimide precursor such as polyamide acid (also called polyamic acid), polyamic acid ester, or a polyimide solution, and forming a film.
Furthermore, when the liquid crystal is to be aligned parallel or inclined to the substrate surface, a surface stretching treatment by rubbing is further carried out after the film formation.
一方、基板に対して垂直に液晶を配向させる場合(垂直配向(VA)方式と呼ばれる)は、長鎖アルキルや環状基又は環状基とアルキル基の組み合わせ(例えば特許文献1参照)、ステロイド骨格(例えば特許文献2参照)などの疎水性基をポリイミドの側鎖に導入した液晶配向膜が用いられている。この場合、基板間に電圧を印加して液晶分子が基板に平行な方向に向かって傾く際に、液晶分子が基板法線方向から基板面内の一方向に向かって傾くようにする必要がある。このための手段として、例えば、基板上に突起を設ける方法、表示用電極にスリットを設ける方法、ラビングにより液晶分子を基板法線方向から基板面内の一方向に向けてわずかに傾けておく(プレチルトさせる)方法、さらには、あらかじめ液晶組成物中に光重合性化合物を添加し、ポリイミド等の垂直配向膜と共に用いて、液晶セルに電圧を印加しながら紫外線を照射することで、液晶をプレチルトさせる方法(例えば、特許文献3参照)などが提案されている。On the other hand, when the liquid crystal is aligned perpendicular to the substrate (called the vertical alignment (VA) method), a liquid crystal alignment film is used in which hydrophobic groups such as long-chain alkyl, cyclic groups, or combinations of cyclic groups and alkyl groups (see, for example, Patent Document 1), or steroid skeletons (see, for example, Patent Document 2) are introduced into the side chains of polyimide. In this case, when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, it is necessary to make the liquid crystal molecules tilt from the substrate normal direction toward one direction in the substrate plane. As a means for this, for example, a method of providing protrusions on the substrate, a method of providing slits in the display electrode, a method of slightly tilting the liquid crystal molecules from the substrate normal direction toward one direction in the substrate plane by rubbing (pretilting), and a method of adding a photopolymerizable compound to the liquid crystal composition in advance, using it together with a vertical alignment film such as polyimide, and applying a voltage to the liquid crystal cell while irradiating ultraviolet light to pretilt the liquid crystal (see, for example, Patent Document 3) have been proposed.
近年、VA方式の液晶配向制御における突起やスリットの形成、及びPSA技術に代わるものとして偏光紫外線照射等による異方的光化学反応を利用する方法(光配向法)も提案されている。すなわち、光反応性を有する垂直配向性のポリイミド膜に、偏光紫外線照射し、配向規制能およびプレチルト角発現性を付与することにより、電圧印加時の液晶分子の傾き方向を均一に制御できることが知られている(特許文献4参照)。この場合も、従来の配向膜と同様に、耐久性に優れ、液晶のプレチルト角の制御に好適なポリイミド系の液晶配向膜が用いられている。ポリイミド系液晶配向膜は200℃以上の高温で焼成されることが一般的である。In recent years, a method (photo-alignment method) that utilizes anisotropic photochemical reactions by irradiation with polarized ultraviolet light, etc., has been proposed as an alternative to the formation of protrusions and slits in the VA method of liquid crystal alignment control and the PSA technology. That is, it is known that the tilt direction of liquid crystal molecules when a voltage is applied can be uniformly controlled by irradiating a photo-reactive vertical alignment polyimide film with polarized ultraviolet light to impart alignment control ability and pretilt angle expression ability (see Patent Document 4). In this case, too, a polyimide-based liquid crystal alignment film that is highly durable and suitable for controlling the pretilt angle of liquid crystals is used, as with conventional alignment films. Polyimide-based liquid crystal alignment films are generally baked at high temperatures of 200°C or higher.
一方、液晶表示素子の基板を、薄くて軽量であるプラスチック基板を用いる検討も精力的になされている。この場合、プラスチック基板の耐熱性が低いため、液晶配向膜を作製する際の焼成を、より低温で行うことが必要になる。同様に、この焼成温度を低温にすることで、液晶表示素子の製造におけるエネルギーコストを削減することも求められている。On the other hand, there is also active research being done on using thin and lightweight plastic substrates as the substrates for liquid crystal display elements. In this case, because plastic substrates have low heat resistance, it is necessary to carry out the baking process at a lower temperature when producing the liquid crystal alignment film. Similarly, there is a demand to reduce the energy costs involved in manufacturing liquid crystal display elements by lowering the baking temperature.
低温での焼成を行った場合、配向膜材料が充分に硬化しない状態で硬化を終了せざるを得ないといった課題があり、信頼性の高い液晶表示素子を得ることが困難であった(例えば、特許文献5参照)。When baking is performed at low temperatures, there is a problem that the curing must be terminated before the alignment film material is sufficiently cured, making it difficult to obtain a highly reliable liquid crystal display element (see, for example, Patent Document 5).
一方、配向方向が異なる領域を複数形成(配向分割)するマルチドメイン化技術の需要が高まっているが、従来の製造法においては、複数の開口部を所定間隔で設けた露光マスクを用いて露光した後に、所定間隔分だけ露光マスクをずらして再度露光する必要があり、露光マスクのアライメントや複数の開口部の形成に高精度が要求され、製造工程が煩雑であり、改善が求められている。ここで、光分解型のポリイミドに垂直配向性基が結合したポリマーを用いるマルチドメイン液晶表示素子の製造方法が知られているが、非常に大きな光照射量が必要であり、製造効率が悪い(例えば、特許文献6、7及び8参照)。マルチドメイン配向膜の製造方法の例はさらに存在するが、どのような配向膜を用いれば発明が実施可能となるかが明らかではなかった(例えば、特許文献9参照)。On the other hand, there is an increasing demand for multi-domain technology that forms multiple regions with different alignment directions (alignment division). In conventional manufacturing methods, after exposure using an exposure mask with multiple openings at a predetermined interval, it is necessary to shift the exposure mask by a predetermined interval and expose again, which requires high precision in aligning the exposure mask and forming multiple openings, making the manufacturing process complicated and requiring improvement. Here, a method for manufacturing a multi-domain liquid crystal display element using a polymer in which a vertical alignment group is bonded to a photodegradable polyimide is known, but it requires a very large amount of light irradiation and is inefficient in manufacturing (see, for example, Patent Documents 6, 7 and 8). There are further examples of methods for manufacturing a multi-domain alignment film, but it was not clear what kind of alignment film would be used to implement the invention (see, for example, Patent Document 9).
本発明は、少ないマスク処理工程で、より簡便に、配向方向が異なる領域を複数形成(配向分割)し、視野角特性に優れたVAモード液晶表示素子およびその製造方法を提供することを目的とする。
また、本発明の目的は、上記目的に加えて、向上した視野角特性を有するECB液晶表示素子及び該素子のための液晶配向膜を提供することにある。
An object of the present invention is to provide a VA mode liquid crystal display element having excellent viewing angle characteristics by more simply forming a plurality of regions with different alignment directions (alignment division) with fewer masking steps, and a method for manufacturing the same.
In addition to the above object, another object of the present invention is to provide an ECB liquid crystal display element having improved viewing angle characteristics and a liquid crystal alignment film for said element.
本発明者らは、以下の<X>を要旨とする発明を見出した。
<X> (A)成分として下記式(pa-1)で表される光配向性基と熱架橋性基Aとを有する重合体及び溶媒を含有するとともに、下記要件Z1及びZ2の少なくとも一方を満たす液晶配向剤を基板上に塗布し、乾燥及び焼成により硬化膜を形成する工程、
当該硬化膜に紫外線を斜め方向から照射する1回目の照射工程、並びに、
当該紫外線照射後の硬化膜に、当該1回目の照射工程とは異なる方向から紫外線照射を行う2回目の照射工程をこの順番で含み、
当該1回目の照射工程と2回目の照射工程の少なくとも一方は、遮光された領域と遮光されていない領域とを含むマスクを介して行われることを特徴とする、マルチドメイン液晶配向膜の製造方法。
Z1:(A)成分である重合体が、熱架橋性基Bをさらに有する。
Z2:(B)成分として、分子内に2個以上の熱架橋性基Bを有する化合物をさらに含有する。
The present inventors have discovered the invention having the following gist <X>.
<X> A process of coating a liquid crystal aligning agent containing, as component (A), a polymer having a photoalignment group represented by the following formula (pa-1) and a thermal crosslinking group A, and a solvent, and satisfying at least one of the following requirements Z1 and Z2, on a substrate, and then drying and baking the resulting mixture to form a cured film;
a first irradiation step of irradiating the cured film with ultraviolet light from an oblique direction; and
a second irradiation step of irradiating the cured film after the ultraviolet irradiation with ultraviolet rays from a direction different from that of the first irradiation step, in this order;
At least one of the first irradiation step and the second irradiation step is performed through a mask including a light-shielded region and a light-unshielded region.
Z1: The polymer which is the component (A) further has a thermally crosslinkable group B.
Z2: The component (B) further contains a compound having two or more thermally crosslinkable groups B in the molecule.
式中、Aは場合によりフッ素、塩素、シアノから選択される基によるか、又は炭素数1~5のアルコキシ基、直鎖状若しくは分岐鎖状のアルキル残基(これは、場合により1個のシアノ基又は1個以上のハロゲン原子で置換されている)で置換されている、ピリミジン-2,5-ジイル、ピリジン-2,5-ジイル、2,5-チオフェニレン、2,5-フラニレン、1,4-若しくは2,6-ナフチレン又はフェニレンを表し、R1は単結合、酸素原子、-COO-または-OCO-であり、R2は2価の芳香族基、2価の脂環式基、2価の複素環式基または2価の縮合環式基であり、R3は単結合、酸素原子、-COO-または-OCO-であり、R4は炭素数1~40の直鎖又は分岐鎖のアルキル基または脂環式基を含む炭素数3~40の1価の有機基であり、Dは、酸素原子、硫黄原子又は-NRd-(ここで、Rdは、水素原子又は炭素数1~3のアルキルを表す)を表し、aは0~3の整数であり、*は結合位置を表す。
熱架橋性基A及び熱架橋性基Bは、それぞれ独立に、カルボキシル基、アミノ基、アルコキシメチルアミド基、ヒドロキシメチルアミド基、水酸基、エポキシ部位含有基、オキセタニル基、チイラニル基、イソシアネート基及びブロックイソシアネート基からなる群から選ばれる有機基であって、熱架橋性基Aと熱架橋性基Bとが熱により架橋反応するように選択されてなり、ただし、熱架橋性基A及び熱架橋性基Bは互いに同じでもよい。
In the formula, A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene or phenylene, which is optionally substituted with a group selected from fluorine, chlorine, cyano, or with an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl residue, which is optionally substituted with one cyano group or one or more halogen atoms; R 1 represents a single bond, an oxygen atom, -COO- or -OCO-; R 2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group; R 3 represents a single bond, an oxygen atom, -COO- or -OCO-; R 4 represents a monovalent organic group having 3 to 40 carbon atoms, which contains a linear or branched alkyl group or an alicyclic group having 1 to 40 carbon atoms; D represents an oxygen atom, a sulfur atom or -NR d- (wherein R d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), a is an integer of 0 to 3, and * represents the bonding position.
The thermally crosslinkable group A and the thermally crosslinkable group B are each independently an organic group selected from the group consisting of a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a blocked isocyanate group, and are selected so that the thermally crosslinkable group A and the thermally crosslinkable group B undergo a crosslinking reaction by heat, however, the thermally crosslinkable group A and the thermally crosslinkable group B may be the same as each other.
本発明により、少ないマスク処理工程で、より簡便に、配向方向が異なる領域を複数形成(配向分割)し、視野角特性に優れたVAモード液晶表示素子を提供することができる。The present invention makes it possible to more easily form multiple regions with different alignment directions (alignment division) with fewer mask processing steps, thereby providing a VA mode liquid crystal display element with excellent viewing angle characteristics.
本発明のマルチドメイン液晶配向膜の製造方法は、(A)成分として上記式(pa-1)で表される光配向性基と熱架橋性基Aとを有する重合体及び溶媒を含有するとともに、下記要件Z1及びZ2の少なくとも一方を満たす液晶配向剤を基板上に塗布し、乾燥及び焼成により硬化膜を形成する工程、
当該硬化膜に紫外線を斜め方向から照射する1回目の照射工程、並びに、
当該紫外線照射後の硬化膜に、当該1回目の照射工程とは異なる方向から紫外線照射を行う2回目の照射工程をこの順番で含み、
当該1回目の照射工程と2回目の照射工程の少なくとも一方は、遮光された領域と遮光されていない領域とを含むマスクを介して行われることを特徴とする、マルチドメイン液晶配向膜の製造方法。
Z1:(A)成分である重合体が、熱架橋性基Bをさらに有する。
Z2:(B)成分として、分子内に2個以上の熱架橋性基Bを有する化合物をさらに含有する。
熱架橋性基A及び熱架橋性基Bは、それぞれ独立に、カルボキシル基、アミノ基、アルコキシメチルアミド基、ヒドロキシメチルアミド基、水酸基、エポキシ部位含有基、オキセタニル基、チイラニル基、イソシアネート基及びブロックイソシアネート基からなる群から選ばれる有機基であって、熱架橋性基Aと熱架橋性基Bとが熱により架橋反応するように選択されてなり、ただし、熱架橋性基A及び熱架橋性基Bは互いに同じでもよい。
The method for producing a multi-domain liquid crystal alignment film of the present invention includes the steps of: applying a liquid crystal alignment agent containing a polymer having a photoalignment group represented by the above formula (pa-1) and a thermal crosslinking group A as component (A) and a solvent, and satisfying at least one of the following requirements Z1 and Z2, onto a substrate; and drying and baking the liquid crystal alignment agent to form a cured film.
a first irradiation step of irradiating the cured film with ultraviolet light from an oblique direction; and
a second irradiation step of irradiating the cured film after the ultraviolet irradiation with ultraviolet rays from a direction different from that of the first irradiation step, in this order;
At least one of the first irradiation step and the second irradiation step is performed through a mask including a light-shielded region and a light-unshielded region.
Z1: The polymer which is the component (A) further has a thermally crosslinkable group B.
Z2: The component (B) further contains a compound having two or more thermally crosslinkable groups B in the molecule.
The thermally crosslinkable group A and the thermally crosslinkable group B are each independently an organic group selected from the group consisting of a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a blocked isocyanate group, and are selected so that the thermally crosslinkable group A and the thermally crosslinkable group B undergo a crosslinking reaction by heat, however, the thermally crosslinkable group A and the thermally crosslinkable group B may be the same as each other.
ここで、「分子内に2個以上」とは、例えばエポキシ基を2個以上など、同種の基を2個以上、分子内に含有する場合の他、例えばエポキシ基とチイラン基という組合せのように、異種の基を合計2個以上、分子内に含有する場合をも含む意である。「分子内に2個以上」は、好ましくは、同種の基を2個以上、分子内に含有するのがよい。Here, "two or more in a molecule" refers to cases where the molecule contains two or more groups of the same type, such as two or more epoxy groups, as well as cases where the molecule contains a total of two or more different groups, such as a combination of an epoxy group and a thiirane group. "Two or more in a molecule" preferably refers to the molecule containing two or more groups of the same type.
本発明の液晶配向剤中に含有される(A)成分である重合体は、光に対して感度が高いため、低露光量の偏光紫外線照射においても、配向制御能を発現できる。The polymer, which is component (A) contained in the liquid crystal alignment agent of the present invention, is highly sensitive to light, and can therefore exhibit alignment control ability even when exposed to low exposure amounts of polarized ultraviolet light.
また、(A)成分である重合体が熱架橋性基Aを含有するとともに、さらに熱架橋性基Bを成分中に含有することによって、液晶配向剤の焼成時間が短い場合でも(A)成分である重合体を含む架橋反応が可能となる。これにより、光配向性部位が光反応により異方性を発現した際に、液晶配向膜に異方性が残存(メモリー)しやすくなるため、液晶配向性を高め、且つ液晶のプレチルト角を発現することが可能となる。 In addition, by containing a thermal crosslinkable group A in the polymer (A) and further containing a thermal crosslinkable group B in the component, a crosslinking reaction involving the polymer (A) is possible even if the baking time of the liquid crystal alignment agent is short. As a result, when the photo-alignable portion exhibits anisotropy due to a photoreaction, the anisotropy tends to remain (memory) in the liquid crystal alignment film, making it possible to enhance the liquid crystal alignment and exhibit a pretilt angle of the liquid crystal.
なお、上記式(pa-1)で表される光配向性基を有する部位(例えば、後述の式(a-1)で表される基)、熱架橋性基A及び熱架橋性基Bは、いずれも重合体における側鎖になりうるものであることから、必要に応じて、「側鎖」と言い換えることもできる。
以下、本発明の各構成要件、につき詳述する。
In addition, the moiety having a photoalignable group represented by the above formula (pa-1) (for example, a group represented by the formula (a-1) described later), the thermally crosslinkable group A, and the thermally crosslinkable group B can all be side chains in a polymer, and therefore can be referred to as "side chains" as necessary.
Each of the constituent elements of the present invention will be described in detail below.
<(A)成分:特定重合体>
[式(pa-1)で表される光配向性基]
本発明において、分子内に上記式(pa-1)で表される光配向性を有する部位は、例えば下記式(a-1)で表すことができる。また、該部位は、下記式(a-1-m)で表されるモノマー由来の構造を挙げることができるがこれに限定されない。式中、Iaは、下記式(pa-1)で表される1価の有機基である。
<Component (A): Specific Polymer>
[Photoalignment group represented by formula (pa-1)]
In the present invention, the moiety having photoalignment property represented by the above formula (pa-1) in the molecule can be represented by, for example, the following formula (a-1). In addition, the moiety can be a structure derived from a monomer represented by the following formula (a-1-m), but is not limited thereto. In the formula, Ia is a monovalent organic group represented by the following formula (pa-1).
式(pa-1)中、Aは場合によりフッ素、塩素、シアノから選択される基によるか、又は炭素数1~5のアルコキシ基、直鎖状若しくは分岐鎖状のアルキル残基(これは、場合により1個のシアノ基又は1個以上のハロゲン原子で置換されている)で置換されている、ピリミジン-2,5-ジイル、ピリジン-2,5-ジイル、2,5-チオフェニレン、2,5-フラニレン、1,4-若しくは2,6-ナフチレン又はフェニレンを表し、R1は単結合、酸素原子、-COO-または-OCO-であり、R2は2価の芳香族基、2価の脂環式基、2価の複素環式基または2価の縮合環式基であり、R3は単結合、酸素原子、-COO-または-OCO-であり、R4は炭素数1~40の直鎖又は分岐鎖のアルキル基または脂環式基を含む炭素数3~40の1価の有機基であり、Dは、酸素原子、硫黄原子又は-NRd-(ここで、Rdは、水素原子又は炭素数1~3のアルキルを表す)を表し、aは0~3の整数であり、*はSaとの結合位置を表す。 In formula (pa-1), A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene or phenylene, which is optionally substituted with a group selected from fluorine, chlorine or cyano, or with an alkoxy group having 1 to 5 carbon atoms, a linear or branched alkyl residue (which is optionally substituted with one cyano group or one or more halogen atoms); R 1 represents a single bond, an oxygen atom, -COO- or -OCO-; R 2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group; R 3 represents a single bond, an oxygen atom, -COO- or -OCO-; R 4 is a monovalent organic group having 3 to 40 carbon atoms containing a linear or branched alkyl group or an alicyclic group having 1 to 40 carbon atoms; D is an oxygen atom, a sulfur atom, or -NR d - (wherein R d is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms); a is an integer of 0 to 3; and * represents the bonding position with S a .
上記式(a-1)又は(a-1-m)中、Saは、スペーサー単位を表し、Saの左の結合基は、第1及び第2の特定重合体の主鎖に、任意にスペーサーを介して結合することを示す。 In the above formula (a-1) or (a-1-m), S a represents a spacer unit, and the bonding group to the left of S a indicates that it is bonded to the main chains of the first and second specific polymers, optionally via a spacer.
Saは、例えば下記式(Sp)の構造で表すことができる。 S a can be represented, for example, by the structure of the following formula (Sp).
式(Sp)中、
W1の左の結合はMbへの結合を表し、
W3の右の結合はIaへの結合を表し、
W1、W2及びW3は、それぞれ独立して、単結合、二価の複素環、-(CH2)n-(式中、nは1~20を表す)、-OCH2-、-CH2O-、―COO-、-OCO-、-CH=CH-、-CF=CF-、-CF2O-、-OCF2-、-CF2CF2-又は-C≡C-を表すが、これらの置換基において非隣接のCH2基の一つ以上は独立して、-O-、-CO-、-CO-O-、-O-CO-、-Si(CH3)2-O-Si(CH3)2―、-NR-、-NR-CO-、-CO-NR-、-NR-CO-O-、-OCO-NR-、-NR-CO-NR-、-CH=CH-、-C≡C-又は-O-CO-O-(式中、Rは独立して水素又は炭素原子数1から5の直鎖又は分岐鎖のアルキル基を表す)で置換することができ、
A1及びA2は、それぞれ独立して、単結合、2価のアルキル基、2価の芳香族基、2価の脂環式基、又は2価の複素環式基から選ばれる基であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良い。
In formula (Sp),
The left bond of W1 represents a bond to Mb ;
the right bond of W3 represents a bond to Ia ;
W 1 , W 2 and W 3 each independently represent a single bond, a divalent heterocycle, -(CH 2 ) n - (wherein n is 1 to 20), -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CH═CH-, -CF═CF-, -CF 2 O-, -OCF 2 -, -CF 2 CF 2 - or -C≡C-, provided that one or more non-adjacent CH 2 groups in these substituents are independently -O-, -CO-, -CO-O-, -O-CO-, -Si(CH 3 ) 2 -O-Si(CH 3 ) 2 may be substituted by —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —OCO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— or —O—CO—O— (wherein R independently represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms);
A1 and A2 each independently represent a group selected from a single bond, a divalent alkyl group, a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group, and each of these groups may be unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group.
式(a-1-m)中、Maは重合性基を表す。該重合性基として、(メタ)アクリレート、フマレート、マレエート、α-メチレン-γ-ブチロラクトン、スチレン、ビニル、マレイミド、ノルボルネン、(メタ)アクリルアミド及びその誘導体のラジカル重合性基、及びシロキサンを挙げることができる。好ましくは(メタ)アクリレート、α-メチレン-γ-ブチロラクトン、スチレン、ビニル、マレイミド、アクリルアミドであるのがよい。
rは、1≦r≦3を満たす整数である。
In formula (a-1-m), M a represents a polymerizable group. Examples of the polymerizable group include radical polymerizable groups of (meth)acrylate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, (meth)acrylamide and derivatives thereof, and siloxane. Preferred are (meth)acrylate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, and acrylamide.
r is an integer satisfying 1≦r≦3.
式(a-1-m)中、Mbは、単結合、(r+1)価の複素環、炭素数1~10の直鎖状又は分岐状アルキル基、(r+1)価の芳香族基、(r+1)価の脂環式基から選ばれる基であり、それぞれの基は無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良い。 In formula (a-1-m), Mb is a group selected from a single bond, a (r+1)-valent heterocycle, a linear or branched alkyl group having 1 to 10 carbon atoms, a (r+1)-valent aromatic group, and a (r+1)-valent alicyclic group, each of which is unsubstituted or has one or more hydrogen atoms substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group.
A1、A2、及びMbにおける芳香族基としては、例えば、ベンゼン、ビフェニル、ナフタレンのような炭素数6~18の芳香族炭化水素を挙げることができる。A1、A2、及びMbにおける脂環式基としては、例えばシクロヘキサン、ビシクロヘキサンのような炭素数6~12の脂環式炭化水素を挙げることができる。A1、A2、及びMbにおける複素環としては、例えばピリジン、ピペリジン、ピペラジン等の窒素含有複素環を挙げることができる。A1、A2におけるアルキル基としては、炭素数1~10の直鎖状又は分岐状アルキル基等を挙げることができる。 Examples of the aromatic groups in A 1 , A 2 and M b include aromatic hydrocarbons having 6 to 18 carbon atoms, such as benzene, biphenyl and naphthalene. Examples of the alicyclic groups in A 1 , A 2 and M b include alicyclic hydrocarbons having 6 to 12 carbon atoms, such as cyclohexane and bicyclohexane. Examples of the heterocycles in A 1 , A 2 and M b include nitrogen-containing heterocycles, such as pyridine, piperidine and piperazine. Examples of the alkyl groups in A 1 and A 2 include linear or branched alkyl groups having 1 to 10 carbon atoms.
良好な垂直配向制御能と安定なプレチルト角を発現し得る観点から、(a-1)の構造として、上記(pa-1)で表される基、又は、下記(pa-1-a)で表される基を挙げることができる。また、該部位は、下記式(pa-1-ma)で表されるモノマー由来の構造を挙げることができるがこれに限定されない。From the viewpoint of being able to realize good vertical alignment control ability and a stable pretilt angle, examples of the structure of (a-1) include the group represented by (pa-1) above or the group represented by (pa-1-a) below. In addition, examples of the moiety include, but are not limited to, a structure derived from a monomer represented by the following formula (pa-1-ma).
式(pa-1-a)又は(pa-1-ma)中、Ma、Mb、及びSaは、上述と同じ定義である。
Zは酸素原子、または硫黄原子である。
Xa及びXbは、それぞれ独立して水素原子、フッ素原子、塩素原子、シアノ基又は炭素数1~3のアルキル基である。
R1は単結合、酸素原子、-COO-または-OCO-である。
R2は2価の芳香族基、2価の脂環式基、又は2価の複素環式基である。
R3は単結合、酸素原子、-COO-または-OCO-である。
R4は炭素数1~40の直鎖又は分岐鎖のアルキル基または脂環式基を含む炭素数3~40の1価の有機基である。
R5は炭素数1~3のアルキル基、炭素数1~3のアルコキシ基、フッ素原子またはシアノ基、好ましくはメチル基、メトキシ基又はフッ素原子である。
aは0~3の整数であり、bは0~4の整数である。
In the formula (pa-1-a) or (pa-1-ma), M a , M b , and S a are defined as above.
Z is an oxygen atom or a sulfur atom.
Xa and Xb each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms.
R 1 is a single bond, an oxygen atom, -COO- or -OCO-.
R2 is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group.
R3 is a single bond, an oxygen atom, -COO- or -OCO-.
R4 is a monovalent organic group having 3 to 40 carbon atoms which contains a linear or branched alkyl group having 1 to 40 carbon atoms or an alicyclic group.
R5 is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, preferably a methyl group, a methoxy group or a fluorine atom.
a is an integer from 0 to 3; b is an integer from 0 to 4.
式(pa-1-a)又は(pa-1-ma)中、Saの炭素数1~10の直鎖又は分岐鎖のアルキレン基として、炭素数1~8の直鎖又は分岐鎖のアルキレン基であることが好ましく、例えばメチレン基、エチレン基、n-プロピレン基、n-ブチレン基、t-ブチレン基、n-ペンチレン基、n-ヘキシレン基、n-ヘプチレン基、n-オクチレン基が好ましい。 In formula (pa-1-a) or (pa-1-ma), the linear or branched alkylene group having 1 to 10 carbon atoms for Sa is preferably a linear or branched alkylene group having 1 to 8 carbon atoms, and for example, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a t-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, or an n-octylene group is preferable.
Saの2価の芳香族基として、例えば1,4-フェニレン基、2-フルオロ-1,4-フェニレン基、3-フルオロ-1,4-フェニレン基、2,3,5,6-テトラフルオロ-1,4-フェニレン基等を挙げることができる。 Examples of the divalent aromatic group for S a include a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, and a 2,3,5,6-tetrafluoro-1,4-phenylene group.
Saの2価の脂環式基として、例えばトランス-1,4-シクロヘキシレン、トランス-トランス-1,4-ビシクロヘキシレン等を挙げることができる。 Examples of the divalent alicyclic group for S a include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene.
Saの2価の複素環式基として、例えば1,4-ピリジレン基、2,5-ピリジレン基、1,4-フラニレン基、1,4-ピペラジン基、1,4-ピペリジン基等を挙げることができる。 Examples of the divalent heterocyclic group for S a include a 1,4-pyridylene group, a 2,5-pyridylene group, a 1,4-furanylene group, a 1,4-piperazine group, and a 1,4-piperidine group.
Saは、炭素数1~8のアルキレン基であることが好ましく、より好ましくは炭素数1~6のアルキレン基であり、さらに好ましくは炭素数1~4のアルキレン基であるのがよい。 S a is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
R2の2価の芳香族基として、例えば1,4-フェニレン基、2-フルオロ-1,4-フェニレン基、3-フルオロ-1,4-フェニレン基、2,3,5,6-テトラフルオロ-1,4-フェニレン基、ナフチレン基等を挙げることができる。 Examples of the divalent aromatic group for R2 include a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 2,3,5,6-tetrafluoro-1,4-phenylene group, and a naphthylene group.
R2の2価の脂環式基として、例えばトランス1,4-シクロヘキシレン、トランス-トランス-1,4-ビシクロヘキシレン等を挙げることができる。 Examples of the divalent alicyclic group of R2 include trans 1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene.
R2の2価の複素環式基として、例えば1,4-ピリジレン基、2,5-ピリジレン基、1,4-フラニレン基、1,4-ピペラジン基、1,4-ピペリジン基等を挙げることができる。 Examples of the divalent heterocyclic group for R2 include a 1,4-pyridylene group, a 2,5-pyridylene group, a 1,4-furanylene group, a 1,4-piperazine group, and a 1,4-piperidine group.
R2は、1,4-フェニレン基、トランス1,4-シクロヘキシレン、トランス-トランス-1,4-ビシクロヘキシレンであるのがよい。 R2 may be a 1,4-phenylene group, trans 1,4-cyclohexylene, or trans-trans-1,4-bicyclohexylene.
R4の炭素数1~40の直鎖又は分岐鎖のアルキル基としては、例えば炭素数1~20の直鎖又は分岐鎖のアルキル基を挙げることができ、このアルキル基の水素原子の一部または全部はフッ素原子により置換されていてもよい。かかるアルキル基の例としては、例えばメチル基、エチル基、n-プロピル、n-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基、n-ラウリル基、n-ドデシル基、n-トリデシル基、n-テトラデシル基、n-ペンタデシル基、n-ヘキサデシル基、n-ヘプタデシル基、n-オクタデシル基、n-ノナデシル基、n-エイコシル基、4,4,4-トリフロロブチル基、4,4,5,5,5-ペンタフルオロペンチル、4,4,5,5,6,6,6-ヘプタフルオロヘキシル基、3,3,4,4,5,5,5-ヘプタフルオロペンチル基、2,2,2-トリフルオロエチル基、2,2,3,3,3-ペンタフルオロプロピル基、2-(パーフルオロブチル)エチル基、2-(パーフルオロオクチル)エチル基、2-(パーフルオロデシル)エチル基等を挙げることができる。 The linear or branched alkyl group having 1 to 40 carbon atoms for R 4 may be, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms. Examples of such alkyl groups include, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-lauryl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, and 4,4,4 -trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 2-(perfluorooctyl)ethyl group, and 2-(perfluorodecyl)ethyl group.
R4の脂環式基を含む炭素数3~40の1価の有機基としては、例えばコレステニル基、コレスタニル基、アダマンチル基、下記式(Alc-1)または(Alc-2)(式中、R7は、それぞれ、水素原子、フッ素原子または炭素数1~20のアルキル基であり、炭素数1~20のアルキル基はフッ素原子で置換されていてもよく、*は結合位置を示す)で表される基等を挙げることができる。 Examples of the monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group for R4 include a cholestenyl group, a cholestanylic group, an adamantyl group, and a group represented by the following formula (Alc-1) or (Alc-2) (wherein R7 is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a fluorine atom, and * indicates a bonding position).
上記式(pa-1-ma)で表されるモノマーとして、式(paa-1-ma1)~(paa-1-ma18)で表される構造を挙げることができるがこれらに限定されない。なお、式中、「E」は、E体であることを表し、「t」は、シクロヘキシル基がトランス型であることを表す。 Examples of the monomer represented by the above formula (paa-1-ma) include, but are not limited to, structures represented by formulas (paa-1-ma1) to (paa-1-ma18). In the formula, "E" indicates that the monomer is an E-form, and "t" indicates that the cyclohexyl group is a trans-form.
[熱架橋性基A及び熱架橋性基B]
熱架橋性基A及び熱架橋性基Bは、それぞれ独立に、カルボキシル基、アミノ基、アルコキシメチルアミド基、ヒドロキシメチルアミド基、水酸基、エポキシ部位含有基、オキセタニル基、チイラニル基、イソシアネート基及びブロックイソシアネート基からなる群から選ばれる有機基であって、熱架橋性基Aと熱架橋性基Bとが熱により架橋反応するように選択されてなり、ただし、熱架橋性基A及び熱架橋性基Bは互いに同じでもよい。
[Thermal crosslinkable group A and thermal crosslinkable group B]
The thermally crosslinkable group A and the thermally crosslinkable group B are each independently an organic group selected from the group consisting of a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a blocked isocyanate group, and are selected so that the thermally crosslinkable group A and the thermally crosslinkable group B undergo a crosslinking reaction by heat, however, the thermally crosslinkable group A and the thermally crosslinkable group B may be the same as each other.
このような熱架橋性基Aと熱架橋性基Bとの組み合わせとしては、一方がカルボキシル基であり、もう一方がエポキシ基、オキセタニル基またはチイラニル基である組み合わせ、一方がヒドロキシ基であり、他方がブロックイソシアネート基である組み合わせ、一方がフェノール性ヒドロキシ基であり、他方がエポキシ基、オキセタニル基またはチイラニル基である組み合わせ、一方がカルボキシル基であり、他方がブロックイソシアネート基である組み合わせ、一方がアミノ基であり、他方がブロックイソシアネート基である組み合わせ、両者がともにN-アルコキシメチルアミドである組み合わせなどである。より好ましい組み合わせは、カルボキシル基とエポキシ基、ヒドロキシ基とブロックイソシアネート基などである。 Such combinations of thermally crosslinkable groups A and B include a combination in which one is a carboxyl group and the other is an epoxy group, an oxetanyl group, or a thiiranyl group, a combination in which one is a hydroxyl group and the other is a blocked isocyanate group, a combination in which one is a phenolic hydroxyl group and the other is an epoxy group, an oxetanyl group, or a thiiranyl group, a combination in which one is a carboxyl group and the other is a blocked isocyanate group, a combination in which one is an amino group and the other is a blocked isocyanate group, a combination in which both are N-alkoxymethylamide, etc. More preferred combinations are a carboxyl group and an epoxy group, a hydroxyl group and a blocked isocyanate group, etc.
かかる熱架橋性基Aを(A)成分である重合体に導入するには、熱架橋性基Aを有するモノマーを共重合させればよい。To introduce such a thermally crosslinkable group A into the polymer, which is component (A), a monomer having a thermally crosslinkable group A may be copolymerized.
また、本発明に用いられる液晶配向剤が要件Z1を満足する場合、(A)成分である重合体を製造する際に、熱架橋性基Aを有するモノマーおよび熱架橋性基Bを有するモノマーの双方を共重合すればよい。 In addition, when the liquid crystal alignment agent used in the present invention satisfies requirement Z1, when producing the polymer which is component (A), both a monomer having a thermally crosslinkable group A and a monomer having a thermally crosslinkable group B may be copolymerized.
熱架橋性基を有するモノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、モノ-(2-(アクリロイルオキシ)エチル)フタレート、モノ-(2-(メタクリロイルオキシ)エチル)フタレート、N-(カルボキシフェニル)マレイミド、N-(カルボキシフェニル)メタクリルアミド、及びN-(カルボキシフェニル)アクリルアミド等のカルボキシル基を有するモノマー; Examples of monomers having a thermal crosslinkable group include monomers having a carboxyl group, such as acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide;
2-ヒドロキシエチルアクリレート、2-ヒドロキシエチルメタクリレート、2-ヒドロキシプロピルアクリレート、2-ヒドロキシプロピルメタクリレート、4-ヒドロキシブチルアクリレート、4-ヒドロキシブチルメタクリレート、2,3-ジヒドロキシプロピルアクリレート、2,3-ジヒドロキシプロピルメタクリレート、ジエチレングリコールモノアクリレート、ジエチレングリコールモノメタクリレート、カプロラクトン2-(アクリロイルオキシ)エチルエステル、カプロラクトン2-(メタクリロイルオキシ)エチルエステル、ポリ(エチレングリコール)エチルエーテルアクリレート、ポリ(エチレングリコール)エチルエーテルメタクリレート、5-アクリロイルオキシ-6-ヒドロキシノルボルネン-2-カルボキシリック-6-ラクトン、及び5-メタクリロイルオキシ-6-ヒドロキシノルボルネン-2-カルボキシリック-6-ラクトン等のヒドロキシ基を有するモノマー; Monomers having a hydroxy group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy)ethyl ester, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone;
ヒドロキシスチレン、N-(ヒドロキシフェニル)メタクリルアミド、N-(ヒドロキシフェニル)アクリルアミド、N-(ヒドロキシフェニル)マレイミド、及びN-(ヒドロキシフェニル)マレイミド等のフェノール性ヒドロキシ基を有するモノマー;Monomers having a phenolic hydroxy group, such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide;
アミノエチルアクリレート、アミノエチルメタクリレート、アミノプロピルアクリレート、及びアミノプロピルメタクリレート等のアミノ基を有するモノマー;Monomers having an amino group, such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate;
N-ヒドロキシメチル(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-エトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド等のヒドロキシメチル基又はアルコキシメチル基で置換された(メタ)アクリルアミド化合物; (Meth)acrylamide compounds substituted with hydroxymethyl groups or alkoxymethyl groups, such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide;
アリルグリシジルエーテル、アクリル酸グリシジル、メタクリル酸グリシジル、メタクリル酸2-メチルグリシジル、α-エチルアクリル酸グリシジル、α-n-プロピルアクリル酸グリシジル、α-n-ブチルアクリル酸グリシジル、アクリル酸3,4-エポキシブチル、メタクリル酸3,4-エポキシブチル、アクリル酸6,7-エポキシヘプチル、メタクリル酸6,7-エポキシヘプチル、α-エチルアクリル酸-6,7-エポキシヘプチル、o-ビニルベンジルグリシジルエーテル、m-ビニルベンジルグリシジルエーテル、p-ビニルベンジルグリシジルエーテル、メタクリル酸3,4-エポキシシクロへキシルメチル、3-エテニル-7-オキサビシクロ[4.1.0]ヘプタン、1,2-エポキシ-5-ヘキセン、1,7-オクタジエンモノエポキサイド等のエポキシ部位含有基を有するモノマー; Allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, and other monomers having an epoxy moiety-containing group;
3-(アクリロイルオキシメチル)オキセタン、3-(アクリロイルオキシメチル)-2-メチルオキセタン、3-(アクリロイルオキシメチル)-3-エチルオキセタン、3-(アクリロイルオキシメチル)-2-トリフルオロメチルオキセタン、3-(アクリロイルオキシメチル)-2-ペンタフルオロエチルオキセタン、3-(アクリロイルオキシメチル)-2-フェニルオキセタン、3-(アクリロイルオキシメチル)-2,2-ジフルオロオキセタン、3-(アクリロイルオキシメチル)-2,2,4-トリフルオロオキセタン、3-(アクリロイルオキシメチル)-2,2,4,4-テトラフルオロオキセタン、3-(2-アクリロイルオキシエチル)オキセタン、3-(2-アクリロイルオキシエチル)-2-エチルオキセタン、3-(2-アクリロイルオキシエチル)-3-エチルオキセタン、3-(2-アクリロイルオキシエチル)-2-トリフルオロメチルオキセタン、3-(2-アクリロイルオキシエチル)-2-ペンタフルオロエチルオキセタン、3-(2-アクリロイルオキシエチル)-2-フェニルオキセタン、3-(2-アクリロイルオキシエチル)-2,2-ジフルオロオキセタン、3-(2-アクリロイルオキシエチル)-2,2,4-トリフルオロオキセタン、3-(2-アクリロイルオキシエチル)-2,2,4,4-テトラフルオロオキセタン等のアクリル酸エステル;3-(メタクリロイルオキシメチル)オキセタン、3-(メタクリロイルオキシメチル)-2-メチルオキセタン、3-(メタクリロイルオキシメチル)-3-エチルオキセタン、3-(メタクリロイルオキシメチル)-2-トリフルオロメチルオキセタン、3-(メタクリロイルオキシメチル)-2-ペンタフルオロエチルオキセタン、3-(メタクリロイルオキシメチル)-2-フェニルオキセタン、3-(メタクリロイルオキシメチル)-2,2-ジフルオロオキセタン、3-(メタクリロイルオキシメチル)-2,2,4-トリフルオロオキセタン、3-(メタクリロイルオキシメチル)-2,2,4,4-テトラフルオロオキセタン、3-(2-メタクリロイルオキシエチル)オキセタン、3-(2-メタクリロイルオキシエチル)-2-エチルオキセタン、3-(2-メタクリロイルオキシエチル)-3-エチルオキセタン、3-(2-メタクリロイルオキシエチル)-2-トリフルオロメチルオキセタン、3-(2-メタクリロイルオキシエチル)-2-ペンタフルオロエチルオキセタン、3-(2-メタクリロイルオキシエチル)-2-フェニルオキセタン、3-(2-メタクリロイルオキシエチル)-2,2-ジフルオロオキセタン、3-(2-メタクリロイルオキシエチル)-2,2,4-トリフルオロオキセタン、3-(2-メタクリロイルオキシエチル)-2,2,4,4-テトラフルオロオキセタン等のオキセタニル基を有するモノマー; 3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2,2-difluorooxetane, 3-(acryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-acryloyloxyethyl)oxetane acrylic acid esters such as 3-(methacryloyloxyethyl)oxetane, 3-(2-acryloyloxyethyl)-2-ethyloxetane, 3-(2-acryloyloxyethyl)-3-ethyloxetane, 3-(2-acryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-acryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-acryloyloxyethyl)-2-phenyloxetane, 3-(2-acryloyloxyethyl)-2,2-difluorooxetane, 3-(2-acryloyloxyethyl)-2,2,4-trifluorooxetane, and 3-(2-acryloyloxyethyl)-2,2,4,4-tetrafluorooxetane; dimethyl)oxetane, 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-methacryloyloxyethyl)oxetane monomers having an oxetanyl group, such as oxetane, 3-(2-methacryloyloxyethyl)-2-ethyloxetane, 3-(2-methacryloyloxyethyl)-3-ethyloxetane, 3-(2-methacryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methacryloyloxyethyl)-2-phenyloxetane, 3-(2-methacryloyloxyethyl)-2,2-difluorooxetane, 3-(2-methacryloyloxyethyl)-2,2,4-trifluorooxetane, and 3-(2-methacryloyloxyethyl)-2,2,4,4-tetrafluorooxetane;
2,3-エピチオプロピルアクリレートまたはメタクリレート、及び2-または3―または4-(β-エピチオプロピルチオメチル)スチレン、2-または3―または4-(β-エピチオプロピルオキシメチル)スチレン、2-または3―または4-(β-エピチオプロピルチオ)スチレン、2-または3―または4-(β-エピチオプロピルオキシ)スチレン等のチイラニル基を有するモノマー; 2,3-epithiopropyl acrylate or methacrylate, and monomers having a thiiranyl group such as 2- or 3- or 4-(β-epithiopropylthiomethyl)styrene, 2- or 3- or 4-(β-epithiopropyloxymethyl)styrene, 2- or 3- or 4-(β-epithiopropylthio)styrene, and 2- or 3- or 4-(β-epithiopropyloxy)styrene;
アクリル酸2-(0-(1’-メチルプロピリデンアミノ)カルボキシアミノ)エチル、アクリル酸2-(3,5-ジメチルピラゾリル)カルボニルアミノ)エチル、メタクリル酸2-(0-(1’-メチルプロピリデンアミノ)カルボキシアミノ)エチル、メタクリル酸2-(3,5-ジメチルピラゾリル)カルボニルアミノ)エチル等のブロックイソシアネート基を有するモノマー;等が挙げられる。なお、(メタ)アクリルアミドとは、アクリルアミドとメタクリルアミドの双方を意味する。 Monomers having a blocked isocyanate group such as 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl acrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl acrylate, 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate, and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate; etc. Note that (meth)acrylamide refers to both acrylamide and methacrylamide.
また、本発明においては、特定共重合体を得る際に、上記式(a-1-m)で表される光配向性基を有するモノマー及び熱架橋性基A及び必要に応じて熱架橋性基Bを有するモノマーの他に、これらのモノマーと共重合可能なその他もモノマーを併用することができる。In addition, in the present invention, when obtaining the specific copolymer, in addition to the monomer having a photoalignable group represented by the above formula (a-1-m) and the monomer having a thermal crosslinkable group A and, if necessary, a thermal crosslinkable group B, other monomers copolymerizable with these monomers can be used in combination.
そのようなその他モノマーの具体例としては、アクリル酸エステル化合物、メタクリル酸エステル化合物、マレイミド化合物、アクリロニトリル、マレイン酸無水物、スチレン化合物、ビニル化合物、N-メトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、アクリルアミド等のアクリルアミド化合物、窒素含有芳香族複素環基と重合性基とを有するモノマーが挙げられる。 Specific examples of such other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, acrylamide compounds such as N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, and acrylamide, and monomers having a nitrogen-containing aromatic heterocyclic group and a polymerizable group.
アクリル酸エステル化合物としては、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、2,2,2-トリフルオロエチルアクリレート、tert-ブチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、2-メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、2-エトキシエチルアクリレート、テトラヒドロフルフリルアクリレート、3-メトキシブチルアクリレート、2-メチル-2-アダマンチルアクリレート、2-プロピル-2-アダマンチルアクリレート、8-メチル-8-トリシクロデシルアクリレート、及び、8-エチル-8-トリシクロデシルアクリレート等が挙げられる。Examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.
メタクリル酸エステル化合物としては、例えば、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ヘキサデシルメタクリレート、オクタデシルメタクリレート、ベンジルメタクリレート、ナフチルメタクリレート、アントリルメタクリレート、アントリルメチルメタクリレート、フェニルメタクリレート、2,2,2-トリフルオロエチルメタクリレート、tert-ブチルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、2-メトキシエチルメタクリレート、メトキシトリエチレングリコールメタクリレート、2-エトキシエチルメタクリレート、テトラヒドロフルフリルメタクリレート、3-メトキシブチルメタクリレート、2-メチル-2-アダマンチルメタクリレート、2-プロピル-2-アダマンチルメタクリレート、8-メチル-8-トリシクロデシルメタクリレート、及び、8-エチル-8-トリシクロデシルメタクリレート等が挙げられる。Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.
前記(メタ)アクリル酸アミド化合物としては、例えば、アクリルアミド、メタクリルアミド、N-メチルアクリルアミド、N,N-ジメチルアクリルアミド、N,N-ジエチルアクリルアミド等が挙げられる。 Examples of the (meth)acrylic acid amide compounds include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, etc.
前記ビニル化合物としては、例えば、メチルビニルエーテル、ベンジルビニルエーテル、ビニルナフタレン、ビニルカルバゾール、アリルグリシジルエーテル、及び3-エテニル-7-オキサビシクロ[4.1.0]ヘプタン等が挙げられる。 Examples of the vinyl compounds include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, and 3-ethenyl-7-oxabicyclo[4.1.0]heptane.
前記スチレン化合物としては、例えば、スチレン、メチルスチレン、クロロスチレン、及びブロモスチレン等が挙げられる。Examples of the styrene compounds include styrene, methylstyrene, chlorostyrene, and bromostyrene.
前記マレイミド化合物としては、例えば、マレイミド、N-メチルマレイミド、N-フェニルマレイミド、及びN-シクロヘキシルマレイミド等が挙げられる。 Examples of the maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
窒素含有芳香族複素環は、下記式[N-a]~[N-b](式中、Z2は炭素数1~5の直鎖または分岐アルキル基である)からなる群から選ばれる構造を少なくとも1個、好ましくは1個~4個含有する芳香族環式炭化水素であるのがよい。 The nitrogen-containing aromatic heterocycle is preferably an aromatic cyclic hydrocarbon having at least one, preferably 1 to 4, structures selected from the group consisting of the following formulas [Na] to [Nb] (wherein Z2 is a linear or branched alkyl group having 1 to 5 carbon atoms):
具体的には、オキサゾール環、チアゾール環、ピリジン環、ピリミジン環、キノリン環、1-ピラゾリン環、イソキノリン環、チアジアゾール環、ピリダジン環、トリアジン環、ピラジン環、フェナントロリン環、キノキサリン環、ベンゾチアゾール環、オキサジアゾール環、アクリジン環などを挙げることができる。さらに、これら窒素含有芳香族複素環の炭素原子には、ヘテロ原子を含む置換基を有していてもよい。これらのうち、例えば、ピリジン環が挙げられる。 Specific examples include an oxazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a 1-pyrazoline ring, an isoquinoline ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazine ring, a phenanthroline ring, a quinoxaline ring, a benzothiazole ring, an oxadiazole ring, and an acridine ring. Furthermore, the carbon atoms of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom. Among these, an example is a pyridine ring.
窒素含有芳香族複素環基と重合性基とを有するモノマーとして、例えば、2-(2-ピリジルカルボニルオキシ)エチル(メタ)アクリレート、2-(3-ピリジルカルボニルオキシ)エチル(メタ)アクリレート、2-(4-ピリジルカルボニルオキシ)エチル(メタ)アクリレート、等が挙げられる。Examples of monomers having a nitrogen-containing aromatic heterocyclic group and a polymerizable group include 2-(2-pyridylcarbonyloxy)ethyl (meth)acrylate, 2-(3-pyridylcarbonyloxy)ethyl (meth)acrylate, 2-(4-pyridylcarbonyloxy)ethyl (meth)acrylate, etc.
本発明に用いるその他のモノマーは1種類単独で用いてもよく、また2種以上のモノマーを組合せて用いてもよい。The other monomers used in the present invention may be used alone or in combination of two or more monomers.
本発明の重合体に含有させる上記式(pa-1)で表される光反応性の部位は1種類単独で用いてもよく、また2種以上の部位を組合せて用いてもよい。
上記式(pa-1)で表される光反応性の部位は、(A)成分である重合体の全繰り返し単位の5~50mol%、10~40mol%、又は15~35mol%の割合で含有されることが好ましい。
The photoreactive moiety represented by the above formula (pa-1) to be contained in the polymer of the present invention may be of one type alone or in combination of two or more types.
The photoreactive site represented by the above formula (pa-1) is preferably contained in a proportion of 5 to 50 mol %, 10 to 40 mol %, or 15 to 35 mol % of all repeating units of the polymer that is the component (A).
本発明の重合体に含有させる熱架橋性基を有する部位は熱架橋性基Aを単独で用いてもよく、また熱架橋性基Aと熱架橋性基Bを含む2種以上の部位を組合せて用いてもよい。
熱架橋性基を有する部位の導入量は、(A)成分である重合体の全繰り返し単位の50~95mol%、60~90mol%、又は65~85mol%であることが好ましい。
As the moiety having a thermal crosslinkable group to be contained in the polymer of the present invention, the thermal crosslinkable group A may be used alone, or two or more kinds of moieties containing the thermal crosslinkable group A and the thermal crosslinkable group B may be used in combination.
The amount of the site having a thermal crosslinkable group introduced is preferably 50 to 95 mol %, 60 to 90 mol %, or 65 to 85 mol % of all repeating units of the polymer which is the component (A).
上記その他のモノマー由来の構造の含有量は、(A)成分である重合体の全繰り返し単位の0~40mol%、0~30mol%、又は0~20mol%含まれることが好ましい。It is preferable that the content of the structures derived from the above-mentioned other monomers is 0 to 40 mol%, 0 to 30 mol%, or 0 to 20 mol% of the total repeating units of the polymer component (A).
<特定重合体の製造方法>
本発明の液晶配向剤に含有される(A)成分の特定重合体は、上記の式(pa-1)で表される光配向性基を有するモノマー、上記の熱架橋性基Aを有するモノマー、及び、所望により上記の熱架橋性基Bを有するモノマーを共重合することによって得られる。また、上記その他のモノマーと共重合することができる。
<Method of Producing Specific Polymer>
The specific polymer of the component (A) contained in the liquid crystal aligning agent of the present invention is obtained by copolymerizing a monomer having a photoaligning group represented by the above formula (pa-1), a monomer having the above thermal crosslinking group A, and, if desired, a monomer having the above thermal crosslinking group B. In addition, it can be copolymerized with the other monomers described above.
本発明における(A)成分の特定重合体の製造方法については、特に限定されるものではなく、工業的に扱われている汎用な方法が利用できる。具体的には、モノマーのビニル基を利用したカチオン重合やラジカル重合、アニオン重合により製造することができる。これらの中では反応制御のしやすさなどの観点からラジカル重合が特に好ましい。
ラジカル重合の重合開始剤としては、ラジカル重合開始剤や、可逆的付加-開裂型連鎖移動(RAFT)重合試薬等の公知の化合物を使用することができる。
The method for producing the specific polymer of the component (A) in the present invention is not particularly limited, and a general-purpose method that is used industrially can be used. Specifically, the specific polymer can be produced by cationic polymerization, radical polymerization, or anionic polymerization using the vinyl group of the monomer. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control.
As the polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators and reversible addition-fragmentation chain transfer (RAFT) polymerization agents can be used.
ラジカル熱重合開始剤は、分解温度以上に加熱することにより、ラジカルを発生させる化合物である。このようなラジカル熱重合開始剤としては、例えば、ケトンパーオキサイド類(メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド等)、ジアシルパーオキサイド類(アセチルパーオキサイド、ベンゾイルパーオキサイド等)、ハイドロパーオキサイド類(過酸化水素、tert-ブチルハイドパーオキサイド、クメンハイドロパーオキサイド等)、ジアルキルパーオキサイド類(ジ-tert-ブチルパーオキサイド、ジクミルパーオキサイド、ジラウロイルパーオキサイド等)、パーオキシケタール類(ジブチルパーオキシシクロヘキサン等)、アルキルパーエステル類(パーオキシネオデカン酸-tert-ブチルエステル、パーオキシピバリン酸-tert-ブチルエステル、パーオキシ 2-エチルシクロヘキサン酸-tert-アミルエステル等)、過硫酸塩類(過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等)、アゾ系化合物(アゾビスイソブチロニトリル、および2,2′-ジ(2-ヒドロキシエチル)アゾビスイソブチロニトリル等)が挙げられる。
このようなラジカル熱重合開始剤は、1種を単独で使用することもできるし、あるいは2種以上を組み合わせて使用することもできる。
The radical thermal polymerization initiator is a compound that generates radicals when heated to a temperature equal to or higher than its decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.).
Such radical thermal polymerization initiators can be used alone or in combination of two or more.
ラジカル光重合開始剤は、ラジカル重合を光照射によって開始する化合物であれば特に限定されない。このようなラジカル光重合開始剤としては、ベンゾフェノン、ミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、キサントン、チオキサントン、イソプロピルキサントン等、公知の化合物を挙げることができる。これらの化合物は単独で使用してもよく、2つ以上を混合して使用することもできる。
ラジカル重合法は、特に制限されるものでなく、乳化重合法、懸濁重合法、分散重合法、沈殿重合法、塊状重合法、溶液重合法等を用いることができる。
The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by irradiation with light. Examples of such radical photopolymerization initiators include known compounds such as benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, and isopropylxanthone. These compounds may be used alone or in combination of two or more.
The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method, etc. can be used.
(A)成分の特定重合体の重合反応に用いる溶媒としては、生成した高分子が溶解するものであれば特に限定されない。具体例としては、後述の<溶媒>の項に記載の溶媒、例えば、N-アルキル-2-ピロリドン類、ジアルキルイミダゾリジノン類、ラクトン類、カーボネート類、ケトン類、式(Sv-1)で表される化合物及び式(Sv-2)で表される化合物、テトラヒドロフラン、1,4-ジオキサン、ジメチルスルホン、ジメチルスルホキシド等が挙げられる。
これら溶媒は単独で使用しても、混合して使用してもよい。さらに、生成する高分子を溶解させない溶媒であっても、生成した高分子が析出しない範囲で、上述の溶媒に混合して使用してもよい。
また、ラジカル重合において溶媒中の酸素は重合反応を阻害する原因となるので、有機溶媒は可能な程度に脱気されたものを用いることが好ましい。
The solvent used in the polymerization reaction of the specific polymer of component (A) is not particularly limited as long as the generated polymer dissolves in the solvent. Specific examples include the solvents described in the section <Solvent> below, such as N-alkyl-2-pyrrolidones, dialkylimidazolidinones, lactones, carbonates, ketones, the compounds represented by formula (Sv-1) and formula (Sv-2), tetrahydrofuran, 1,4-dioxane, dimethyl sulfone, and dimethyl sulfoxide.
These solvents may be used alone or in combination. Furthermore, even if a solvent does not dissolve the polymer to be produced, it may be mixed with the above-mentioned solvent to the extent that the polymer to be produced does not precipitate.
In addition, since oxygen in a solvent in radical polymerization can inhibit the polymerization reaction, it is preferable to use an organic solvent that has been degassed to the greatest extent possible.
ラジカル重合の際の重合温度は30~150℃の任意の温度を選択することができるが、好ましくは50~100℃の範囲である。また、反応は任意の濃度で行うことができるが、モノマー濃度は、好ましくは1~50質量%、より好ましくは5~30質量%であるのがよい。反応初期は高濃度で行い、その後、有機溶媒を追加することができる。
上述のラジカル重合反応においては、ラジカル重合開始剤の比率がモノマーに対して多いと得られる高分子の分子量が小さくなり、少ないと得られる高分子の分子量が大きくなるので、ラジカル開始剤の比率は重合させるモノマーに対して0.1~10mol%であることが好ましい。また重合時には各種モノマー成分や溶媒、開始剤などを追加することもできる。
The polymerization temperature during radical polymerization can be selected from any temperature between 30 and 150° C., but is preferably in the range of 50 to 100° C. The reaction can be carried out at any concentration, but the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration in the early stage, and then an organic solvent can be added.
In the above-mentioned radical polymerization reaction, if the ratio of the radical polymerization initiator is high relative to the monomer, the molecular weight of the resulting polymer will be small, and if the ratio is low, the molecular weight of the resulting polymer will be large, so the ratio of the radical initiator is preferably 0.1 to 10 mol% relative to the monomer to be polymerized. In addition, various monomer components, solvents, initiators, etc. can also be added during polymerization.
[重合体の回収]
上述の反応により得られた反応溶液から、生成した高分子を回収する場合には、反応溶液を貧溶媒に投入して、それら重合体を沈殿させれば良い。沈殿に用いる貧溶媒としては、メタノール、アセトン、ヘキサン、ヘプタン、ブチルセルソルブ、ヘプタン、エタノール、トルエン、ベンゼン、ジエチルエーテル、メチルエチルエーテル、水等を挙げることができる。貧溶媒に投入して沈殿させた重合体は、濾過して回収した後、常圧あるいは減圧下で、常温あるいは加熱して乾燥することができる。また、沈殿回収した重合体を、有機溶媒に再溶解させ、再沈殿回収する操作を2回~10回繰り返すと、重合体中の不純物を少なくすることができる。この際の貧溶媒として、例えば、アルコール類、ケトン類、炭化水素等が挙げられ、これらの中から選ばれる3種類以上の貧溶媒を用いると、より一層精製の効率が上がるので好ましい。
[Polymer Recovery]
When recovering the polymer generated from the reaction solution obtained by the above-mentioned reaction, the reaction solution may be poured into a poor solvent to precipitate the polymer. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer precipitated by pouring into the poor solvent can be recovered by filtration, and then dried at room temperature or by heating under normal or reduced pressure. In addition, the polymer precipitated and recovered can be redissolved in an organic solvent and the reprecipitation and recovery operation can be repeated two to ten times to reduce impurities in the polymer. Examples of poor solvents in this case include alcohols, ketones, and hydrocarbons. It is preferable to use three or more poor solvents selected from these because the efficiency of purification is further improved.
(A)成分の特定重合体の分子量は、得られる塗膜の強度、塗膜形成時の作業性、および塗膜の均一性を考慮した場合、GPC(Gel Permeation Chromatography)法で測定した重量平均分子量が、2000~1000000が好ましく、より好ましくは、5000~100000である。The molecular weight of the specific polymer of component (A) is preferably a weight average molecular weight of 2,000 to 1,000,000, more preferably 5,000 to 100,000, measured by GPC (Gel Permeation Chromatography), taking into consideration the strength of the resulting coating film, the workability during coating film formation, and the uniformity of the coating film.
<(B)成分>
本発明に用いられる液晶配向剤が要件Z2を満たす場合には、(B)成分として架橋剤を含有する。(B)成分としては、熱架橋性基Bを2個以上有する架橋剤が挙げられる。
<Component (B)>
When the liquid crystal aligning agent used in the present invention satisfies the requirement Z2, it contains a crosslinking agent as the component (B). As the component (B), a crosslinking agent having two or more thermal crosslinkable groups B can be mentioned.
(B)成分である架橋剤としては、エポキシ化合物、アミノ基を2個以上有する化合物、メチロール化合物、イソシアネート化合物、フェノプラスト化合物、ブロックイソシアネート化合物等の低分子化合物、N-アルコキシメチルアクリルアミドの重合体、エポキシ基を有する化合物の重合体、イソシアネート基を有する化合物の重合体等の重合体が挙げられる。 Examples of the crosslinking agent, which is component (B), include low molecular weight compounds such as epoxy compounds, compounds having two or more amino groups, methylol compounds, isocyanate compounds, phenoplast compounds, and blocked isocyanate compounds, as well as polymers such as polymers of N-alkoxymethylacrylamide, polymers of compounds having epoxy groups, and polymers of compounds having isocyanate groups.
上述したエポキシ化合物の具体例としては、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、2,2-ジブロモネオペンチルグリコールジグリシジルエーテル、1,3,5,6-テトラグリシジル-2,4-ヘキサンジオール、N,N,N’,N’,-テトラグリシジル-m-キシレンジアミン、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、及びN,N,N’,N’-テトラグリシジル-4、4’-ジアミノジフェニルメタン等が挙げられる。Specific examples of the above-mentioned epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.
アミノ基を2個以上有する化合物の例としては、脂環式ジアミン、芳香族ジアミン、芳香族-脂肪族ジアミン、脂肪族ジアミン等のジアミンが挙げられる。Examples of compounds having two or more amino groups include diamines such as alicyclic diamines, aromatic diamines, aromatic-aliphatic diamines, and aliphatic diamines.
脂環式ジアミン類の例としては、1,4-ジアミノシクロヘキサン、1,3-ジアミノシクロヘキサン、4,4’-ジアミノジシクロヘキシルメタン、4,4’-ジアミノ-3,3’-ジメチルジシクロヘキシルアミン、イソホロンジアミン等が挙げられる。Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, isophoronediamine, etc.
芳香族ジアミン類の例としては、o-フェニレンジアミン、m-フェニレンジアミン、p-フェニレンジアミン、2,4-ジアミノトルエン、2,5-ジアミノトルエン、3,5-ジアミノトルエン、1,4-ジアミノ-2-メトキシベンゼン、2,5-ジアミノ-p-キシレンおよび1,3-ジアミノ-4-クロロベンゼンなどが挙げられる。Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, and 1,3-diamino-4-chlorobenzene.
芳香族-脂肪族ジアミンの例としては、3-アミノベンジルアミン、4-アミノベンジルアミン、3-アミノ-N-メチルベンジルアミン、4-アミノ-N-メチルベンジルアミン、3-アミノフェネチルアミン、4-アミノフェネチルアミン、3-アミノ-N-メチルフェネチルアミン、4-アミノ-N-メチルフェネチルアミン、3-(3-アミノプロピル)アニリン、4-(3-アミノプロピル)アニリン、3-(3-メチルアミノプロピル)アニリン、4-(3-メチルアミノプロピル)アニリン、3-(4-アミノブチル)アニリン、4-(4-アミノブチル)アニリン、3-(4-メチルアミノブチル)アニリン、4-(4-メチルアミノブチル)アニリン、3-(5-アミノペンチル)アニリン、4-(5-アミノペンチル)アニリン、3-(5-メチルアミノペンチル)アニリン、4-(5-メチルアミノペンチル)アニリン、2-(6-アミノナフチル)メチルアミン、3-(6-アミノナフチル)メチルアミン、2-(6-アミノナフチル)エチルアミン、3-(6-アミノナフチル)エチルアミンなどが挙げられる。Examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3-(3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3-(4-aminopropyl)aniline, 4 ... Examples of such amines include 4-(4-aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylaminobutyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl)aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, and 3-(6-aminonaphthyl)ethylamine.
脂肪族ジアミン類の例としては、1,2-ジアミノエタン、1,3-ジアミノプロパン、1,4-ジアミノブタン、1,5-ジアミノペンタン、1,6-ジアミノヘキサン、1,7-ジアミノヘプタン、1,8-ジアミノオクタン、1,9-ジアミノノナン、1,10-ジアミノデカン、1,3-ジアミノ-2,2-ジメチルプロパン、1,6-ジアミノ-2,5-ジメチルヘキサン、1,7-ジアミノ-2,5-ジメチルヘプタン、1,7-ジアミノ-4,4-ジメチルヘプタン、1,7-ジアミノ-3-メチルヘプタン、1,9-ジアミノ-5-メチルヘプタンなどが挙げられる。Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, and 1,9-diamino-5-methylheptane.
メチロール化合物の具体例としては、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、及びアルコキシメチル化メラミン等の化合物が挙げられる。 Specific examples of methylol compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
アルコキシメチル化グリコールウリルの具体例としては、例えば、1,3,4,6-テトラキス(メトキシメチル)グリコールウリル、1,3,4,6-テトラキス(ブトキシメチル)グリコールウリル、1,3,4,6-テトラキス(ヒドロキシメチル)グリコールウリル、1,3-ビス(ヒドロキシメチル)尿素、1,1,3,3-テトラキス(ブトキシメチル)尿素、1,1,3,3-テトラキス(メトキシメチル)尿素、1,3-ビス(ヒドロキシメチル)-4,5-ジヒドロキシ-2-イミダゾリノン、および1,3-ビス(メトキシメチル)-4,5-ジメトキシ-2-イミダゾリノン等が挙げられる。市販品として、三井サイテック(株)製グリコールウリル化合物(商品名:サイメル(登録商標)1170、パウダーリンク(登録商標)1174)等の化合物、メチル化尿素樹脂(商品名:UFR(登録商標)65)、ブチル化尿素樹脂(商品名:UFR(登録商標)300、U-VAN10S60、U-VAN10R、U-VAN11HV)、DIC(株)製尿素/ホルムアルデヒド系樹脂(高縮合型、商品名:ベッカミン(登録商標)J-300S、同P-955、同N)等が挙げられる。Specific examples of alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (product names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174), methylated urea resins (product names: UFR (registered trademark) 65), butylated urea resins (product names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea/formaldehyde resins (high condensation type, product names: Beckamin (registered trademark) J-300S, P-955, and N) manufactured by DIC Corporation.
アルコキシメチル化ベンゾグアナミンの具体例としては、例えば、テトラメトキシメチルベンゾグアナミン等が挙げられる。市販品として、三井サイテック(株)製(商品名:サイメル(登録商標)1123)、(株)三和ケミカル製(商品名:ニカラック(登録商標)BX-4000、同BX-37、同BL-60、同BX-55H)等が挙げられる。Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (product name: Cymel (registered trademark) 1123) and those manufactured by Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).
アルコキシメチル化メラミンの具体例としては、例えば、ヘキサメトキシメチルメラミン等が挙げられる。市販品として、三井サイテック(株)製メトキシメチルタイプメラミン化合物(商品名:サイメル(登録商標)300、同301、同303、同350)、ブトキシメチルタイプメラミン化合物(商品名:マイコート(登録商標)506、同508)、三和ケミカル製メトキシメチルタイプメラミン化合物(商品名:ニカラック(登録商標)MW-30、同MW-22、同MW-11、同MS-001、同MX-002、同MX-730、同MX-750、同MX-035)、ブトキシメチルタイプメラミン化合物(商品名:ニカラック(登録商標)MX-45、同MX-410、同MX-302)等が挙げられる。Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine. Commercially available products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (product names: Cymel (registered trademark) 300, 301, 303, and 350), butoxymethyl type melamine compounds (product names: Mycoat (registered trademark) 506 and 508), methoxymethyl type melamine compounds manufactured by Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, and MX-035), and butoxymethyl type melamine compounds (product names: Nikalac (registered trademark) MX-45, MX-410, and MX-302).
また、このようなアミノ基の水素原子がメチロール基又はアルコキシメチル基で置換されたメラミン化合物、尿素化合物、グリコールウリル化合物及びベンゾグアナミン化合物を縮合させて得られる化合物であってもよい。例えば、米国特許第6323310号に記載されているメラミン化合物およびベンゾグアナミン化合物から製造される高分子量の化合物が挙げられる。前記メラミン化合物の市販品としては、商品名:サイメル(登録商標)303(三井サイテック(株)製)等が挙げられ、前記ベンゾグアナミン化合物の市販品としては、商品名:サイメル(登録商標)1123(三井サイテック(株)製)等が挙げられる。 It may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound described in U.S. Pat. No. 6,323,310 may be mentioned. Commercially available products of the melamine compound include the product name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the benzoguanamine compound include the product name: Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).
イソシアネート化合物の具体例としては、例えば、VESTANAT B1358/100、VESTAGON BF 1540(以上、イソシアヌレート型変性ポリイソシアネート、デグサジャパン(株)製)、タケネート(登録商標)B-882N、同B-7075(以上、イソシアヌレート型変性ポリイソシアネート、三井化学(株)製)等が挙げられる。Specific examples of isocyanate compounds include VESTANAT B1358/100, VESTAGON BF 1540 (both are isocyanurate-type modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, Takenate B-7075 (both are isocyanurate-type modified polyisocyanates, manufactured by Mitsui Chemicals, Inc.), etc.
フェノプラスト化合物の具体例としては以下の化合物が挙げられるが、フェノプラスト化合物は以下の化合物例に限定されるものではない。 Specific examples of phenoplast compounds include the following compounds, but phenoplast compounds are not limited to the following compound examples.
前記分子末端にヒドロキシアルキルアミド基を2個以上有する化合物の具体的な例としては、例えば下記の化合物やPrimid XL-552、Primid SF-4510が挙げられる。 Specific examples of compounds having two or more hydroxyalkylamide groups at the molecular end include the following compounds, Primid XL-552, and Primid SF-4510.
ブロックイソシアネート化合物としては、例えば、コロネートAPステーブルM、コロネート2503、2515、2507、2513、2555、ミリオネートMS-50(以上、日本ポリウレタン工業(株)製)、タケネートB-830、B-815N、B-820NSU、B-842N、B-846N、B-870N、B-874N、B-882N(以上、三井化学(株)製)等を挙げることができる。Examples of blocked isocyanate compounds include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.), etc.
さらに、上述したN-アルコキシメチルアクリルアミドの重合体としては、例えば、N-ヒドロキシメチル(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-エトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド等のヒドロキシメチル基又はアルコキシメチル基で置換されたアクリルアミド化合物又はメタクリルアミド化合物を使用して製造されるポリマーが挙げられる。Furthermore, examples of the above-mentioned N-alkoxymethylacrylamide polymers include polymers produced using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl groups or alkoxymethyl groups, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide.
そのようなポリマーの具体例としては、例えば、ポリ(N-ブトキシメチルアクリルアミド)、N-ブトキシメチルアクリルアミドとスチレンとの共重合体、N-ヒドロキシメチルメタクリルアミドとメチルメタクリレートとの共重合体、N-エトキシメチルメタクリルアミドとベンジルメタクリレートとの共重合体、及びN-ブトキシメチルアクリルアミドとベンジルメタクリレートと2-ヒドロキシプロピルメタクリレートとの共重合体等が挙げられる。このようなポリマーの重量平均分子量は、1,000乃至200,000であり、より好ましくは3,000乃至150,000であり、さらに好ましくは3,000乃至50,000である。 Specific examples of such polymers include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. The weight average molecular weight of such polymers is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.
エポキシ基を有する化合物の重合体としては、例えば、グリシジルメタクリレート、3,4-エポキシシクロヘキシルメチルメタクリレート、3,4-エポキシシクロヘキシルメチルメタクリレート等のエポキシ基を有する化合物を使用して製造されるポリマーが挙げられる。Examples of polymers of compounds having epoxy groups include polymers produced using compounds having epoxy groups such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate.
そのようなポリマーの具体例としては、例えば、ポリ(3,4-エポキシシクロヘキシルメチルメタクリレート)、ポリ(グリシジルメタクリレート)、グリシジルメタクリレートとメチルメタクリレートとの共重合体、3,4-エポキシシクロヘキシルメチルメタクリレートとメチルメタクリレートとの共重合体、グリシジルメタクリレートとスチレンとの共重合体等が挙げられる。このようなポリマーの重量平均分子量は、1,000乃至200,000であり、より好ましくは3,000乃至150,000であり、さらに好ましくは3,000乃至50,000である。 Specific examples of such polymers include poly(3,4-epoxycyclohexylmethyl methacrylate), poly(glycidyl methacrylate), a copolymer of glycidyl methacrylate and methyl methacrylate, a copolymer of 3,4-epoxycyclohexylmethyl methacrylate and methyl methacrylate, a copolymer of glycidyl methacrylate and styrene, etc. The weight average molecular weight of such polymers is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.
上述したイソシアネート基を有する化合物の重合体としては、例えば、2-イソシアナトエチルメタクリレート(カレンズMOI[登録商標]、昭和電工(株)製)、2-イソシアナトエチルアクリレート(カレンズAOI[登録商標]、昭和電工(株)製)等のイソシアネート基を有する化合物、または2-(0-[1’-メチルプロピリデンアミノ]カルボキシアミノ)エチルメタクリレート(カレンズMOI-BM[登録商標]、昭和電工(株)製)、2-[(3,5-ジメチルピラゾリル)カルボニルアミノ]エチルメタクリレート(カレンズMOI-BP[登録商標]、昭和電工(株)製)等のブロックイソシアネート基を有する化合物を使用して製造されるポリマーが挙げられる。Examples of polymers of compounds having an isocyanate group as described above include polymers produced using compounds having an isocyanate group such as 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko K.K.) and 2-isocyanatoethyl acrylate (Karenz AOI [registered trademark], manufactured by Showa Denko K.K.), or compounds having a blocked isocyanate group such as 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karenz MOI-BM [registered trademark], manufactured by Showa Denko K.K.) and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko K.K.).
そのようなポリマーの具体例としては、例えば、ポリ(2-イソシアナトエチルアクリレート)、ポリ(2-(0-[1’-メチルプロピリデンアミノ]カルボキシアミノ)エチルメタクリレート)、2-イソシアナトエチルメタクリレートとスチレンとの共重合体、2-[(3,5-ジメチルピラゾリル)カルボニルアミノ]エチルメタクリレートとメチルメタクリレートとの共重合体等が挙げられる。このようなポリマーの重量平均分子量は、1,000乃至200,000であり、より好ましくは3,000乃至150,000であり、さらに好ましくは3,000乃至50,000である。 Specific examples of such polymers include poly(2-isocyanatoethyl acrylate), poly(2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate), a copolymer of 2-isocyanatoethyl methacrylate and styrene, and a copolymer of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and methyl methacrylate. The weight average molecular weight of such polymers is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.
これらの架橋剤は、単独で又は2種以上を組み合わせて使用することができる。These crosslinking agents can be used alone or in combination of two or more.
本発明に用いる液晶配向剤に(B)成分の架橋剤を含有させる場合の含有量は、(A)成分である樹脂の100質量部に基づいて1質量部乃至100質量部であることが好ましく、より好ましくは1質量部乃至80質量部である。When the liquid crystal alignment agent used in the present invention contains a crosslinking agent (B), the content is preferably 1 to 100 parts by mass based on 100 parts by mass of the resin (A), and more preferably 1 to 80 parts by mass.
[液晶配向剤の調製]
本発明に用いられる液晶配向剤は、液晶配向膜の形成に好適となるように塗布液として調製されることが好ましい。すなわち、本発明の液晶配向剤は、樹脂被膜を形成するための樹脂成分が有機溶媒に溶解した溶液として調製されることが好ましい。ここで、その樹脂成分とは、既に説明した(A)成分である特定重合体である。その際、特定重合体の含有量は、液晶配向剤全体に対して0.5~20質量%が好ましく、より好ましくは1~20質量%、さらに好ましくは1~15質量%、特に好ましくは1~10質量%であるのがよい。
[Preparation of liquid crystal alignment agent]
The liquid crystal aligning agent used in the present invention is preferably prepared as a coating liquid suitable for forming a liquid crystal alignment film. That is, the liquid crystal aligning agent of the present invention is preferably prepared as a solution in which a resin component for forming a resin coating is dissolved in an organic solvent. Here, the resin component is the specific polymer, which is the component (A) already explained. In this case, the content of the specific polymer is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, even more preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass, based on the entire liquid crystal aligning agent.
<溶媒>
本発明に用いられる液晶配向剤に含有する溶媒は、(A)成分及び必要に応じて有する(B)成分を溶解させる溶媒であれば特に限定されない。液晶配向剤に含有する溶媒は1種でも良く、2種類以上混合して使用しても良い。また、(A)成分や(B)成分を溶解させる溶媒でなくとも、(A)成分や(B)成分を溶解させる溶媒と併用することができる。この場合、(A)成分や(B)成分を溶解させない溶媒の表面エネルギーが(A)成分や(B)成分を溶解させる溶媒よりも低いと、液晶配向剤の基板への塗布性を良くすることができるため好ましい。
<Solvent>
The solvent contained in the liquid crystal alignment agent used in the present invention is not particularly limited as long as it dissolves the (A) component and the (B) component, if necessary. The solvent contained in the liquid crystal alignment agent may be one type, or two or more types may be mixed and used. In addition, even if the solvent does not dissolve the (A) component or the (B) component, it can be used in combination with a solvent that dissolves the (A) component or the (B) component. In this case, it is preferable that the surface energy of the solvent that does not dissolve the (A) component or the (B) component is lower than that of the solvent that dissolves the (A) component or the (B) component, because the liquid crystal alignment agent can be applied to the substrate with good properties.
具体例として、水、N-メチル-2-ピロリドン、N-エチル-2-ピロリドンなどのN-アルキル-2-ピロリドン類、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルカプロラクタム、テトラメチル尿素、3-メトキシ-N,N-ジメチルプロパンアミド、3-エトキシ-N,N-ジメチルプロパンアミド、3-ブトキシ-N,N-ジメチルプロパンアミド、1,3-ジメチル-2-イミダゾリジノンなどのジアルキルイミダゾリジノン類、γ-ブチロラクトン、γ-バレロラクトン、δ-バレロラクトンなどのラクトン類、エチレンカーボネート、プロピレンカーボネートなどのカーボネート類、メタノール、エタノール、プロパノール、イソプロパノール、3-メチル-3-メトキシブタノール、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、イソアミルメチルケトン、メチルイソプロピルケトン、ジイソブチルケトン、シクロヘキサノン、シクロペンタノン、メチルイソブチルケトン、4-ヒドロキシ-4-メチル-2-ペンタノンなどのケトン類、下記式(Sv-1)で表される化合物及び下記式(Sv-2)で表される化合物、酢酸4-メチル-2-ペンチル、酢酸2-エチルブチル、酢酸2-エチルヘキシル、酢酸シクロヘキシル、酢酸2-メチルシクロヘキシル、酪酸ブチル、酪酸イソアミル、ジイソブチルカルビノール、ジイソペンチルエーテル等をあげることができる。 Specific examples include water, N-alkyl-2-pyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam, tetramethylurea, dialkylimidazolidinones such as 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and 1,3-dimethyl-2-imidazolidinone, lactones such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone, carbonates such as ethylene carbonate and propylene carbonate, methanol, ethanol, and propanol. , isopropanol, 3-methyl-3-methoxybutanol, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone and other ketones, a compound represented by the following formula (Sv-1) and a compound represented by the following formula (Sv-2), 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isoamyl butyrate, diisobutyl carbinol, diisopentyl ether and the like.
式(Sv-1)~(Sv-2)中、Y1及びY2はそれぞれ独立に水素原子又は炭素数1~6の1価の炭化水素基であり、X1は酸素原子又は-COO-であり、X2は単結合又はカルボニル基であり、R1は炭素数2~4のアルカンジイル基である。n1は1~3の整数である。n1が2又は3の場合、複数のR1は同じでも異なっていてもよい。Z1は炭素数1~6の2価の炭化水素基であり、Y3及びY4はそれぞれ独立に水素原子又は炭素数1~6の1価の炭化水素基である)等が挙げられる。 In formulas (Sv-1) to (Sv-2), Y 1 and Y 2 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, X 1 is an oxygen atom or -COO-, X2 is a single bond or a carbonyl group, and R 1 is an alkanediyl group having 2 to 4 carbon atoms. n 1 is an integer of 1 to 3. When n 1 is 2 or 3, multiple R 1s may be the same or different. Z 1 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Y 3 and Y 4 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
式(Sv-1)中、Y1及びY2の炭素数1~6の1価の炭化水素基として、例えば炭素数1~6の1価の鎖状炭化水素基、炭素数1~6の1価の脂環式炭化水素基及び炭素数1~6の1価の芳香族炭化水素基などが挙げられる。炭素数1~6の1価の鎖状炭化水素基としては、炭素数1~6のアルキル基等を挙げることができる。R1のアルカンジイル基は直鎖状でも分岐状でもよい。 In formula (Sv-1), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms for Y1 and Y2 include a monovalent chain hydrocarbon group having 1 to 6 carbon atoms, a monovalent alicyclic hydrocarbon group having 1 to 6 carbon atoms, and a monovalent aromatic hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent chain hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms. The alkanediyl group for R1 may be linear or branched.
式(Sv-2)中、Z1の炭素数1~6の2価の炭化水素基として、例えば炭素数1~6のアルカンジイル基等を挙げることができる。
Y3及びY4の炭素数1~6の1価の炭化水素基としては、炭素数1~6の1価の鎖状炭化水素基、炭素数1~6の1価の脂環式炭化水素基及び炭素数1~6の1価の芳香族炭化水素基などが挙げられる。炭素数1~6の1価の鎖状炭化水素基としては炭素数1~6のアルキル基などが挙げられる。
In formula (Sv-2), examples of the divalent hydrocarbon group having 1 to 6 carbon atoms for Z 1 include an alkanediyl group having 1 to 6 carbon atoms.
Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms for Y3 and Y4 include a monovalent chain hydrocarbon group having 1 to 6 carbon atoms, a monovalent alicyclic hydrocarbon group having 1 to 6 carbon atoms, and a monovalent aromatic hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent chain hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms.
式(Sv-1)で表される溶媒の具体例としては、例えばエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコール-n-プロピルエーテル、エチレングリコール-i-プロピルエーテル、エチレングリコールモノブチルエーテル(ブチルセロソルブ)、エチレングリコールモノヘキシルエーテル、エチレングリコールジメチルエーテル、エチレングルコールモノアセタート、エチレングリコールジアセタート、エチレングリコールエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテルアセタート、プロピレングリコールモノブチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールジアセテート、エチレングリコール、1,4-ブタンジオール、3-メトキシブチルアセテート、3-エトキシブチルアセタート等を;Specific examples of the solvent represented by formula (Sv-1) include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol i-propyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetate, ethylene glycol, 1,4-butanediol, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, etc.;
(Sv-2)で表される溶媒の具体例としては、例えばグリコール酸メチル、グリコール酸エチル、グリコール酸ブチル、乳酸エチル、乳酸ブチル、乳酸イソアミル、エチル-3-エトキシプロピオネート、メチル-3-メトキシプロピオネート、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸、3-メトキシプロピオン酸、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチルなどをそれぞれ挙げることができる。 Specific examples of solvents represented by (Sv-2) include, for example, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, and butyl 3-methoxypropionate.
前記溶媒としては沸点が80~200℃にあることが好ましい。より好ましくは、80℃~180℃であり、好ましい溶媒として、N,N-ジメチルホルムアミド、テトラメチル尿素、3-メトキシ-N,N-ジメチルプロパンアミド、プロパノール、イソプロパノール、3-メチル-3-メトキシブタノール、エチルアミルケトン、メチルエチルケトン、イソアミルメチルケトン、メチルイソプロピルケトン、ジイソブチルケトン、シクロヘキサノン、シクロペンタノン、メチルイソブチルケトン、4-ヒドロキシ-4-メチル-2-ペンタノン、酢酸4-メチル-2-ペンチル、酢酸2-エチルブチル、酢酸シクロヘキシル、酢酸2-メチルシクロヘキシル、酪酸ブチル、酪酸イソアミル、ジイソブチルカルビノール、ジイソペンチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコール-n-プロピルエーテル、エチレングリコール-i-プロピルエーテル、エチレングリコールモノブチルエーテル(ブチルセロソルブ)、エチレングリコールジメチルエーテル、エチレングルコールモノアセタート、エチレングリコールエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、 プロピレングリコールモノエチルエーテルアセタート、プロピレングリコールモノブチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、3-メトキシブチルアセテート、グリコール酸メチル、グリコール酸エチル、グリコール酸ブチル、乳酸エチル、乳酸ブチル、乳酸イソアミル、エチル-3-エトキシプロピオネート、メチル-3-メトキシプロピオネート、3-メトキシプロピオン酸エチル、等を挙げることができる。
沸点がこの範囲であることは、特に、前記溶媒を含む液晶配向剤が後述するプラスチック基板上に塗布される場合に好ましい。
The solvent preferably has a boiling point of 80 to 200° C., more preferably 80 to 180° C., and examples of preferred solvents include N,N-dimethylformamide, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, propanol, isopropanol, 3-methyl-3-methoxybutanol, ethyl amyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone, 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, and butyl ether. Examples of the lactate include isoamyl lactate, diisobutyl carbinol, diisopentyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutyl acetate, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and ethyl 3-methoxypropionate.
The boiling point being in this range is particularly preferred when the liquid crystal aligning agent containing the solvent is applied onto a plastic substrate, which will be described later.
<他の成分>
本発明に用いられる液晶配向剤は、上記(A)成分及び(B)成分以外の他の成分を含有してもよい。このような他の成分としては、架橋触媒や、液晶配向剤を塗布した際の、膜厚均一性や表面平滑性を向上させる化合物、液晶配向膜と基板との密着性を向上させる化合物、等を挙げることができるが、これに限定されない。
<Other Ingredients>
The liquid crystal aligning agent used in the present invention may contain other components in addition to the above-mentioned components (A) and (B). Examples of such other components include, but are not limited to, a crosslinking catalyst, a compound that improves the film thickness uniformity and surface smoothness when the liquid crystal aligning agent is applied, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, and the like.
<架橋触媒>
本発明に用いられる液晶配向剤に、熱架橋性基Aと熱架橋性基Bとの反応を促進させる目的で、架橋触媒を添加してもよい。このような架橋触媒としては、p-トルエンスルホン酸、カンファスルホン酸、トリフルオロメタンスルホン酸、p-フェノールスルホン酸、2-ナフタレンスルホン酸、メシチレンスルホン酸、p-キシレン-2-スルホン酸、m-キシレン-2-スルホン酸、4-エチルベンゼンスルホン酸、1H,1H,2H,2H-パーフルオロオクタンスルホン酸、パーフルオロ(2-エトキシエタン)スルホン酸、ペンタフルオロエタンスルホン酸、ノナフルオロブタン-1-スルホン酸、ドデシルベンゼンスルホン酸等のスルホン酸またはその水和物や塩等が挙げられる。熱により酸を発生する化合物としては、例えば、ビス(トシルオキシ)エタン、ビス(トシルオキシ)プロパン、ビス(トシルオキシ)ブタン、p-ニトロベンジルトシレート、o-ニトロベンジルトシレート、1,2,3-フェニレントリス(メチルスルホネート)、p-トルエンスルホン酸ピリジニウム塩、p-トルエンスルホン酸モルフォニウム塩、p-トルエンスルホン酸エチルエステル、p-トルエンスルホン酸プロピルエステル、p-トルエンスルホン酸ブチルエステル、p-トルエンスルホン酸イソブチルエステル、p-トルエンスルホン酸メチルエステル、p-トルエンスルホン酸フェネチルエステル、シアノメチルp-トルエンスルホネート、2,2,2-トリフルオロエチルp-トルエンスルホネート、2-ヒドロキシブチルp-トルエンスルホネート、N-エチル-p-トルエンスルホンアミド等が挙げられる。
<Crosslinking catalyst>
A crosslinking catalyst may be added to the liquid crystal aligning agent used in the present invention for the purpose of promoting the reaction between the thermally crosslinkable group A and the thermally crosslinkable group B. Examples of such crosslinking catalysts include sulfonic acids such as p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctane sulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid, or hydrates or salts thereof. Examples of the compound that generates an acid when heated include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene tris(methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, and N-ethyl-p-toluenesulfonamide.
[膜厚の均一性や表面平滑性を向上させる化合物]
膜厚の均一性や表面平滑性を向上させる化合物としては、フッ素系界面活性剤、シリコーン系界面活性剤およびノ二オン系界面活性剤等が挙げられる。
具体的には、例えば、エフトップ(登録商標)301、EF303、EF352(トーケムプロダクツ社製)、メガファック(登録商標)F171、F173、R-30(DIC社製)、フロラードFC430、FC431(住友スリーエム社製)、アサヒガード(登録商標)AG710(旭硝子社製)、サーフロン(登録商標)S-382、SC101、SC102、SC103、SC104、SC105、SC106(AGCセイミケミカル社製)等が挙げられる。
これらの界面活性剤の使用割合は、重合体組成物に含有される樹脂成分の100質量部に対して、好ましくは0.01質量部~2質量部、より好ましくは0.01質量部~1質量部である。
[Compounds that improve film thickness uniformity and surface smoothness]
Compounds that improve the uniformity of the film thickness and the surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
Specific examples include EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited), ASAHIGUARD (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), SURFLOON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and the like.
The proportion of these surfactants used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the polymer composition.
[液晶配向膜と基板との密着性を向上させる化合物]
液晶配向膜と基板との密着性を向上させる化合物の具体例としては、次に示す官能性シラン含有化合物などが挙げられる。
例えば、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、2-アミノプロピルトリメトキシシラン、2-アミノプロピルトリエトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリメトキシシラン、N-エトキシカルボニル-3-アミノプロピルトリエトキシシラン、N-トリエトキシシリルプロピルトリエチレントリアミン、N-トリメトキシシリルプロピルトリエチレントリアミン、10-トリメトキシシリル-1,4,7-トリアザデカン、10-トリエトキシシリル-1,4,7-トリアザデカン、9-トリメトキシシリル-3,6-ジアザノニルアセテート、9-トリエトキシシリル-3,6-ジアザノニルアセテート、N-ベンジル-3-アミノプロピルトリメトキシシラン、N-ベンジル-3-アミノプロピルトリエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリメトキシシラン、N-ビス(オキシエチレン)-3-アミノプロピルトリエトキシシラン等のアミノ系シラン含有化合物が挙げられる。
基板との密着性を向上させる化合物を使用する場合、その使用量は、重合体組成物に含有される樹脂成分100質量部に対して0.1質量部~30質量部であることが好ましく、より好ましくは1質量部~20質量部である。
[Compound for improving adhesion between liquid crystal alignment film and substrate]
Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine , 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, and N-bis(oxyethylene)-3-aminopropyltriethoxysilane, and other amino-based silane-containing compounds.
When a compound for improving adhesion to a substrate is used, the amount used is preferably 0.1 parts by mass to 30 parts by mass, and more preferably 1 part by mass to 20 parts by mass, relative to 100 parts by mass of the resin component contained in the polymer composition.
ある実施形態において、光配向性基の光反応性を向上させるために添加剤として、光増感剤を用いることもできる。具体例として、芳香族2-ヒドロキシケトン(ベンゾフェノン)、クマリン、ケトクマリン、カルボニルビスクマリン、アセトフェノン、アントラキノン、キサントン、チオキサントン、およびアセトフェノンケタール等を挙げることができる。In some embodiments, a photosensitizer can be used as an additive to improve the photoreactivity of the photoalignment group. Specific examples include aromatic 2-hydroxyketones (benzophenones), coumarins, ketocoumarins, carbonyl biscoumarins, acetophenones, anthraquinones, xanthones, thioxanthones, and acetophenone ketals.
本発明に用いられる液晶配向剤において、前述の樹脂成分は、全てが上述した特定重合体であってもよいが、それら以外の他の重合体(以下、「その他の重合体」ともいう)が混合されていてもよい。その際、樹脂成分中におけるその他の重合体の含有量として、(A)成分とその他の重合体の合計100質量部に対し、5~95質量部、又は10~90質量部を挙げることができる。
そのような他の重合体としては、例えば、ポリ(メタ)アクリレートやポリアミック酸、ポリアミック酸エステルやポリイミド等であって、上記特定重合体の構成要件のうち、少なくとも1つを満たさない重合体が挙げられる。
In the liquid crystal aligning agent used in the present invention, the above-mentioned resin components may all be the above-mentioned specific polymers, or may contain other polymers (hereinafter also referred to as "other polymers") mixed in. In this case, the content of the other polymers in the resin components may be 5 to 95 parts by mass or 10 to 90 parts by mass relative to 100 parts by mass of the total of the component (A) and the other polymers.
Examples of such other polymers include poly(meth)acrylates, polyamic acids, polyamic acid esters, polyimides, etc., which do not satisfy at least one of the constituent requirements of the above-mentioned specific polymers.
当該他の重合体としては、ポリイミド及びその前駆体(以下、ポリイミド成分ともいう)であって、(A)成分である重合体と表面エネルギーが近い重合体が好ましい。(A)成分のようなアクリル成分は基本的に極性が低く、表面エネルギーが低い。一方、ポリイミド成分は極性が高く、表面エネルギーが高い。しかし、この二成分の表面エネルギーの差異が大きすぎると、うまく相溶せず凝集が発生することにより、凹凸のある膜ができたり、ハジキやムラが発生することによりプロセスマージンが狭くなってしまうといった問題を生じる恐れがある。そこで、ポリイミド成分の極性を低くすることにより、表面エネルギーをアクリル成分よりは高いものの、差異が小さい値に制御することができる。ポリイミド成分の極性を下げる方法として、化学的イミド化をしたのちに(A)成分と混ぜる方法や、側鎖を導入する方法がある。As the other polymer, polyimide and its precursor (hereinafter also referred to as polyimide component) are preferable, which have a surface energy close to that of the polymer of component (A). Acrylic components such as component (A) are basically low in polarity and low in surface energy. On the other hand, polyimide components are high in polarity and high in surface energy. However, if the difference in surface energy between these two components is too large, they may not be compatible and may aggregate, resulting in a film with unevenness, or the process margin may be narrowed due to repelling or unevenness. Therefore, by lowering the polarity of the polyimide component, the surface energy can be controlled to a value higher than that of the acrylic component, but with a small difference. Methods for lowering the polarity of the polyimide component include mixing it with component (A) after chemical imidization, and introducing a side chain.
そのような重合体としては、公知のテトラカルボン酸二無水物等のテトラカルボン酸誘導体と公知のジアミンとを重合したのち、化学的イミド化して得られる重合体、側鎖を有するジアミンを用いて得られるポリイミド前駆体、それをイミド化して得られるポリイミド、ターシャリーブトキシカルボニルオキシ基を有するジアミンを用いて得られるポリイミド前駆体、それをイミド化して得られるポリイミドなどが挙げられる。このような側鎖や化学的イミド化により、表面エネルギーを(A)成分であるアクリルポリマーに近づけることができるため、液晶配向剤を塗布、焼成して硬化膜を形成した際に、凝集等が起こらず、平坦な硬化膜を与えることができる。側鎖を有するジアミンとしては、国際特許出願公開WO2016/125870の段落[0023]~[0039]に記載の、式(2)、(3)、(4)、(5)で表されるジアミン及びその具体例としての式[A-1]~[A-32]で表されるジアミンが挙げられる。ターシャリーブトキシカルボニルオキシ基を有するジアミンとしては、国際特許出願公開WO2017/119461の段落[0011]~[0034]に記載の式[A-1]、[A-2]、[A-3]の構造を有するジアミンおよびその具体例として例示されているジアミンが挙げられる。 Examples of such polymers include polymers obtained by polymerizing a tetracarboxylic acid derivative such as a known tetracarboxylic acid dianhydride with a known diamine and then chemically imidizing the polymer, polyimide precursors obtained by using diamines having side chains, polyimides obtained by imidizing the polyimide precursors, polyimide precursors obtained by using diamines having tertiary butoxycarbonyloxy groups, polyimides obtained by imidizing the polyimide precursors, and the like. By using such side chains or chemical imidization, the surface energy can be made closer to that of the acrylic polymer, which is the component (A), so that when a liquid crystal alignment agent is applied and baked to form a cured film, no aggregation or the like occurs, and a flat cured film can be obtained. Examples of diamines having side chains include diamines represented by formulas (2), (3), (4), and (5) described in paragraphs [0023] to [0039] of International Patent Application Publication WO2016/125870, and specific examples thereof represented by formulas [A-1] to [A-32]. Examples of diamines having a tertiary-butoxycarbonyloxy group include diamines having structures of formulas [A-1], [A-2], and [A-3] described in paragraphs [0011] to [0034] of International Patent Application Publication WO2017/119461, and diamines exemplified as specific examples thereof.
<液晶配向膜及び液晶表示素子>
本発明の液晶配向剤は、基板上に塗布、焼成した後、ラビング処理や光照射などで配向処理をして、又は一部の垂直配向用途などでは配向処理無しで液晶配向膜とすることができる。基板としては、例えばフロートガラス、ソーダガラスなどのガラス;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリプロピレン、ポリスチレン、ポリエーテルスルホン、ポリカーボネート、ポリ(脂環式オレフィン)、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリエーテルエーテルケトン(PEEK)樹脂フィルム、ポリサルホン(PSF)、ポリエーテルサルホン(PES)、ポリアミド、ポリイミド、アクリル及びトリアセチルセルロースなどのプラスチックからなる透明基板を用いることができる。
基板の一面に設けられる透明導電膜としては、酸化スズ(SnO2)からなるNESA膜(米国PPG社登録商標)、酸化インジウム-酸化スズ(In2O3-SnO2)からなるITO膜などを用いることができる。
<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment agent of the present invention can be applied to a substrate, baked, and then subjected to an alignment treatment such as rubbing or light irradiation to form a liquid crystal alignment film, or in some vertical alignment applications, no alignment treatment can be performed. As the substrate, for example, a transparent substrate made of glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polypropylene, polystyrene, polyethersulfone, polycarbonate, poly(alicyclic olefin), polyvinyl chloride, polyvinylidene chloride, polyetheretherketone (PEEK) resin film, polysulfone (PSF), polyethersulfone (PES), polyamide, polyimide, acrylic, triacetyl cellulose, or other plastics can be used.
The transparent conductive film provided on one side of the substrate may be a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2 O 3 —SnO 2 ), or the like.
<塗膜形成工程>
本発明の液晶配向剤の塗布方法は特に限定されないが、スクリーン印刷、フレキソ印刷、オフセット印刷、インクジェット、ディップコーティング、ロールコーティング、スリットコーティング、スピンコーティングなどがあり、目的に応じてこれらを用いてもよい。これらの方法により基板上に塗布した後、ホットプレートなどの加熱手段により溶媒を蒸発させて、塗膜を形成させることができる。
<Coating film formation process>
The method of applying the liquid crystal alignment agent of the present invention is not particularly limited, and may be screen printing, flexographic printing, offset printing, inkjet, dip coating, roll coating, slit coating, spin coating, etc., which may be used depending on the purpose. After applying the agent to a substrate by these methods, the solvent is evaporated by a heating means such as a hot plate to form a coating film.
液晶配向剤を塗布した後の焼成は、40~300℃の任意の温度で行うことができるが、好ましくは40℃~250℃であり、より好ましくは40℃~230℃である。プラスチック基板からなる透明基板を用いる場合は、40~150℃とすることが好ましく、80~140℃とすることがより好ましい。焼成時間は、0.1~15分とすることが好ましく、1~10分とすることがより好ましい。
基板上に形成される塗膜の膜厚は、好ましくは5~1,000nmであり、より好ましくは10~500nm又は10~300nmである。この焼成はホットプレート、熱風循環炉、赤外線炉などで行うことができる。
The baking after application of the liquid crystal alignment agent can be carried out at any temperature between 40 and 300° C., preferably between 40 and 250° C., and more preferably between 40 and 230° C. When a transparent substrate made of a plastic substrate is used, the baking temperature is preferably between 40 and 150° C., and more preferably between 80 and 140° C. The baking time is preferably between 0.1 and 15 minutes, and more preferably between 1 and 10 minutes.
The thickness of the coating film formed on the substrate is preferably 5 to 1,000 nm, more preferably 10 to 500 nm or 10 to 300 nm. This baking can be carried out using a hot plate, a hot air circulating oven, an infrared oven, or the like.
<光照射工程>
本発明における光照射工程は、前記塗膜形成工程で得られた硬化膜に紫外線を斜め方向から照射する1回目の照射工程、並びに、当該紫外線照射後の硬化膜に、当該1回目の照射工程とは異なる方向から紫外線照射を行う2回目の照射工程をこの順番で含み、当該1回目の照射工程と2回目の照射工程の少なくとも一方は、遮光された領域と遮光されていない領域とを含むマスクを介して行われる。
<Light irradiation process>
The light irradiation process in the present invention includes a first irradiation process in which the cured film obtained in the coating film formation process is irradiated with ultraviolet light from an oblique direction, and a second irradiation process in which the cured film after the ultraviolet light irradiation is irradiated with ultraviolet light from a direction different from that of the first irradiation process, in this order, and at least one of the first irradiation process and the second irradiation process is carried out through a mask including a light-shielded region and a light-unshielded region.
光照射による配向処理で照射する光としては、例えば150~800nmの波長の光を含む紫外線、可視光線などを挙げることができる。これらのうち、300~400nmの波長の光を含む紫外線が好ましい。照射光は偏光であっても非偏光であってもよい。偏光としては、直線偏光を含む光を使用することが好ましい。 Examples of light to be irradiated in the alignment treatment by photoirradiation include ultraviolet light containing light with a wavelength of 150 to 800 nm, visible light, etc. Of these, ultraviolet light containing light with a wavelength of 300 to 400 nm is preferred. The irradiated light may be polarized or unpolarized. As the polarized light, it is preferable to use light containing linearly polarized light.
光の照射量は、0.1mJ/cm2以上1,000mJ/cm2未満とすることが好ましく、1~500mJ/cm2とすることがより好ましく、2~200mJ/cm2とすることがさらに好ましい。 The amount of light irradiation is preferably 0.1 mJ/cm 2 or more and less than 1,000 mJ/cm 2 , more preferably 1 to 500 mJ/cm 2 , and even more preferably 2 to 200 mJ/cm 2 .
紫外線の照射方向は、通常、基板法線に対して1°から89°であるが、好ましくは20°~70°、特に好ましくは30°~60°である。この角度が小さすぎる場合はプレチルト角が小さくなるという問題があり、大きすぎる場合は照射装置の設計が難しくなるという問題がある。The direction of ultraviolet light irradiation is usually 1° to 89° with respect to the substrate normal, but is preferably 20° to 70°, and particularly preferably 30° to 60°. If this angle is too small, there is a problem that the pretilt angle becomes small, and if it is too large, there is a problem that it becomes difficult to design the irradiation device.
照射方向を上記の角度に調節する方法としては、基板自体を傾ける方法と、光源を傾ける方法があるが、光源自体を傾けるのがスループットの観点からより好ましい。 There are two ways to adjust the irradiation direction to the above angle: tilting the substrate itself or tilting the light source. From the standpoint of throughput, however, tilting the light source itself is more preferable.
なお、本発明は、特定の組成物を用いることにより、ある方向からの紫外線の照射により形成されたプレチルト角を、別方向からの紫外線の照射によりキャンセルし、異なるプレチルト角を形成することができる。
これにより、例えば紫外線の全面露光により特定方向のプレチルト角を形成したあと、マスクを介して別方向から紫外線を照射することにより、簡便に、配向方向が異なる領域を複数形成(配向分割)することが可能となり、効率的にマルチドメイン液晶表示素子を製造することが可能である。
In addition, in the present invention, by using a specific composition, a pretilt angle formed by irradiation with ultraviolet light from one direction can be cancelled by irradiation with ultraviolet light from another direction, thereby forming a different pretilt angle.
As a result, for example, after forming a pretilt angle in a specific direction by exposing the entire surface to ultraviolet light, it is possible to easily form multiple regions with different alignment directions (alignment division) by irradiating ultraviolet light from another direction through a mask, and thus it is possible to efficiently manufacture a multi-domain liquid crystal display element.
本発明の製造方法で得られるマルチドメイン液晶配向膜は、プレチルト角が、垂直配向モードに適したプレチルト角として90°からマイナス0.1°~マイナス10°傾いた領域1と、90°からプラス0.1°~プラス10°傾いた領域2を有することが好ましい。すなわち、プレチルト角として80°~89.9°の領域1および90.1°~100°の領域2を有することが好ましく、85°~89°の領域1および91°~95°の領域2を有することがさらに好ましい。The multi-domain liquid crystal alignment film obtained by the manufacturing method of the present invention preferably has a pretilt angle suitable for the vertical alignment mode, that is, region 1 inclined at -0.1° to -10° from 90°, and region 2 inclined at +0.1° to +10° from 90°. In other words, it is preferable that the pretilt angle be region 1 of 80° to 89.9° and region 2 of 90.1° to 100°, and it is even more preferable that the pretilt angle be region 1 of 85° to 89° and region 2 of 91° to 95°.
なお、上記領域1および領域2を形成する際、1回目の照射工程で領域1を形成し、2回目の照射工程で領域2を形成してもよく、1回目の照射工程で領域2を形成し、2回目の照射工程で領域1を形成してもよい。1回目の照射工程がマスクを介さずに行われる場合、二回目の照射工程における光の照射量は、1回目の照射工程における光の照射量よりも多い方が好ましい。一方、1回目の照射工程がマスクを介して行われる場合、2回目の照射工程における光の照射量は、1回目の照射工程における光の照射量よりも少ない方が好ましい。When forming the above regions 1 and 2, region 1 may be formed in the first irradiation step and region 2 may be formed in the second irradiation step, or region 2 may be formed in the first irradiation step and region 1 may be formed in the second irradiation step. When the first irradiation step is performed without using a mask, it is preferable that the amount of light irradiation in the second irradiation step is greater than the amount of light irradiation in the first irradiation step. On the other hand, when the first irradiation step is performed through a mask, it is preferable that the amount of light irradiation in the second irradiation step is less than the amount of light irradiation in the first irradiation step.
本発明によれば、1回目の照射工程と2回目の照射工程でともにパターン状のマスクを用いた場合、マスクがずれた場合であっても、2回目の照射領域では1回目の照射領域のチルトをキャンセルして、2回目の照射によるチルト角に書き換えることができるため、マスクがずれた場合に「暗線」となってしまうことがない。 According to the present invention, when a patterned mask is used in both the first and second irradiation processes, even if the mask is misaligned, the tilt of the first irradiation area can be cancelled in the second irradiation area and rewritten with the tilt angle due to the second irradiation, so that "dark lines" do not appear when the mask is misaligned.
本発明の液晶表示素子は、本発明で得られたマルチドメイン液晶配向膜を用いて、通常の方法により作製することができ、その作製方法は特に限定されるものではない。 上記一対の基板が、適正なギャップを介して対向し、基板間に挟持される液晶の厚さを均一とする目的で、基板間にスペーサーを配置することが好ましい。このスペーサーとしては、旧来からの散布型スペーサー、感光性のスペーサー形成用組成物から形成されたスペーサーなどの公知のスペーサー材料を使用することができるほか、液晶硬化物からなる層に形成した凹凸をスペーサーとして使用することも可能である。The liquid crystal display element of the present invention can be produced by a normal method using the multi-domain liquid crystal alignment film obtained by the present invention, and the production method is not particularly limited. It is preferable that the pair of substrates face each other with an appropriate gap therebetween, and spacers are disposed between the substrates in order to make the thickness of the liquid crystal sandwiched between the substrates uniform. As the spacer, known spacer materials such as conventional scattered spacers and spacers formed from a photosensitive spacer-forming composition can be used, and it is also possible to use unevenness formed in a layer made of a liquid crystal cured product as a spacer.
<液晶挟持工程>
基板間に液晶を挟持して液晶セルを構成するには、例えば以下の2つの方法を挙げることができる。第1の方法として、各液晶配向膜が対向するように間隙(セルギャップ)を介して一対の基板を対向配置し、該一対の基板の周辺部をシール剤を用いて貼り合わせ、基板表面および適当なシール剤により区画されたセルギャップ内に液晶を注入充填した後、注入孔を封止することにより、液晶セルを製造する方法を挙げることができる。
<Liquid crystal clamping process>
There are two methods for constructing a liquid crystal cell by sandwiching liquid crystal between substrates, for example: In the first method, a pair of substrates are arranged opposite each other with a gap (cell gap) between them so that the liquid crystal alignment films face each other, the peripheries of the pair of substrates are bonded together using a sealant, liquid crystal is injected and filled on the substrate surfaces and in the cell gap defined by a suitable sealant, and then the injection hole is sealed to produce a liquid crystal cell.
第2の方法として、液晶配向膜を形成した2枚の基板のうちの一方の基板上の所定の場所に例えば紫外光硬化性のシール材を塗布し、さらに液晶配向膜面上の所定の数カ所に液晶を滴下した後、液晶配向膜が対向するように他方の基板を貼り合わせるとともに液晶を基板全面に押し広げ、次いで基板の全面に紫外光を照射してシール剤を硬化することにより、液晶セルを製造する方法(ODF(One Drop Fill)法)を挙げることができる。 A second method is to manufacture a liquid crystal cell by applying, for example, an ultraviolet light-curable sealant to a predetermined location on one of the two substrates on which a liquid crystal alignment film has been formed, and then dripping liquid crystal onto several predetermined locations on the liquid crystal alignment film surface, and then bonding the other substrate so that the liquid crystal alignment film faces the other substrate and spreading the liquid crystal over the entire surface of the substrate, and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealant (ODF (One Drop Fill) method).
液晶としては、用途に応じて正や負の誘電率異方性を有するフッ素系液晶やシアノ系液晶、また加熱および光照射のうちの少なくとも1種の処理によって重合する液晶化合物または液晶組成物(以下、重合性液晶又は硬化性液晶組成物ともいう)を用いても良い。
ある実施形態において、前記液晶配向剤の塗膜を形成する工程が、ロール・ツー・ロール方式によって行われてもよい。ロール・ツー・ロール方式によって行われると、液晶表示素子の製造工程を簡略化し、もって製造コストを削減することが可能となる。
そして、前記液晶セルの外側両面に偏光板を貼付することにより、液晶表示素子を得ることができる。
As the liquid crystal, a fluorine-based liquid crystal or a cyano-based liquid crystal having positive or negative dielectric anisotropy may be used depending on the application, or a liquid crystal compound or liquid crystal composition that is polymerized by at least one of heating and light irradiation (hereinafter also referred to as a polymerizable liquid crystal or a curable liquid crystal composition).
In one embodiment, the step of forming a coating film of the liquid crystal alignment agent may be performed by a roll-to-roll process, which simplifies the manufacturing process of the liquid crystal display element and thereby reduces the manufacturing cost.
Then, polarizing plates are attached to both outer surfaces of the liquid crystal cell to obtain a liquid crystal display element.
液晶セルの外側に使用される偏光板としては、ポリビニルアルコールを延伸配向させながらヨウ素を吸収させた「H膜」と呼ばれる偏光膜を酢酸セルロース保護膜で挟んだ偏光板、またはH膜そのものからなる偏光板などを挙げることができる。
上記のようにして本発明の液晶配向剤から得られる液晶配向膜は、液晶配向性が良好であり、プレチルト角発現能にも優れ、且つ高い信頼性が得られる。また、本発明の方法によって製造された液晶表示素子は優れた表示特性を有する。
Examples of polarizing plates used on the outside of a liquid crystal cell include a polarizing plate in which a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine is sandwiched between cellulose acetate protective films, or a polarizing plate made of an H film itself.
The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention as described above has good liquid crystal alignment properties, is excellent in pretilt angle expression ability, and has high reliability. Moreover, the liquid crystal display element produced by the method of the present invention has excellent display characteristics.
実施例において使用した化合物の構造を以下に示す。
なお、式中、「t」は、シクロヘキシル基がトランス型であることを示す。
The structures of the compounds used in the examples are shown below.
In the formula, "t" indicates that the cyclohexyl group is in a trans configuration.
MA-1、MA-2、MA-3、MA-4は光配向性モノマーであり、CR-1、CR-2、MOI-BP、HEMA、MAAは熱架橋性モノマーである。 MA-1, MA-2, MA-3, and MA-4 are photoalignable monomers, and CR-1, CR-2, MOI-BP, HEMA, and MAA are thermally crosslinkable monomers.
X-1、X-2、X-3はテトラカルボン酸二無水物モノマーである。 X-1, X-2, and X-3 are tetracarboxylic dianhydride monomers.
X-4は側鎖ジアミンモノマーであり、X-5、X-6はその他ジアミンモノマーである。 X-4 is a side chain diamine monomer, and X-5 and X-6 are other diamine monomers.
実施例等で使用した有機溶媒の略号は以下の通りである。
PGME:プロピレングリコールモノメチルエーテル
CHN:シクロヘキサノン
実施例等で使用した重合開始剤の略称は以下の通りである。
AIBN:2,2’-アゾビスイソブチロニトリル
The abbreviations for the organic solvents used in the examples are as follows.
PGME: propylene glycol monomethyl ether CHN: cyclohexanone The abbreviations of the polymerization initiators used in the examples are as follows.
AIBN: 2,2'-azobisisobutyronitrile
<ポリマー分子量測定>
合成例におけるポリマーの分子量はセンシュー科学社製 常温ゲル浸透クロマトグラフィー(GPC)装置(SSC-7200、Shodex社製カラム(KD-803、KD-805)を用い以下のようにして測定した。
カラム温度:50℃
溶離液:DMF(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L、リン酸・無水結晶(o-リン酸)が30mmol/L、THFが10ml/L)
流速:1.0ml/分
検量線作成用標準サンプル:東ソー社製 TSK 標準ポリエチレンオキサイド(分子量約9000,000、150,000、100,000、30,000)、及び、ポリマーラボラトリー社製 ポリエチレングリコール(分子量約12,000、4,000、1,000)。
<Polymer molecular weight measurement>
The molecular weight of the polymer in the synthesis examples was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd.
Column temperature: 50 ° C.
Eluent: DMF (additives: lithium bromide hydrate (LiBr.H 2 O) 30 mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) 30 mmol/L, THF 10 ml/L)
Flow rate: 1.0 ml/min. Standard samples for preparing calibration curves: TSK standard polyethylene oxide (molecular weights: approximately 9,000,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weights: approximately 12,000, 4,000, and 1,000) manufactured by Polymer Laboratory.
<参考例1>
MA-1(4.95g、12.0mmol)とMOI-BP(7.04g、28.0mmol)をCHN(69.8g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.33g、2.0mmol)を加え再び脱気を行った。この後55℃で13時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノールと純水=5/5の混合溶媒(1000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末(A)を得た。このポリマーの数平均分子量は44200、重量平均分子量は141800であった。
得られたメタクリレートポリマー粉末(A)(1.5g)にCHN(18.0g)を加え、室温で5時間攪拌して溶解させた。この溶液にCR-1(0.15g)及びPGME(18.0g)を加え攪拌することにより液晶配向剤(A1)を得た。
<Reference Example 1>
MA-1 (4.95 g, 12.0 mmol) and MOI-BP (7.04 g, 28.0 mmol) were dissolved in CHN (69.8 g), and the mixture was degassed using a diaphragm pump. AIBN (0.33 g, 2.0 mmol) was added and degassed again. After that, the mixture was reacted at 55°C for 13 hours to obtain a methacrylate polymer solution. This polymer solution was dropped into a mixed solvent (1000 ml) of methanol and pure water = 5/5, and the obtained precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder (A). The number average molecular weight of this polymer was 44,200 and the weight average molecular weight was 141,800.
CHN (18.0 g) was added to the obtained methacrylate polymer powder (A) (1.5 g), and the mixture was stirred at room temperature for 5 hours to dissolve. CR-1 (0.15 g) and PGME (18.0 g) were added to the solution and stirred to obtain a liquid crystal alignment agent (A1).
<実施例1-0>
[液晶セルの作製]
参考例1で得られた液晶配向剤(A1)を、ITO膜からなる透明電極付きガラス基板のITO面にスピンコートし、40℃のホットプレートで300秒間乾燥を行った。次いで、120℃のホットプレートで10分間焼成を行い、膜厚100nmの液晶配向膜を形成した。その後、配向膜の塗膜面に偏光板を介して、照射強度4.3mW/cm2の313nmの直線偏光紫外光を基板法線方向から40°傾斜した角度から50mJ/cm2照射することで、液晶配向膜付き基板を得た。照射する313nmの直線偏光紫外光は高圧水銀ランプから出射される紫外光を313nmのバンドパスフィルターとブリュースター偏光板を通過させることで取り出した。
上記の基板を2枚用意し、一方の基板の液晶配向膜上に4μmのビーズスペーサーを散布した後、シール剤(三井化学製、XN-1500T)を塗布した。次いで、もう一方の基板を、液晶配向膜面が向き合い、入射する偏光紫外光の照射方向が、対向する基板に入射した紫外光の照射方向に対して180°になるようにして張り合わせた後、120℃で90分シール剤を熱硬化させることで空セルを作製した。この空セルにネガ型液晶(メルク社製、MLC-3022)を減圧注入法によって注入し、液晶セルを作製した。
<Example 1-0>
[Preparation of Liquid Crystal Cell]
The liquid crystal alignment agent (A1) obtained in Reference Example 1 was spin-coated on the ITO surface of a glass substrate with a transparent electrode made of an ITO film, and dried for 300 seconds on a hot plate at 40 ° C. Then, the substrate was baked for 10 minutes on a hot plate at 120 ° C. to form a liquid crystal alignment film with a thickness of 100 nm. Thereafter, the coating surface of the alignment film was irradiated with 313 nm linearly polarized ultraviolet light with an irradiation intensity of 4.3 mW / cm 2 at an angle inclined by 40 ° from the substrate normal direction at 50 mJ / cm 2 through a polarizing plate, thereby obtaining a substrate with a liquid crystal alignment film. The irradiated 313 nm linearly polarized ultraviolet light was extracted by passing the ultraviolet light emitted from a high-pressure mercury lamp through a 313 nm bandpass filter and a Brewster polarizing plate.
Two of the above substrates were prepared, and 4 μm bead spacers were dispersed on the liquid crystal alignment film of one of the substrates, followed by application of a sealant (Mitsui Chemicals, XN-1500T). Next, the other substrate was attached so that the liquid crystal alignment film faces each other and the irradiation direction of the incident polarized ultraviolet light was 180° to the irradiation direction of the ultraviolet light incident on the opposing substrate, and then the sealant was thermally cured at 120° C. for 90 minutes to prepare an empty cell. Negative liquid crystal (Merck, MLC-3022) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell.
[プレチルト角の評価]
液晶セルのプレチルト角の測定はAxo Metrix社製の「AxoScan」を用いてミューラーマトリックス法により測定した。結果を表1にまとめる。
[Evaluation of pretilt angle]
The pretilt angle of the liquid crystal cell was measured by the Mueller matrix method using "AxoScan" manufactured by Axo Metrix, Inc. The results are summarized in Table 1.
[液晶配向性の評価]
液晶セル作製後、120℃で1時間等方相処理を行った後に偏光顕微鏡にてセル観察を行い、光抜けやドメイン発生などの配向不良が無い場合や液晶セルに電圧印可した際に均一な液晶の駆動が得られる場合を配向性良好とした。結果を表1にまとめる。
[Evaluation of Liquid Crystal Alignment]
After preparing the liquid crystal cell, the cell was subjected to isotropic phase treatment at 120° C. for 1 hour, and then the cell was observed under a polarizing microscope. The alignment was deemed to be good if there was no alignment defect such as light leakage or domain generation, or if uniform liquid crystal drive was obtained when a voltage was applied to the liquid crystal cell. The results are summarized in Table 1.
<実施例1-1>
実施例1-0の[液晶セルの作製]において、基板法線方向から40°傾斜した角度から直線偏光紫外線を50mJ/cm2照射した後、さらに基板法線方向から40°傾斜した角度から50mJ/cm2照射を行った以外、実施例1-0と同様な方法により、液晶セルを得た。なお、1回目の照射と2回目の照射は、それぞれ法線方向から反対方向に40°傾斜させた。また、実施例1-0と同様な方法でプレチルト角と液晶セル配向性を評価した。
<Example 1-1>
A liquid crystal cell was obtained in the same manner as in Example 1-0 [Preparation of liquid crystal cell], except that linearly polarized ultraviolet light was irradiated at 50 mJ/ cm2 from an angle tilted at 40° from the substrate normal direction, and then irradiated at 50 mJ/cm2 from an angle tilted at 40° from the substrate normal direction. The first and second irradiations were tilted at 40° in opposite directions from the normal direction. The pretilt angle and liquid crystal cell alignment were evaluated in the same manner as in Example 1-0.
<実施例1-2、1-3>
実施例1-1の[液晶セルの作製]において、2回目の偏光紫外線照射量を100mJ/cm2(実施例1-2)、150mJ/cm2(実施例1-3)に変更した以外、実施例1-1と同様な方法により、液晶セルを得た。また、実施例1-0と同様な方法でプレチルト角と液晶セル配向性を評価した。
<Examples 1-2 and 1-3>
In the [Preparation of liquid crystal cell] of Example 1-1, except that the second polarized UV irradiation dose was changed to 100 mJ/ cm2 (Example 1-2) or 150 mJ/ cm2 (Example 1-3), liquid crystal cells were obtained in the same manner as in Example 1-1. The pretilt angle and liquid crystal cell alignment were evaluated in the same manner as in Example 1-0.
<参考例2>
MA-1(4.95g、12.0mmol)とMOI-BP(3.52g、14.0mmol)、HEMA(1.82g、14.0mmol)をCHN(60.2g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.33g、2.0mmol)を加え再び脱気を行った。この後55℃で13時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノールと純水=5/5の混合溶媒(1000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末(B)を得た。このポリマーの数平均分子量は33800、重量平均分子量は123500であった。
得られたメタクリレートポリマー粉末(B)(1.5g)にCHN(18.0g)を加え、室温で5時間攪拌して溶解させた。この溶液にPGME(18.0g)を加え攪拌することにより液晶配向剤(B1)を得た。
<Reference Example 2>
MA-1 (4.95 g, 12.0 mmol), MOI-BP (3.52 g, 14.0 mmol), and HEMA (1.82 g, 14.0 mmol) were dissolved in CHN (60.2 g), and the mixture was degassed using a diaphragm pump. Then, AIBN (0.33 g, 2.0 mmol) was added and degassed again. After this, the mixture was reacted at 55°C for 13 hours to obtain a methacrylate polymer solution. This polymer solution was dropped into a mixed solvent (1000 ml) of methanol and pure water = 5/5, and the obtained precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder (B). The number average molecular weight of this polymer was 33,800 and the weight average molecular weight was 123,500.
CHN (18.0 g) was added to the obtained methacrylate polymer powder (B) (1.5 g), and the mixture was stirred at room temperature for 5 hours to dissolve the mixture. PGME (18.0 g) was added to the solution and stirred to obtain a liquid crystal alignment agent (B1).
<参考例3>
MA-1(3.30g、8.0mmol)とMAA(2.75g、32.0mmol)をCHN(36.2g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.33g、2.0mmol)を加え再び脱気を行った。この後55℃で13時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノールと純水=5/5の混合溶媒(1000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末(C)を得た。このポリマーの数平均分子量は51500、重量平均分子量は143000であった。
得られたメタクリレートポリマー粉末(C)(1.5g)にCHN(18.0g)を加え、室温で5時間攪拌して溶解させた。この溶液にCR-2(0.45g)とPGME(18.0g)を加え攪拌することにより液晶配向剤(C1)を得た。
<Reference Example 3>
MA-1 (3.30 g, 8.0 mmol) and MAA (2.75 g, 32.0 mmol) were dissolved in CHN (36.2 g), and the mixture was degassed using a diaphragm pump. Then, AIBN (0.33 g, 2.0 mmol) was added and degassed again. After this, the mixture was reacted at 55°C for 13 hours to obtain a methacrylate polymer solution. This polymer solution was dropped into a mixed solvent (1000 ml) of methanol and pure water = 5/5, and the obtained precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder (C). The number average molecular weight of this polymer was 51,500 and the weight average molecular weight was 143,000.
CHN (18.0 g) was added to the obtained methacrylate polymer powder (C) (1.5 g), and the mixture was stirred at room temperature for 5 hours to dissolve. CR-2 (0.45 g) and PGME (18.0 g) were added to the solution and stirred to obtain a liquid crystal alignment agent (C1).
<参考例4>
X-4(2.28g、3.00mmol)、X-5(1.22g、4.00mmol)、X-6(1.45g、3.00mmol)及びX-1(2.23g、6.00mmol)をNMP(27.2g)中に溶解し、60℃で5時間反応させた後、X-2(1.00g、2.00mmol)及びX-3(0.87g、2.00mmol)とNMP(9.1g)を加え、40℃で10時間反応させポリアミック酸ポリマー溶液を得た。
ポリアミック酸ポリマー溶液(50g)にNMPを加え6.5質量%に希釈した後、イミド化触媒として無水酢酸(8.8g)及びピリジン(2.7g)を加え、75℃で2.5時間反応させた。この反応溶液をメタノール(700ml)に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミドポリマー粉末を得た。このポリイミドポリマーのイミド化率は71%であり、数平均分子量は13000、重量平均分子量は42000であった。
得られたポリイミド粉末(6.0g)にNMP(44.0g)を加え、70℃にて20時間攪拌して溶解させた。この溶液にNMP(10.0g)、BCS(40.0g)を加え、室温で5時間攪拌することによりポリイミドポリマー溶液(H1)を得た。
得られたポリイミドポリマー溶液(H1)(14.0g)と、参考例2で得られた液晶配向剤(B1)(6.0g)を室温で5時間攪拌することにより液晶配向剤(D1)を得た。
<Reference Example 4>
X-4 (2.28 g, 3.00 mmol), X-5 (1.22 g, 4.00 mmol), X-6 (1.45 g, 3.00 mmol) and X-1 (2.23 g, 6.00 mmol) were dissolved in NMP (27.2 g) and reacted at 60° C. for 5 hours, after which X-2 (1.00 g, 2.00 mmol) and X-3 (0.87 g, 2.00 mmol) and NMP (9.1 g) were added and reacted at 40° C. for 10 hours to obtain a polyamic acid polymer solution.
The polyamic acid polymer solution (50 g) was diluted to 6.5% by mass with NMP, and then acetic anhydride (8.8 g) and pyridine (2.7 g) were added as imidization catalysts and reacted at 75° C. for 2.5 hours. The reaction solution was poured into methanol (700 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100° C. to obtain a polyimide polymer powder. The imidization rate of this polyimide polymer was 71%, the number average molecular weight was 13,000, and the weight average molecular weight was 42,000.
NMP (44.0 g) was added to the obtained polyimide powder (6.0 g), and the mixture was dissolved by stirring at 70° C. for 20 hours. NMP (10.0 g) and BCS (40.0 g) were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a polyimide polymer solution (H1).
The obtained polyimide polymer solution (H1) (14.0 g) and the liquid crystal aligning agent (B1) (6.0 g) obtained in Reference Example 2 were stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (D1).
<参考例5>
参考例(4)で得られたポリイミドポリマー溶液(H1)(14.0g)と、参考例3で得られた液晶配向剤(C1)(6.0g)を室温で5時間攪拌することにより液晶配向剤(E1)を得た。
<Reference Example 5>
The polyimide polymer solution (H1) (14.0 g) obtained in Reference Example (4) and the liquid crystal alignment agent (C1) (6.0 g) obtained in Reference Example 3 were stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (E1).
<実施例2-0~5-3>
参考例1で得られた液晶配向剤(A1)の代わりに、表1に記載の液晶配向剤を用いた以外は、実施例1-0~1-3と同様に試験を行なった。評価結果を表1に記す。
<Examples 2-0 to 5-3>
Tests were carried out in the same manner as in Examples 1-0 to 1-3, except that the liquid crystal aligning agent shown in Table 1 was used instead of the liquid crystal aligning agent (A1) obtained in Reference Example 1. The evaluation results are shown in Table 1.
<参考例6>
MA-2(13.74g、24.0mmol)とMA-3(7.02g、16.0mmol)をCHN(119.5g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.33g、2.0mmol)を加え再び脱気を行った。この後55℃で13時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノールと純水=5/5の混合溶媒(1000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末(D)を得た。このポリマーの数平均分子量は35700、重量平均分子量は126000であった。
得られたメタクリレートポリマー粉末(D)(1.5g)にCHN(18.0g)を加え、室温で5時間攪拌して溶解させた。この溶液にCHN(18.0g)を加え攪拌することにより液晶配向剤(F1)を得た。
<Reference Example 6>
MA-2 (13.74 g, 24.0 mmol) and MA-3 (7.02 g, 16.0 mmol) were dissolved in CHN (119.5 g), and the mixture was degassed using a diaphragm pump. Then, AIBN (0.33 g, 2.0 mmol) was added and the mixture was degassed again. After that, the mixture was reacted at 55°C for 13 hours to obtain a methacrylate polymer solution. This polymer solution was dropped into a mixed solvent (1000 ml) of methanol and pure water = 5/5, and the obtained precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder (D). The number average molecular weight of this polymer was 35,700 and the weight average molecular weight was 126,000.
CHN (18.0 g) was added to the obtained methacrylate polymer powder (D) (1.5 g), and the mixture was stirred at room temperature for 5 hours to dissolve the mixture. CHN (18.0 g) was added to the solution and stirred to obtain a liquid crystal alignment agent (F1).
<比較例1-0>
[液晶セルの作製]
参考例6で得られた液晶配向剤(F1)を、ITO膜からなる透明電極付きガラス基板のITO面にスピンコートし、40℃のホットプレートで300秒間乾燥を行い、膜厚100nmの液晶配向膜を形成した。塗膜面に偏光板を介して、照射強度4.3mW/cm2の313nmの直線偏光紫外線を基板法線方向から40°傾斜した角度から50mJ/cm2照射した。次いで、120℃のホットプレートで10分間焼成を行い、液晶配向膜付き基板を得た。入直線偏光UVは高圧水銀ランプの紫外光に313nmのバンドパスフィルターを通した後、313nmの偏光板を通すことで調製した。
上記の基板を2枚用意し、一方の基板の液晶配向膜上に4μmのビーズスペーサーを散布した後、シール剤(協立化学製、XN-1500T)を塗布した。次いで、もう一方の基板を、液晶配向膜面が向き合い配向方向が180°になるようにして張り合わせた後、120℃で90分シール剤を熱硬化させることで空セルを作製した。この空セルにネガ型液晶(メルク社製、MLC-3022)を減圧注入法によって注入し、液晶セルを作製した。
また、実施例1-0と同様な方法でプレチルト角と液晶セル配向性を評価した。
<Comparative Example 1-0>
[Preparation of Liquid Crystal Cell]
The liquid crystal alignment agent (F1) obtained in Reference Example 6 was spin-coated on the ITO surface of a glass substrate with a transparent electrode made of an ITO film, and dried for 300 seconds on a hot plate at 40 ° C. to form a liquid crystal alignment film with a thickness of 100 nm. The coating surface was irradiated with 313 nm linearly polarized ultraviolet light with an irradiation intensity of 4.3 mW / cm 2 at an angle inclined by 40 ° from the substrate normal direction at 50 mJ / cm 2 through a polarizing plate. Then, the substrate was baked for 10 minutes on a hot plate at 120 ° C. to obtain a substrate with a liquid crystal alignment film. The incident linearly polarized UV was prepared by passing the ultraviolet light of a high-pressure mercury lamp through a 313 nm bandpass filter and then through a 313 nm polarizing plate.
Two of the above substrates were prepared, and 4 μm bead spacers were dispersed on the liquid crystal alignment film of one of the substrates, after which a sealant (XN-1500T, manufactured by Kyoritsu Chemical Co., Ltd.) was applied. Next, the other substrate was attached so that the liquid crystal alignment film faces each other and the alignment direction was 180°, and then the sealant was thermally cured at 120°C for 90 minutes to prepare an empty cell. Negative liquid crystal (MLC-3022, manufactured by Merck & Co., Ltd.) was injected into this empty cell by the reduced pressure injection method to prepare a liquid crystal cell.
Moreover, the pretilt angle and the liquid crystal cell alignment were evaluated in the same manner as in Example 1-0.
<比較例1-1>
比較例1-0の[液晶セルの作製]において、基板法線方向から40°傾斜した角度から直線偏光紫外線を50mJ/cm2照射した後、さらに基板法線方向から40°傾斜した角度から50mJ/cm2照射を行った以外、比較例1-0と同様な方法により、液晶セルを得た。なお、1回目の照射と2回目の照射は、それぞれ法線方向から反対方向に40°傾斜させた。また、実施例1-0と同様な方法でプレチルト角と液晶セル配向性を評価した。
<Comparative Example 1-1>
A liquid crystal cell was obtained in the same manner as in Comparative Example 1-0 [Preparation of liquid crystal cell], except that linearly polarized ultraviolet light was irradiated at 50 mJ/ cm2 from an angle tilted at 40° from the substrate normal direction, and then irradiated at 50 mJ/ cm2 from an angle tilted at 40° from the substrate normal direction. The first and second irradiations were tilted at 40° in opposite directions from the normal direction. The pretilt angle and liquid crystal cell alignment were evaluated in the same manner as in Example 1-0.
<比較例1-2、1-3>
比較例1-0の[液晶セルの作製]において、2回目の偏光紫外線照射量を100mJ/cm2(比較例1-2)、150mJ/cm2(比較例1-3)に変更した以外、比較例1と同様な方法により、液晶セルを得た。また、実施例1-0と同様な方法でプレチルト角と液晶セル配向性を評価した。
<Comparative Examples 1-2 and 1-3>
In [Preparation of liquid crystal cell] of Comparative Example 1-0, except that the second polarized ultraviolet light irradiation dose was changed to 100 mJ/ cm2 (Comparative Example 1-2) or 150 mJ/ cm2 (Comparative Example 1-3), liquid crystal cells were obtained in the same manner as in Comparative Example 1. In addition, the pretilt angle and liquid crystal cell alignment were evaluated in the same manner as in Example 1-0.
<参考例7>
MA-2(17.18g、30.0mmol)とMAA(1.72g、20.0mmol)をNMP(108.51g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.25g、1.5mmol)を加え再び脱気を行った。この後55℃で13時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノールと純水=5/5の混合溶媒(1000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末(E)を得た。このポリマーの数平均分子量は22700、重量平均分子量は131000であった。
得られたメタクリレートポリマー粉末(E)(1.5g)にCHN(18.0g)を加え、室温で5時間攪拌して溶解させた。この溶液にCHN(18.0g)を加え攪拌することにより液晶配向剤(G1)を得た。
<Reference Example 7>
MA-2 (17.18 g, 30.0 mmol) and MAA (1.72 g, 20.0 mmol) were dissolved in NMP (108.51 g), and the mixture was degassed using a diaphragm pump. Then, AIBN (0.25 g, 1.5 mmol) was added and the mixture was degassed again. After that, the mixture was reacted at 55°C for 13 hours to obtain a methacrylate polymer solution. This polymer solution was dropped into a mixed solvent (1000 ml) of methanol and pure water = 5/5, and the obtained precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder (E). The number average molecular weight of this polymer was 22700 and the weight average molecular weight was 131000.
CHN (18.0 g) was added to the obtained methacrylate polymer powder (E) (1.5 g), and the mixture was stirred at room temperature for 5 hours to dissolve the mixture. CHN (18.0 g) was added to the solution and stirred to obtain a liquid crystal alignment agent (G1).
<比較例2-0~2-3>
参考例7で得られた液晶配向剤(G1)を用いて、焼成温度を120℃から150℃に変更した以外は比較例1-0~1-3と同様に試験を行った。
<Comparative Examples 2-0 to 2-3>
Using the liquid crystal alignment agent (G1) obtained in Reference Example 7, tests were carried out in the same manner as in Comparative Examples 1-0 to 1-3, except that the baking temperature was changed from 120°C to 150°C.
<参考例8>
MA-4(4.05g、8.0mmol)とMAA(2.75g、32.0mmol)をCHN(28.5g)中に溶解し、ダイアフラムポンプで脱気を行った後、AIBN(0.33g、2.0mmol)を加え再び脱気を行った。この後55℃で13時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をメタノールと純水=5/5の混合溶媒(1000ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をメタノールで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末(H)を得た。このポリマーの数平均分子量は47000、重量平均分子量は140000であった。
得られたメタクリレートポリマー粉末(H)(1.5g)にCHN(18.0g)を加え、室温で5時間攪拌して溶解させた。この溶液にCR-2(0.45g)とPGME(18.0g)を加え攪拌することにより液晶配向剤(I1)を得た。
<Reference Example 8>
MA-4 (4.05 g, 8.0 mmol) and MAA (2.75 g, 32.0 mmol) were dissolved in CHN (28.5 g), and the mixture was degassed using a diaphragm pump. AIBN (0.33 g, 2.0 mmol) was added and the mixture was degassed again. After that, the mixture was reacted at 55°C for 13 hours to obtain a methacrylate polymer solution. This polymer solution was dropped into a mixed solvent (1000 ml) of methanol and pure water = 5/5, and the obtained precipitate was filtered. This precipitate was washed with methanol and dried under reduced pressure in an oven at 40°C to obtain a methacrylate polymer powder (H). The number average molecular weight of this polymer was 47,000 and the weight average molecular weight was 140,000.
CHN (18.0 g) was added to the obtained methacrylate polymer powder (H) (1.5 g), and the mixture was stirred at room temperature for 5 hours to dissolve. CR-2 (0.45 g) and PGME (18.0 g) were added to the solution and stirred to obtain a liquid crystal alignment agent (I1).
<参考例9>
参考例(4)で得られたポリイミドポリマー溶液(H1)(14.0g)と、参考例(8)で得られた液晶配向剤(I1)(6.0g)を室温で5時間攪拌することにより液晶配向剤(J1)を得た。
<Reference Example 9>
The polyimide polymer solution (H1) (14.0 g) obtained in Reference Example (4) and the liquid crystal alignment agent (I1) (6.0 g) obtained in Reference Example (8) were stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent (J1).
<実施例6-0~7-3>
参考例1で得られた液晶配向剤(A1)の代わりに、表2に記載の液晶配向剤を用いた以外は、実施例1-0~1-3と同様に試験を行なった。評価結果を表2に記す。
<Examples 6-0 to 7-3>
Tests were carried out in the same manner as in Examples 1-0 to 1-3, except that the liquid crystal aligning agent shown in Table 2 was used instead of the liquid crystal aligning agent (A1) obtained in Reference Example 1. The evaluation results are shown in Table 2.
表1、2から明らかなように、実施例ではいずれも2回目の照射を行うことによりチルト角の書き換えが可能であり、書き換えた後の液晶配向性も良好であった。一方、比較例では、いずれもチルト角の書き換えが不可能であった。As is clear from Tables 1 and 2, in all of the Examples, the tilt angle could be rewritten by performing the second irradiation, and the liquid crystal alignment after rewriting was also good. On the other hand, in all of the Comparative Examples, the tilt angle could not be rewritten.
本発明の製造方法によれば、マルチドメイン液晶配向膜を効率的に製造することができる。また、得られたマルチドメイン液晶配向膜を用いた液晶表示素子は、ECB用液晶表示素子等に好適に用いることができる。According to the manufacturing method of the present invention, a multi-domain liquid crystal alignment film can be efficiently manufactured. Furthermore, a liquid crystal display element using the obtained multi-domain liquid crystal alignment film can be suitably used as an ECB liquid crystal display element, etc.
Claims (4)
液晶配向剤を基板上に塗布し、乾燥及び焼成により硬化膜を形成する工程、
前記硬化膜に紫外線を斜め方向から照射する1回目の照射によりプレチルト角を形成する工程、並びに、
前記1回目の照射工程により得られた、紫外線照射後の硬化膜に、前記1回目の照射工程における照射方向とは異なる方向から紫外線を照射する2回目の照射により、1回目の照射により形成されたプレチルト角とは異なるプレチルト角を形成する工程をこの順番で含み、
前記1回目の照射工程と前記2回目の照射工程の少なくとも一方は、遮光された領域と遮光されていない領域とを含むマスクを介して行われることにより、配向方向が異なる領域が複数形成されたマルチドメイン液晶配向膜を得ることを特徴とし、
前記2回目の照射工程のみが前記マスクを介して行われる場合、前記2回目の照射工程における紫外線の照射量が、前記1回目の照射工程における紫外線の照射量よりも多く、
前記1回目の照射工程のみが前記マスクを介して行われる場合、前記2回目の照射工程における紫外線の照射量が、前記1回目の照射工程における紫外線の照射量よりも少なく、
前記液晶配向剤は、(A)下記式(pa-1)
で表される光配向性基と熱架橋性基Aとを有する重合体、及び
溶媒を含有し、かつ
前記液晶配向剤は、
Z1:前記(A)重合体が熱架橋性基Bをさらに有するか、及び/又は
Z2:(B)分子内に2個以上の熱架橋性基Bを有する化合物をさらに含有する
(熱架橋性基A及び熱架橋性基Bは、それぞれ独立に、カルボキシル基、アミノ基、アルコキシメチルアミド基、ヒドロキシメチルアミド基、水酸基、エポキシ部位含有基、オキセタニル基、チイラニル基、イソシアネート基及びブロックイソシアネート基からなる群から選ばれる基であって、熱架橋性基Aと熱架橋性基Bとが熱により架橋反応するように選択されてなり、ただし、熱架橋性基A及び熱架橋性基Bは互いに同じでもよい。)
ことを特徴とする、方法。 A method for manufacturing a multi-domain liquid crystal alignment film, the method comprising the steps of:
A step of applying a liquid crystal alignment agent onto a substrate, and forming a cured film by drying and baking;
forming a pretilt angle by a first irradiation of the cured film with ultraviolet light from an oblique direction; and
the step of irradiating the cured film after the ultraviolet irradiation obtained in the first irradiation step with ultraviolet light in a direction different from the irradiation direction in the first irradiation step, thereby forming a pretilt angle different from the pretilt angle formed by the first irradiation, in this order;
At least one of the first irradiation step and the second irradiation step is performed through a mask including a light-shielded region and a light-unshielded region, thereby obtaining a multi-domain liquid crystal alignment film having a plurality of regions with different alignment directions;
When only the second irradiation step is performed through the mask, the irradiation amount of the ultraviolet light in the second irradiation step is greater than the irradiation amount of the ultraviolet light in the first irradiation step,
When only the first irradiation step is performed through the mask, the irradiation amount of the ultraviolet light in the second irradiation step is smaller than the irradiation amount of the ultraviolet light in the first irradiation step,
The liquid crystal aligning agent is represented by the following formula (pa-1):
and a solvent, and the liquid crystal alignment agent is
Z1: the polymer (A) further has a thermally crosslinkable group B, and/or Z2: (B) further contains a compound having two or more thermally crosslinkable groups B in the molecule (thermally crosslinkable group A and thermally crosslinkable group B are each independently a group selected from the group consisting of a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a blocked isocyanate group, and are selected so that the thermally crosslinkable group A and the thermally crosslinkable group B undergo a crosslinking reaction by heat, but the thermally crosslinkable group A and the thermally crosslinkable group B may be the same as each other).
A method comprising:
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