JP2004131666A - Optically active vinyl ether and cholesteric liquid crystal polymer derived therefrom - Google Patents
Optically active vinyl ether and cholesteric liquid crystal polymer derived therefrom Download PDFInfo
- Publication number
- JP2004131666A JP2004131666A JP2002300067A JP2002300067A JP2004131666A JP 2004131666 A JP2004131666 A JP 2004131666A JP 2002300067 A JP2002300067 A JP 2002300067A JP 2002300067 A JP2002300067 A JP 2002300067A JP 2004131666 A JP2004131666 A JP 2004131666A
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- Prior art keywords
- diyl
- formula
- hydrogen
- copolymer
- replaced
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 title abstract description 25
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 title abstract description 24
- 229920000106 Liquid crystal polymer Polymers 0.000 title abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 49
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 29
- 150000002367 halogens Chemical class 0.000 claims abstract description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 89
- 229920001577 copolymer Polymers 0.000 claims description 86
- -1 pyridine-2,5-diyl Chemical group 0.000 claims description 60
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- 239000001257 hydrogen Substances 0.000 claims description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 32
- 230000003287 optical effect Effects 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000004973 liquid crystal related substance Substances 0.000 claims description 26
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 18
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 230000003098 cholesteric effect Effects 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- 238000002983 circular dichroism Methods 0.000 claims description 11
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 230000001747 exhibiting effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 17
- 239000007788 liquid Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000001939 inductive effect Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 48
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 34
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 29
- 239000000203 mixture Substances 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000011295 pitch Substances 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- LKUOJDGRNKVVFF-UHFFFAOYSA-N 4-(2,5-dioxopyrrol-1-yl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N1C(=O)C=CC1=O LKUOJDGRNKVVFF-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 229920005603 alternating copolymer Polymers 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- QGEMDVYNSYDQQK-UHFFFAOYSA-N furan;pyrrole-2,5-dione Chemical compound C=1C=COC=1.O=C1NC(=O)C=C1 QGEMDVYNSYDQQK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000006880 cross-coupling reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- RTCUCQWIICFPOD-VIFPVBQESA-N (1s)-1-naphthalen-1-ylethanamine Chemical compound C1=CC=C2C([C@@H](N)C)=CC=CC2=C1 RTCUCQWIICFPOD-VIFPVBQESA-N 0.000 description 2
- CGEOYYBCLBIBLG-UHFFFAOYSA-N (4-carbonochloridoylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C(Cl)=O)C=C1 CGEOYYBCLBIBLG-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- VVYHWYFUTOHXRH-UHFFFAOYSA-N 4-(6-hydroxyhexoxy)benzoic acid Chemical compound OCCCCCCOC1=CC=C(C(O)=O)C=C1 VVYHWYFUTOHXRH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical class CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- FCMCSZXRVWDVAW-UHFFFAOYSA-N 6-bromo-1-hexanol Chemical compound OCCCCCCBr FCMCSZXRVWDVAW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)(*)Nc(c(N)c(c(C(C)(C)OC(C)(C)N)c1)N)c1N Chemical compound CC(C)(*)Nc(c(N)c(c(C(C)(C)OC(C)(C)N)c1)N)c1N 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- 238000006751 Mitsunobu reaction Methods 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 229940117803 phenethylamine Drugs 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 2
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- RTCUCQWIICFPOD-SECBINFHSA-N (1r)-1-naphthalen-1-ylethanamine Chemical compound C1=CC=C2C([C@H](N)C)=CC=CC2=C1 RTCUCQWIICFPOD-SECBINFHSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-SSDOTTSWSA-N (R)-1-phenylethanol Chemical compound C[C@@H](O)C1=CC=CC=C1 WAPNOHKVXSQRPX-SSDOTTSWSA-N 0.000 description 1
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- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明の第１は、共重合体に誘導しても液晶性を保つ、選択反射帯域が可視光近辺であるような短いピッチのコレステリックフィルムに必要な強いねじれを誘起する光学活性なビニルエーテルに関する。第２は、大面積体も容易に効率よく製造できる塗布方式に適用でき、配向性、耐熱性に優れたグランジャン配向するようなコレステリック相を持つマレイミド−ビニルエーテル共重合体およびそれを用いた光学素子である。第３は、配向した共重合体に、電磁波の照射を行うことによりコレステリック相を固定化するフィルムの製造法である。
【０００２】
【従来の技術】
コレステリック液晶重合体を配向した光学フィルムは、円偏光二色性を示す。そこで、液晶表示素子における色補償板、光学位相板、ノッチフィルターなどに用いることが提案されている。
【０００３】
このようなコレステリック液晶フィルムを製造するには、ラビング処理した配向膜を有する２枚の基板を均一な間隔を保つようにギャップ剤などを用いて張り合わせ、そこへ低分子の重合性コレステリック液晶組成物を注入して、コレステリック相のモノドメイン状態に配向させた後、紫外線等により重合処理して配向フィルムを製造する方法が知られている（例えば、特許文献１参照。）。この方法で得られるフィルムは熱による配向に変化がほとんどなく、その結果として、熱による光学変化が少ない耐熱性に優れたフィルムを製造できる。ところが、フィルムの膜厚はモノマーを配向させる基板に依存するため、大画面の配向フィルムを製造するには、大きな基板が必要となり、大面積になれば基板の均一な間隔を制御することが難しくなり、均一な膜厚制御したフィルムの製造が難しかった。すなわち、耐熱性の高いフィルムの製造法としては優れているが、製造効率に劣っていた。
【０００４】
一方、均一な膜厚を大画面で保ったコレステリック液晶フィルムを効率良く製造する方法として、コレステリック液晶重合体の溶液を、配向膜が形成された基板に均一に塗布して乾燥後、ガラス転移温度以上に加熱し、ついで冷却して配向させる方法が提案された（例えば、特許文献２参照。）。しかしながら、このようにして製造したコレステリック液晶重合体のフィルムは、配向がガラス転移点温度以下では固定化されるが、ガラス転移点温度以上の温度条件ではフィルムにかかる引っ張り、ねじれ等の応力に対して、配向が乱れるなどの問題があった。すなわち、この方法は製造効率には優れているが、フィルムの耐熱性が乏しかった。
【０００５】
フィルムの耐熱性を改善する目的で重合体を構成するモノマー単位に架橋基を含有する共重合体も提案された（例えば、特許文献３参照。）が、構成モノマーの種類が多く、また重合物に対してジアクリル化合物などの２官能基を有する架橋性のモノマーを添加しなくてはならないなど、材料の構成が複雑になっていて、工業的ではなかった。
【０００６】
【特許文献１】
特開平６−２８１８１４号公報
【特許文献２】
特開平９−１３３８１０号公報
【特許文献３】
特開２０００−３３６３６２公報
【０００７】
【発明が解決しようとする課題】
本発明は、液晶重合体へ誘導しても液晶性を損なわず、強いねじれを誘起させる光学活性ビニルエーテルである。
また、コレステリック液晶重合体の塗布方式に適用でき、従って大面積体も容易に効率よく製造できて、しかも架橋を必要とせず、紫外線の照射により耐熱性に優れた配向フィルムを形成しうるコレステリック液晶重合体である。
さらに、コレステリック液晶重合体配向フィルムの製造方法を提供する。
【０００８】
【課題を解決するための手段】
本発明者は上記の目的を解決すべく、コレステリック液晶重合体の構造、重合体の原料となるモノマーの構造、フィルムの製造法などを鋭意検討したところ、液晶性基を有するマレイミドと光学活性基を有するビニルエーテルの共重合反応により得られるコレステリック液晶重合体が大画面の均一な塗布に適しており、しかも、塗布、乾燥後、加熱処理することで容易にグランジャン配向すること、さらに、できた配向フィルムに電磁波を照射することでフィルムの配向が固定化され、耐熱性が向上することを見い出し、本発明を完成した。
【０００９】
本発明は、下記の構成からなる。
１． 式（１）で表される光学活性な化合物。
２． 式（１）において、ｏが０である項１記載の化合物。
３． 式（１）において、ｏが１である項１記載の化合物。
４． 式（１）において、ｐが３〜６である項１〜３のいずれか１項記載の化合物。
【００１１】
５． 式（２）で表される化合物と項１〜４のいずれか１項記載の化合物との共重合体。
【００１２】
６． 式（ａ）〜（ｆ）で表される化合物と項１〜４のいずれか１項記載の化合物との共重合体。
【００１３】
７． 式（３）で表されるモノマー単位の骨格と式（４）で表されるモノマー単位で表される骨格とからなる共重合体。
８． 式（４）において、ｏが０である項７記載の共重合体。
９． 式（４）において、ｏが１である項７記載の共重合体。
１０． 式（４）において、ｐが３〜６である項７〜９のいずれか１項記載の共重合体。
【００１５】
１１． 式（３）において、ｍが０である項７〜１０のいずれか１項記載の共重合体。
１２． 式（３）において、ｍが１である項７〜１０のいずれか１項記載の共重合体。
１３． 項７記載の式（３）で表されるモノマー単位６０〜９５モル％と、項７記載の式（４）で表されるモノマー単位５〜４０モル％からなる項７〜１２のいずれか１項記載の共重合体を成分とし、重量平均分子量が２０００〜５万である共重合体。
【００１６】
１４． 項７〜１３のいずれか１項記載の共重合体からなる光学素子。
１５． コレステリック相を示し、その共重合体をグランジャン配向させた円偏光二色性を有する項１４記載の光学素子。
１６． 可視光域にて円偏光二色性を示す項１４または１５記載の光学素子。
【００１７】
１７． 円偏光二色性を示す波長域が相違する２層以上の重合体からなる項１４〜１６のいずれか１項記載の光学素子。
１８． 項１４〜１７のいづれか１項記載の光学素子に、円偏光を直線偏光に変えることが可能な位相差層を設けた光学部材。
１９． 項７〜１３のいずれか１項に記載の重合体を含有する光学補償膜。
【００１８】
２０． 項７〜１３のいずれか１項に記載の重合体を含有する光書き込み記録材料。
２１． 項７〜１３のいずれか１項に記載の重合体を含有する液晶配向膜。
２２． 項７〜１３のいづれか１項に記載の共重合体を配向処理した後、電磁波の照射により配向を固定化する配向フィルムの製造方法。
【００１９】
【発明の実施形態】
本発明の第一は、式（１）で表されるビニルエーテルであり、光学活性体である。本発明の第二は、式（３）で表されるモノマー単位と式（４）で表されるモノマー単位を構成単位として有する側鎖型のコレステリック液晶共重合体である。以下の説明においては、本発明のコレステリック液晶共重合体を共重合体と表記することがある。そして、式（３）の部分構造である下記の基を液晶骨格（ＭＳＧ）と称することがある。
【００２０】
共重合体は少なくとも２種類のモノマーの共重合反応により製造する。それぞれのモノマーは共重合体の機能発現に以下の効果がある。
１）式（１）で表される光学活性なビニルエーテルは、マレイミドとの共重合性に優れており、また、ねじれを誘起する力が大きい。そこで、マレイミドに対して４０モル％以下の組成で、選択反射帯域が可視光波長近辺にあるような短いピッチに調整できる。また、マレイミドとの混合比率を小さくできるので、共重合体の液晶性を損ないにくい。
【００２２】
２）式（２）で表されるマレイミドは液晶性を高めるために液晶骨格（ＭＳＧ）をメチレン鎖などのスペーサを用いてマレイミドまたはフェニルマレイミドに対してＮ置換しており、その混合比率または種類により共重合体の液晶温度範囲を調整できる。
【００２４】
原料マレイミドである式（２）および、モノマー単位となる式（３）の式中、Ｒ１は水素、フッ素、塩素、−ＮＣＯ、−ＣＮまたは炭素数１〜２０のアルキルであり、このアルキルにおいて、任意の−ＣＨ２−は、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、または−ＣＯ−で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく；Ａ１、Ａ２およびＡ３、独立して、１，４−シクロへキシレン、少なくとも１つの水素がフッ素で置き換えられた１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がハロゲンで置き換えられた１，４−フェニレン、ピリジン−２，５−ジイル、ピリダジン−３，６−ジイル、ピリミジン−２，５−ジイル、ナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、５，６，７，８−テトラヒドロナフタレン−２，６−ジイル、フルオレン−２，７−ジイル、または１，３−ジオキサン−２，５−ジイルであり；Ａ４は単結合、１，４−フェニレン、少なくとも１つの水素がメチル、またはハロゲンで置き換えられた１，４−フェニレンであり；Ｚ１およびＺ２は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＨ２Ｏ−、−ＯＣＨ２−、−ＣＨ＝ＣＨ−、−ＣＨ２ＣＨ２−、または−Ｃ≡Ｃ−であり；Ｚ３は単結合、−ＣＯＯ−、−ＯＣＯ−、または−Ｏ−であり；ｍは１または０であり；そして、ｎは１〜２０の整数である。
【００２６】
好ましいＲ１は、水素、フッ素、塩素、−ＮＣＯ、−ＣＮ、炭素数１〜３のフッ素化アルキル、炭素数１〜３のフッ素化アルキルオキシ、炭素数１〜１２の直鎖のアルキル、および炭素数１〜１２の直鎖のアルコキシである。好ましいフッ素化アルキルおよびフッ素化アルキルオキシは、−ＣＦ３、−ＣＦ２Ｈ、−ＯＣＦ３、および−ＯＣＦ２Ｈである。好ましいアルキルおよびアルコキシは、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、メトキシ、エトキシ、プロピルオキシ、ブチルオキシ、ペンチルオキシ、ヘキシルオキシ、ヘプチルオキシ、オクチルオキシ、ノニルオキシ、およびデシルオキシである。Ｒ１が−ＣＦ３、−ＯＣＦ３、−ＮＣＯ、フッ素、または塩素であるときの液晶骨格は、化合物（２）が正の誘電率異方性を有し易い構造である。化合物（２）の特性は、共重合体の特性に相関する。
【００２７】
式（２）中のＡ１〜Ａ４は環構造の２価基である。好ましいＡ１、Ａ２またはＡ３の例を次に示す。
【００２８】
Ａ４は単結合、１，４−フェニレン、少なくとも１つの水素がメチル、またはハロゲンで置き換えられた１，４−フェニレンである。好ましいＡ４の例として、単結合以外のより具体的な構造を以下に示す。
【００３０】
式（２）および式（３）中のＺ１およびＺ２は結合基である。好ましいＺ１またはＺ２は、単結合、−ＣＯＯ−、−ＯＣＯ−、−Ｃ≡Ｃ−、−ＣＨ２Ｏ−、−ＯＣＨ２−、および−ＣＨ２ＣＨ２−である。化合物（１）において、Ｚ１およびＺ２の少なくとも１つが、単結合、−ＣＯＯ−、−ＯＣＯ−、または−Ｃ≡Ｃ−である場合は、光学異方性値の大きな重合体が得られる傾向がある。Ｚ１およびＺ２の少なくとも１つが、−ＣＨ２Ｏ−、−ＯＣＨ２−、または−ＣＨ２ＣＨ２−である場合は、液晶骨格の分子間力が減少する傾向があるので、比較的小さい粘度の共重合体が得られる。
【００３２】
Ａ１〜Ａ３とＺ１およびＺ２の組み合わせについて説明する。室温において共重合体が比較的低い温度領域に液晶相を有するためには、液晶骨格においてｍが０であることが好ましい。好ましい液晶骨格を、以下に示す。
【００３３】
これらの式中のＲ１、Ａ１、およびＡ２の意味は、前記と同じである。
【００３５】
ｍが１である液晶骨格は３つの環を有する。３環の液晶骨格を有する共重合体は、液晶相の上限温度が一般的に高い。３環構造であるときの、Ａ１〜Ａ３とＺ１およびＺ２の好ましい組み合わせを以下に示す。
【００３６】
これらの式中のＲ１、Ａ１、Ａ２およびＡ３の意味は、前記と同じである。
【００３９】
式（１）および式（４）において、共重合体がコレステリック相を有するために好ましいｎまたはｐは１〜２０の整数である。より好ましいｎまたはｐは３〜１１である。そして、共重合体が１，４−シクロへキシレンまたは１，３−ジオキサン−２，５−ジイルを有する場合には、その立体配置はシス型よりトランス型が好ましい。化合物の物性に大きな差異がないので、共重合体は２Ｈ（重水素）、１３Ｃなどの同位体を天然存在比の量より多く含んでもよい。
【００４０】
また、式（２）および式（３）において、共重合体が液晶相を有するために好ましいｎは１〜２０の整数である。より好ましいｎは３〜１１である。化合物（２）が１，４−シクロへキシレンまたは１，３−ジオキサン−２，５−ジイルを有する場合には、その立体配置はシス型よりトランス型が好ましい。化合物の物性に大きな差異がないので、化合物（２）は２Ｈ（重水素）、１３Ｃなどの同位体を天然存在比の割合より多く含んでもよい。
【００４１】
化合物（２）の好ましい例は化合物（２−１）〜（２−２９）である。
【００４４】
化合物（２）のさらに好ましい例は、化合物（２−１）〜（１−２９）において、Ａ１が１，４−シクロへキシレンまたは１，４−フェニレンであり、Ａ２が１，４−フェニレンまたは少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレンである。Ａ２が１，４−フェニレンであると相溶性の点で好ましい 。Ａ２が少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレンであると大きな誘電率異方性の点で好ましい。
【００４５】
光学活性ビニルエーテルにおける式（１）、および光学活性基を有するモノマー単位である式（４）において、Ｒ＊は、式（Ｐｈ１）、（Ｐｈ２）、（Ｐｈ３）、（Ｐｈ４）、（Ｐｈ５）、または（Ｐｈ６）で表される基であり、その式中の＊は不斉炭素であり；Ｚ４は単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ２Ｏ−、−ＯＣＨ２−、−ＣＨ＝ＣＨ−、−ＣＨ２ＣＨ２−、または−Ｃ≡Ｃ−であり；Ｇ１、Ｇ２、Ｇ３、Ｇ４、Ｇ５、またはＧ６はそれぞれ独立に水素、ハロゲンまたはメチルであり；ｏは１または０であり、；そして、ｐは１〜２０の整数である。
【００４６】
式（１）および式（４）中、Ｚ４は単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ２Ｏ−、−ＯＣＨ２−、−ＣＨ＝ＣＨ−、−ＣＨ２ＣＨ２−、または−Ｃ≡Ｃ−が好ましいが、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ２ＣＨ２−または−Ｃ≡Ｃ−が共重合体の液晶相温度範囲の上限を高くする効果が期待できるので、より好ましい。
【００４７】
Ｇ１、Ｇ２、Ｇ３、Ｇ４、Ｇ５またはＧ６はそれぞれ独立に水素、ハロゲンまたはメチルである。フェニレンに置換した特に好ましい例を次に示す。
【００４８】
本発明の共重合体には、他の共重合体成分となる化合物または、他の共重合体骨格を含んでもよい。
【００５０】
式（１）で表される光学活性なビニルエーテル誘導体の製造法を示す。
＜式（１）において、Ｒ＊＝（Ｐｈ１）、Ｚ４＝−ＣＯＯ−の化合物の製造＞
先ず、ω−ブロモアルカノールと４−ヒドロキシ安息香酸を炭酸カリウム、水酸化ナトリウム、水酸化カリウムなどの塩基によりエーテル化を行うことでω−ヒドロキシアルコキシ安息香酸誘導体［ａ］を得る。
【００５１】
４−アセトキシ安息香酸誘導体を塩化チオニルあるいはオキサリルクロライドなどの塩素化剤で対応する酸クロライドとし、Ｒ体またはＳ体の光学活性なフェネチルアミン［ＯＰ１］とピリジンあるいはトリエチルアミンなどの塩基の存在下でアミド化、さらにアンモニア、ジエチルアミンにより加溶媒分解することでフェノール誘導体［ｂ］を製造する。ω−ヒドロキシアルコキシ安息香酸誘導体［ａ］とフェノール誘導体［ｂ］をジシクロヘキシルカルボジイミドあるいは１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド塩酸塩などの縮合剤によりエステル化することでアルコール誘導体［ｃ］を得る。パラジウム触媒を用いて、［ｃ］をビニルエーテル化することにより化合物（１−１）を製造する。
【００５３】
＜一般式（１）において、Ｒ＊＝（Ｐｈ１）、Ｚ４＝−≡−の化合物の製造＞
ｐ−ブロモ安息香酸クロライド誘導体と［ＯＰ１］をピリジンあるいはトリエチルアミンなどの塩基の存在下でアミド化を行い対応するアミド［ｄ］を得る。トリメチルシリルアセチレンとのクロスカップリング反応、脱トリメチルシリル化反応、［ｅ］とのクロスカップリング反応、脱保護により［ｆ］を得る。次に［ｆ］をパラジウム触媒をもちいてビニルエーテル化することにより光学活性なビニルエーテル誘導体（１−２）を製造する。
【００５５】
＜式（１）において、Ｒ＊＝（Ｐｈ１）、Ｚ４＝−ＣＨ２ＣＨ２−の化合物の製造＞
化合物（１−３）は［ｆ］をパラジウム炭素などを触媒にして水素添加した後、ビニルエーテル化することで製造する。
【００５７】
＜式（１）において、Ｒ＊＝（Ｐｈ１）、Ｚ４＝単結合の化合物の製造＞
アミド［ｄ］とホウ素酸誘導体［ｇ］とパラジウム触媒を用いたクロスカップリング反応により（１−４）を製造する。
【００５９】
＜式（１）において、Ｒ＊＝（Ｐｈ１）、ｎ＝０の化合物の製造＞
フェノール誘導体［ｂ］とω−ブロモアルカノールを炭酸カリウム、水酸化ナトリウム、水酸化カリウムなどの塩基によりエーテル化を行うことでアルコール誘導体［ｈ］を得る。パラジウム触媒を用いて［ｈ］をビニルエーテル化することにより光学活性なビニルエーテル誘導体（１−５）を製造する。
【００６１】
Ｒ＊＝（Ｐｈ２）の化合物を製造するには（Ｒ）−（＋）−１−（ナフチル）エチルアミンまたは（Ｓ）−（−）−１−（ナフチル）エチルアミン
Ｒ＊＝（Ｐｈ３）の化合物を製造するには（Ｒ）−（−）−２−フェニルグリシンメチルエステルまたは（Ｓ）−（＋）−２−フェニルグリシンメチルエステル
Ｒ＊＝（Ｐｈ４）の化合物を製造するには（Ｒ）−（＋）−１−フェニルエタノールまたは（Ｓ）−（−）−１−フェニルエタノール
Ｒ＊＝（Ｐｈ５）の化合物を製造するには、（Ｒ）−１−ビフェニルエタノールまたは（Ｓ）−１−ビフェニルエタノール
Ｒ＊＝（Ｐｈ６）の化合物を製造するには（１Ｒ、２Ｓ、５Ｒ）−（−）−メントールまたは（１Ｓ、２Ｒ、５Ｓ）−（−）−メントールを、それぞれ［ＯＰ１］の代わりに用いる。このようにして（ＫＶ１）〜（ＫＶ５５）の化合物を製造する。
【００６３】
＜マレイミド誘導体モノマーの製造＞
式（２）で表されるマレイミド誘導体の製造法を示す。
＜式（２）においてＺ３＝単結合、Ａ４＝単結合の化合物の製造＞
マレイミドとフランとのＤｉｅｌｓ−Ａｌｄｅｒ反応によって、マレイミドのフラン付加体［ｉ］を製造する。液晶骨格（ＭＳＧ）を有し末端がヒドロキシル基である化合物とω−ブロモアルカノールとを、塩基を用いてエーテル化することにより、アルコール誘導体［ｊ］を製造する。塩基の例は、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、水素化ナトリウムなどである。マレイミドのフラン付加体［ｉ］とアルコール誘導体［ｊ］を光延反応によりＮ−アルキル化した後、ｒｅｔｒｏ−Ｄｉｅｌｓ−Ａｌｄｅｒ反応により熱分解して化合物（２−Ａ）を製造する。
【００７０】
＜式（２）においてＺ３＝−ＯＣＯ−、Ａ４＝１，４−フェニレンの化合物の製造＞
無水マレイン酸とパラ置換アニリン誘導体との反応によって［ｋ］を製造する。続いて［ｋ］の分子内縮合反応によりＮ−４−ヒドロキシ、またはＮ−４−カルボキシフェニルマレイミド［ｌ］を製造する。Ｙ＝ＣＯＯＨであるフェニルマレイミド［ｌ］とアルコール誘導体［ｊ］をエステル化反応により化合物（２−Ｂ）を製造する。
【００７２】
＜式（２）においてＺ３＝−Ｏ−、Ａ４＝１，４−フェニレンの化合物の製造＞
Ｙ＝ＯＨであるフェニルマレイミド［ｌ］と［ｊ］を光延反応によりエーテル化することで化合物（２−Ｃ）を製造できる。
【００７４】
＜式（２）においてＺ３＝−ＣＯＯ−、Ａ４＝１，４−フェニレンの化合物の製造＞
液晶骨格（ＭＳＧ）を有し末端がヒドロキシル基である化合物とω−ブロモアルカン酸とを塩基を用いてエーテル化することによりカルボン酸誘導体を製造する。Ｙ＝ＯＨであるフェニルマレイミド［ｌ］とエステル化することで化合物（５−Ｄ）を製造する。
【００７６】
＜マレイミド−ビニルエーテル共重合体の製造＞
次に、本発明のマレイミド−ビニルエーテル共重合体について説明する。光学活性ビニルエーテル（式（１））とマレイミド（式（２））の組成物を重合させると共重合体が得られる。共重合体は、側鎖に液晶骨格を有するモノマー単位（３）、コレステリック相の螺旋ピッチと調整するための光学活性なモノマー単位（４）により構成されている。共重合体の液晶性を保つためには、式（３）のモノマー単位を４０％以上にすることが好ましい。コレステリック液晶相の螺旋ピッチを十分に短くするためには、式（４）のモノマー単位が４０モル％以下にすることが好ましい。従って、本発明の共重合体は、式（３）で表されるモノマ単位６０〜９５モル％と、式（４）で表されるモノマー単位５〜４０モル％からなる共重合体を成分とする重合体が好ましい。
【００７８】
共重合体における構成単位の配列は、ランダム、ブロック、交互、グラフトなどのいずれであってもよい。共重合体の分子量は、過小では成膜性に乏しくなり、過大では液晶としての配向性、特にラビング配向膜によるモノドメイン化が乏しくなって均一な配向状態が形成しにくくなることから、重量平均分子量２０００から５万が好ましい。
【００７９】
共重合体は、熱または光により重合させて製造する。熱重合の反応温度は０〜１５０℃、反応時間は１〜１００時間であり、通常ラジカル重合開始剤を用いる。ラジカル重合開始剤の例は、過酸化ベンゾイル、ジイソプロピルパーオキシジカーボネート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシピバレート、ｔ−ブチルパーオキシジイソブチレート、過酸化ラウロイル、２，２′−アゾビスイソ酪酸ジメチル（ＭＡＩＢ）、ジｔ−ブチルパーオキシド（ＤＴＢＰＯ）、アゾビスイソブチロニトリル（ＡＩＢＮ）、アゾビスシクロヘキサンカルボニトリル（ＡＣＮ）などである。
【００８０】
光または電子線等の照射による重合においては、通常光ラジカル重合開始剤を用いる。光ラジカル重合開始剤の例は、チバ・スペシャリティー・ケミカル（株）の製品のうちから、ダロキュアー１１７３（２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン）、イルガキュアー１８４（１−ヒドロキシシクロヘキシルフェニルケトン）、イルガキュアー６５１（２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン）、イルガキュアー５００、イルガキュアー２９５９、イルガキュアー９０７、イルガキュアー３６９、イルガキュアー１３００、イルガキュアー８１９、イルガキュアー１７００、イルガキュアー１８００、イルガキュアー１８５０、ダロキュアー４２６５、イルガキュアー７８４などが挙げられる。
【００８１】
光ラジカル重合開始剤のその他の例は、ｐ−メトキシフェニル−２，４−ビス（トリクロロメチル）トリアジン、２−（ｐ−ブトキシスチリル）−５−トリクロロメチル−１，３，４−オキサジアゾール、９−フェニルアクリジン、９，１０−ベンズフェナジン、ベンゾフェノン／ミヒラーズケトン混合物、ヘキサアリールビイミダゾール／メルカプトベンズイミダゾール混合物、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、ベンジルジメチルケタール、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノプロパン−１−オン、２，４−ジエチルキサントン／ｐ−ジメチルアミノ安息香酸メチル混合物などである。
【００８２】
共重合体は、アニオン重合法、配位重合法、またはリビング重合法によっても製造することができる。これらの重合法で用いる好ましい触媒は、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔ−ブチルリチウム、ｔ−ブチルリチウム−トリアルキルアルミニウムなどのアルカリ金属アルキル、アルミニウム化合物、遷移金属化合物などである。
【００８３】
重合反応には溶剤を用いてもよい。好ましい溶剤は、ベンゼン、トルエン、キシレン、メシチレン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、テトラヒドロフラン、１，４−ジオキサン、Ｎ−メチルピロリドン、ジメチルホルムアミド、ジメチルスルホキシドなどである。これらの少なくとも２つを混合した溶剤を用いてもよい。
【００８４】
＜光学素子の製造＞
本発明の配向フィルムの製造方法は、共重合体を配向処理した後、紫外線照射により配向の固定化処理をするものである。このような配向フィルムの形成は有機溶剤に溶解した共重合体を、配向処理した基材に塗布し、これをガラス転移点以上の温度に加熱し、次いで放冷することにより、均一に配向した重合体の薄膜（光学異方性薄膜）を形成させ、さらに紫外線の照射により配向を固定化処理をすることにより製造する。
【００８５】
共重合体の溶液を調製するに際して用いる溶媒としては、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドジメチルアセタール、テトラヒドロフラン、クロロホルム、１，４−ジオキサン、ビス（メトキシエチル）エーテル、γ−ブチロラクトン、テトラメチル尿素、トリフルオロ酢酸、トリフルオロ酢酸エチル、ヘキサフルオロ−２−プロパノールなどである。しかし、使用可能な溶剤はこれらに制限されない。これらの溶剤同士、または、これらの溶剤と、アセトン、ベンゼン、トルエン、ヘプタン、塩化メチレンなどの一般的な有機溶剤との混合物も用いることができる。
【００８６】
基材との重畳物からなる配向フィルムとする場合、ガラス板またはプラスチックフィルム、位相差板等の延伸フィルムや偏光板の如き光学フィルムなどを用いる。プラスチックフィルムの例としては、トリアセチルセルロース、ポリビニルアルコール、ポリイミド、ポリエステル、ポリアリレート、ポリエーテルイミド、ポリエチレンテレフタレートである。その他の具体的な商品名ではＪＳＲ（株）製の「アートン」、日本ゼオン（株）製の「ゼオネックス」および「ゼオノア」、三井化学（株）製の「アペル」などを用いることができる。
【００８７】
共重合体の溶液の塗布方法は、スピンコート法、ロールコート法、フローコート法、プリント法、マイクログラビアコート法、グラビアコート法、ワイヤーバーコード法、デップコート法、スプレーコート法、メニスカスコート法や流延成膜法など方法で薄膜展開し、それを乾燥処理して溶媒を除去する方法などにより行うことができる。
【００８８】
配向処理面としては、例えば一般に用いられるポリイミドやポリビニルアルコールなどからなる薄膜を形成して、それをレーヨン布などでラビング処理したものや、酸化ケイ素を斜方蒸着したもの、あるいは延伸フィルムなどが用いられる。
【００８９】
共重合体の溶液を基材に塗布、乾燥した後、配向させるために加熱処理を行う。加熱処理は共重合体のガラス転移点から等方相を呈する状態までの温度範囲で一定時間、加熱することにより行う。配向処理を終えた展開層は、紫外線または電子線等の電磁波を照射することにより配向の固定を行うが、この際、光重合開始剤などを添加する必要はない。紫外線を用いるには共重合体の吸収のない３００ｎｍより長波長が好ましく。電子線を用いる場合は、照射量が多すぎると共重合体が崩壊するので１〜２００Ｍｒａｄが好ましい。電磁波照射の際の温度は、配向処理の温度と同じ温度が好ましい。
【００９０】
配向を固定した薄膜の厚さは所望の位相差値により異なり、その位相差値は光学異方性薄膜の複屈折率により異なる。好ましい位相差値は大体０．０５〜５０μｍの範囲であり、より好ましい位相差値は大体０．１〜２０μｍの範囲である。そして、さらに好ましい位相差値は大体０．５〜１０μｍの範囲である。光学異方性薄膜のヘイズ値は、１．５％以下、より好ましくは１．０％以下であり、透過率で８０％以上、より好ましくは８５％以上である。可視光領域で透過率がこれらの割合を満たすことが好ましい。ヘイズ値の範囲１．５％以下は、偏光性能に問題を生じさせないために好ましい条件である。透過率の範囲８０％以上は、この光学異方性薄膜を液晶表示素子に用いるとき、明るさを維持するために好ましい条件である。
【００９１】
本発明による好ましい円偏光分離板は、上下の層で螺旋ピッチが異なる２層以上のコレステリック液晶重合体層の密着重畳体であり、上下の層は螺旋ピッチの異なるコレステリック液晶重合体で構成され、厚さ方向に螺旋ピッチが多段階に変化したものである。これにより広い波長領域の光を反射できる円偏光分離板を製造できる。反射光の波長域は可視領域の１５０ｎｍ以上、好ましくは１８０ｎｍ以上、特に２２０ｎｍから全可視光域の帯域の及ぶものがよい。
【００９２】
本発明の円偏光分離板に１／４波長板などの直線偏光化する層を設けることにより、円偏光分離板より出射した円偏光の位相を変化させて直線偏光に変換する。これにより偏光板による光の吸収ロスを低減して液晶表示装置の輝度の向上を達成できる。
【００９３】
【実施例】
以下、実施例により本発明を詳細に説明する。実施例中に記載した相転移温度において、Ｃは結晶、Ｎはネマチック相、Ｃｈはコレステリック相、ＳｍＡはスメクチックＡ相、ＳｍＸは未同定のスメクチック相、Ｉは等方性液体、Ｔｍは重合体の融点を示す。重合体の重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、多分散度（Ｍｗ／Ｍｎ）は、ＧＰＣ（ゲル・パーミェーション・クロマトグラフィー）による測定値（排除限界１０００万のカラムを用い、分子量公知の標準ポリスチレンから換算）から算出した。なお、単位記号Ｌはリットル（ｌｉｔｅｒ）を示す。ＨＴＰ（ヘリカルツイストパワー）は公式ｐ＝１／ＨＴＰ・１／ｃ（式中ｐはピッチ、ｃはホスト液晶中の化合物の重量濃度）を用い計算した。ピッチの測定はメルク社製の液晶組成物ＺＬＩ−１１３２に試料を１重量％溶解し、楔型セルを用いて測定した。
【００９４】
実施例１
＜マレイミドとフランのＤｉｅｌｓ−Ａｌｄｅｒ反応＞
マレイミド２７５ｇをジエチルエーテル３．５Ｌに溶解した溶液に、フラン１Ｌを加え４８時間還流した。この間、反応が進むに従って反応器の周りに結晶が析出してきた。還流を止めて、室温（２０℃）で１日静置すると結晶がさらに析出した。この結晶を濾過して、減圧下で乾燥することによりマレイミドのフラン付加体［ｉ］４３４ｇを得た。
融点：１３０〜１３２℃
【００９５】
＜Ｎ−（４−カルボキシフェニル）マレイミドの製造＞
第１段階
無水マレイン酸１９６ｇをジメチルホルムアミド６４０ｍＬに溶解した溶液に、４−アミノ安息香酸２７４ｇを加え室温で６時間撹拌した。反応液を２Ｌの水に注ぎ込むことによって析出した白色の結晶を、濾過によって分取した。この結晶を、減圧下で乾燥することによりＮ−（４−カルボキシフェニル）マレイン酸４４９ｇを得た。
融点：２１７〜２２０℃
【００９６】
第２段階
Ｎ−（４−カルボキシフェニル）マレイン酸４０５ｇ、酢酸ナトリウム２３ｇを無水酢酸９３０ｍｌに加え、６０℃で２時間攪拌した。反応液を氷水３Ｌに注ぎ込むことによって析出した白色の結晶を、濾過によって分取した。得られた結晶を水でよく洗浄した後乾燥して、メタノール／水（２／１）で再結晶を行い、Ｎ−（４−カルボキシフェニル）マレイミド２５９ｇを得た。
融点：２０８〜２１０℃
【００９７】
＜液晶骨格の製造１＞
４−（トランス−４−ｎ−プロピルシクロヘキシル）フェノール３０ｇ、６−ブロモヘキサノール２７．３ｇ、および炭酸カリウム３９ｇをジメチルホルムアミド３００ｍｌに加え、９０℃で３時間攪拌した。反応液を３Ｎの塩酸１Ｌに注ぎ込むことによって析出した白色の結晶を、濾過によって分取した。得られた結晶を水でよく洗浄した後乾燥して、２５ｇの化合物（ＬＣ１）を得た。
【００９８】
前記と同様の方法により、以下の化合物を製造した。
【０１００】
＜液晶骨格の製造２＞
４−シアノ−４′−ヒドロキシビフェニル１２．３ｇと４−（６−ヒドロキシヘキシルオキシ）安息香酸１５ｇ、ジメチルアミノピリジン０．０２ｇを塩化メチレン２５０ｍｌに溶解した溶液を５℃に冷やし、そこへ１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド塩酸塩１４ｇを数回に分けて加え、室温で１２時間かくはんした。反応液を水、５％水酸化ナトリウム水、５％塩酸、飽和炭酸ナトリウム水で順次洗浄した後、無水硫酸マグネシウムで乾燥した。溶媒を留去して得られた残査をエタノールで２回再結晶することで１４ｇの化合物（ＬＣ１３）を得た。
【０１０１】
前記と同様の方法により、以下の化合物を製造した。
【０１０３】
＜マレイミド誘導体の製造＞
マレイミドのフラン付加体［ｉ］５．２ｇ、化合物（ＬＣ１３）１３ｇ、トリフェニルホスフィン８．９ｇ、テトラヒドロフラン２００ｍｌからなる溶液にアゾジカルボン酸ジエチルの４０％トルエン溶液１１ｍｌを０℃で加え、室温で１２時間攪拌した。水５０ｍｌ、酢酸エチル２００ｍｌを加えて分液し、有機層を無水硫酸マグネシウムで乾燥した。溶剤を留去して得られた残査にトルエン２００ｍｌを加え１２時間還流した。トルエンを留去して得られた残査をシリカゲルクロマトグラフィーで精製、エタノールで再結晶を行い、７．５ｇの化合物（ＭＡ１）を得た。
【０１０５】
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ１．２〜１．９（８Ｈ、ｍ）、３．５４（２Ｈ、ｔ、Ｊ＝７Ｈｚ）、４．０４（２Ｈ、ｔ、Ｊ＝６．１Ｈｚ）６．６８（２Ｈ、ｓ）６．９７（２Ｈ、ｄ、Ｊ＝９Ｈｚ）、７．３１（２Ｈ、ｄ、Ｊ＝９Ｈｚ）、７．６０（２Ｈ、ｄ、Ｊ＝９Ｈｚ）、７．７０（４Ｈ、ｓ）、８．１５（２Ｈ、ｄ、Ｊ＝９Ｈｚ）
【０１０７】
＜フェニルマレイミド誘導体の製造＞
Ｎ−（４−カルボキシフェニル）マレイミド３ｇ、ＬＣ１３４．５４ｇ、ジクロロメタン１００ｍｌからなる溶液にＤＣＣ３．１４ｇ、ＤＭＡＰ０．０２ｇを０℃で加え、室素で１２時間攪拌した。水１００ｍｌを加えて分液し、有機層を無水硫酸マグネシウムで乾燥した。溶剤を留去して得られた残査をシリカゲルクロマトグラフィー（トルエン／酢酸エチル＝９／１）で精製、ヘプタンで再結晶を行い、４．８ｇの化合物（ＭＡ２）を得た。
【０１０８】
前記と同様の方法により、以下の化合物を製造した。
実施例２
＜光学活性なビニルエーテル誘導体の製造＞
第１段階
化合物（Ｋ１）の製造
【０１１２】
４−アセトキシ安息香酸２６０ｇ、塩化チオニル５００ｍｌに数滴のジメチルホルムアミドを加えた溶液を５時間還流した後、塩化チオニルを減圧下留去して４−アセトキシ安息香酸クロライドを得た。Ｌ−（−）−フェネチルアミン１６８ｇ、ピリジン３００ｍｌ、クロロホルム８００ｍｌを混合した溶液に、先に合成した４−アセトキシ安息香酸クロライドをクロロホルム５００ｍｌに溶かした溶液を室温で滴下し、滴下後、さらに４時間還流した。反応液に水を加えて分液し、クロロホルム層を５％塩酸で酸性になるまで洗浄、飽和炭酸ナトリウム水、水で順次洗浄し、無水硫酸マグネシウムで乾燥した。クロロホルムを留去して得られた結晶をエタノールで再結晶して２８７ｇの化合物（Ｋ１）を得た。融点１５５℃。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ１．５７（３Ｈ、ｄ、Ｊ＝７Ｈｚ）、２．２９（３Ｈ、ｓ）、５．３０（１Ｈ、ｍ）、６．４４（１Ｈ、ｄ、Ｊ＝７．２Ｈｚ）、７．１１（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、７．３６（５Ｈ、ｓ）、７．７７（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）
【０１１４】
第２段階
化合物（Ｋ２）の製造
【０１１５】
化合物（Ｋ１）２８７ｇをメタノール２Ｌに溶かした溶液に２８％アンモニア水１００ｍｌを加え、１時間撹拌した。反応溶液に６Ｎ塩酸を中性になるまで加え反応を終了させ、この溶液を水３Ｌに注いだ。析出した結晶を濾過して分取し、減圧乾燥した後、クロロホルムで再結晶して２５０ｇの化合物（Ｋ２）を得た。融点１９２〜１９４℃。
１Ｈ−ＮＭＲ（ＣＤ３ＯＤ）δ１．５５（３Ｈ、ｄ、Ｊ＝７Ｈｚ）、５．２３（１Ｈ、ｍ）、６．８２（２Ｈ、ｄ、Ｊ＝８．５Ｈｚ）、７．３３（５Ｈ、ｓ）、７．７３（２Ｈ、ｄ、Ｊ＝８．５Ｈｚ）
第３段階
化合物（Ｋ３）の製造
【０１１７】
化合物（Ｋ２）５０ｇ、４−（６−ヒドロキシヘキシルオキシ）安息香酸４７．６ｇ、を塩化メチレン１．３Ｌに溶かし５℃まで冷やし、そこへジメチルアミノピリジン１．５ｇ、１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド塩酸塩４２ｇを加え室温で１２時間攪拌した。水３００ｍｌを加え分液、有機層を６Ｎ塩酸、飽和炭酸ナトリウム水、水で順次洗浄し、無水硫酸マグネシウムで乾燥した。溶媒を留去して得られた残査をエタノールで再結晶を行い５７ｇの化合物（Ｋ３）を得た。融点１７０℃。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ１．３０〜１．９０（８Ｈ）、１．６０（３Ｈ、ｄ、Ｊ＝７Ｈｚ）、３．６６（２Ｈ、ｄ、Ｊ＝６．２Ｈｚ）、４．０４（２Ｈ、ｄ、Ｊ＝６．２Ｈｚ）５．３３（１Ｈ、ｍ）、６．４０（１Ｈ、ｄ、Ｊ＝７．８Ｈｚ）、６．９６（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、７．２３（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、７．３５（５Ｈ、ｓ）、７．８２（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、８．１２（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）
【０１１９】
第４段階
化合物（ＫＶ１３）の製造
【０１２０】
ｎ−ブチルビニルエーテル５００ｍｌ、クロロホルム１２０ｍｌを混合した溶媒にジアセト（１，１０−フェナントロリン）パラジウム２ｇを加え室温で１０分かくはんした。そこへ化合物（Ｋ３）２２．８ｇを加え６５℃まで温度を上げて２４時間かくはんした。反応溶液を濾過して不溶物を取り除き、濃縮した残査をシリカゲルカラムクロマトグラフィー、再結晶により精製して１０．２ｇの化合物（ＫＶ１３）を得た。融点１５１〜１５２℃。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ１．３０〜１．９０（８Ｈ）、１．６０（３Ｈ、ｄ、Ｊ＝７Ｈｚ）、３．６６（２Ｈ、ｄ、Ｊ＝６．２Ｈｚ）、４．０４（２Ｈ、ｄ、Ｊ＝６．２Ｈｚ）、４．１０ ａｎｄ ４．２５ （１Ｈ、２ｓ）、５．３３（１Ｈ、ｍ）、６．４０（１Ｈ、ｄ、Ｊ＝７．８Ｈｚ）、６．４７（１Ｈ、ｑ）、６．９６（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、７．２３（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、７．３５（５Ｈ、ｓ）、７．８２（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、８．１２（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）
【０１２２】
原料に（Ｓ）−（−）−１−（ナフチル）エチルアミンを用いた以外は、実施例２と同様の製造法により化合物（ＫＶ１９）を製造した。融点：８９℃
【０１２３】
実施例３
第１段階
化合物（Ｋ４）の製造
【０１２５】
化合物（Ｋ２）２６．５ｇ、６−ブロモヘキサノール２５ｇ、炭酸カリウム３１ｇをジメチルホルムアミド２００ｍｌ中で攪拌しながら５時間還流した。水２００ｍｌに反応液を注ぎ、酢酸エチルで抽出し、酢酸エチル層を水で数回洗浄して無水硫酸マグネシウムで乾燥した。溶媒を留去して得られた固形物をクロロホルムで再結晶して化合物（Ｋ４）２３ｇを得た。融点１０５〜１０６℃
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ１．３０〜１．９０（８Ｈ）、１．６０（３Ｈ、ｄ、Ｊ＝７Ｈｚ）、３．６２（２Ｈ、ｄ、Ｊ＝６．２Ｈｚ）、３．９８（２Ｈ、ｄ、Ｊ＝６．２Ｈｚ）５．３１（１Ｈ、ｍ）、６．２８（１Ｈ、ｄ、Ｊ＝７．７Ｈｚ）、６．８８（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、７．３４（５Ｈ、ｓ）、７．７２（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）
【０１２７】
第２段階
化合物（ＫＶ２）の製造
【０１２８】
ｎ−ブチルビニルエーテル３００ｍｌ、クロロホルム８０ｍｌを混合した溶媒にジアセト（１，１０−フェナントロリン）パラジウム１．８ｇを加え室温で１０分かくはんした。そこへ化合物（Ｋ４）１５ｇを加え６５℃まで温度を上げて２４時間かくはんした。反応溶液を濾過して不溶物を取り除き、濃縮した残査をシリカゲルカラムクロマトグラフィー、再結晶により精製して１０．２ｇの化合物（ＫＶ２）を得た。融点８５℃。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ１．３０〜１．９０（８Ｈ）、１．６０（３Ｈ、ｄ、Ｊ＝７Ｈｚ）、３．６２（２Ｈ、ｄ、Ｊ＝６．２Ｈｚ）、３．９８（２Ｈ、ｄ、Ｊ＝６．２Ｈｚ）４．１０ ａｎｄ ４．２５ （１Ｈ、２ｓ）、５．３１（１Ｈ、ｍ）、６．２８（１Ｈ、ｄ、Ｊ＝７．７Ｈｚ）、６．４７（１Ｈ、ｑ）、６．８８（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、７．３４（５Ｈ、ｓ）、７．７２（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）
【０１３０】
実施例４
第１段階
【０１３１】
第１段階
化合物（Ｋ５）の製造
【０１３２】
Ｌ−（−）−フェネチルアミン（７８ｇ）、ピリジン（１８０ｍｌ）、クロロホルム（４００ｍｌ）を混合した溶液に、４−ブロモ−２−フルオロ安息香酸クロライドをクロロホルム（２００ｍｌ）に溶かした溶液を室温で滴下し、滴下後、さらに４時間還流した。反応液に水を加えて分液し、クロロホルム層を５％塩酸で酸性になるまで洗浄、飽和炭酸ナトリウム水、水で順次洗浄し、無水硫酸マグネシウムで乾燥した。クロロホルムを留去して得られた結晶をシクロヘキサンで再結晶して１３１ｇの化合物（Ｋ５）を得た。融点９１℃
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ１．５９（３Ｈ、ｄ、Ｊ＝８Ｈｚ）、５．３３（１Ｈ、ｍ）、７．２〜７．５（７Ｈ、ｍ）、７．９７（１Ｈ、ｔ、Ｊ＝８Ｈｚ）
【０１３４】
第２段階
化合物（Ｋ６）の製造
【０１３５】
化合物（Ｋ５）（５０ｇ）、トリメチルシリルアセチレン（３８ｇ）、ＰｄＣｌ２（ＰＰｈ３）２（１．１６ｇ）、ヨウ化銅（０．３ｇ）、トリフェニルフォスフィン（０．８４ｇ）をトリエチルアミン（４００Ｌ）に溶かした溶液を３時間還流した。反応溶液中の不溶物を減圧濾過で取り除き、溶媒を留去して得られた濃縮物をトルエンに溶解し、６Ｎ塩酸で中性になるまで洗浄、次に飽和炭酸ナトリウム水で洗浄、無水硫酸マグネシウムで乾燥、溶媒を留去して油状物を得た。この油状物をシリカゲルカラムクロマトグラフィー（トルエン：酢酸エチル＝９５：５）で精製した。精製した油状物をテトラヒドロフラン３００ｍｌに溶解し、一旦−５０℃に冷却した。そこへテトラブチルアンモニウムフロライドの１ｍｏｌ／ｌ溶液（１８０ｍｌ）を滴下した。−５０℃で１時間かくはんして、その後０℃に温度を上げ水（５０ｍｌ）を加え室温で１時間かくはんした。反応液を酢酸エチル４００ｍｌで抽出、有機層を６Ｎ塩酸、飽和炭酸ナトリウム水、無水硫酸マグネシウムで乾燥した。溶媒を留去して得られた残査をシクロヘキサンで再結晶して２６ｇの（Ｋ６）を得た。融点９４℃
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ１．６０（３Ｈ、ｄ、Ｊ＝７Ｈｚ）、３．２２（１Ｈ、ｓ）、５．３３（１Ｈ、ｍ）、７．２〜７．５（７Ｈ、ｍ）、８．０４（１Ｈ、ｔ、Ｊ＝８Ｈｚ）
【０１３７】
第３段階
化合物（Ｋ７）の製造
【０１３８】
化合物（Ｋ６）（１３ｇ）、 ４−（３−ヒドロキシプロピルオキシ）ブロモベンゼンのテトラヒドロピラニルエーテル（１５ｇ）、ＰｄＣｌ２（ＰＰｈ３）２（０．３４ｇ）、ヨウ化銅（０．０９ｇ）、トリフェニルフォスフィン（０．２５ｇ）をトリエチルアミン（１００Ｌ）に溶かした溶液を６時間還流した。反応溶液中の不溶物を減圧濾過で取り除き、溶媒を留去して得られた残査をトルエンに溶解し、６Ｎ塩酸で酸性になるまで洗浄、次に飽和炭酸ナトリウム水で洗浄、無水硫酸マグネシウムで乾燥、溶媒を留去して固形物を得た。この油状物をシリカゲルカラムクロマトグラフィー（クロロホルム：メタノール＝９７：３）を通して触媒を取り除き、濃縮物をシクロヘキサンで再結晶して４ｇの（Ｋ７）を得た。融点１３３〜１３５℃。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ１．６０（３Ｈ、ｄ、Ｊ＝７Ｈｚ）、２．１４（２Ｈ、ｍ）、３．８７（２Ｈ、ｔ、Ｊ＝６．０Ｈｚ）、４．１４（２Ｈ、ｔ、Ｊ＝６．０Ｈｚ）、５．３３（１Ｈ、ｍ）、６．８８（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、７．２〜７．６（９Ｈ、ｍ）、８．０５（１Ｈ、ｔ、Ｊ＝８Ｈｚ）
【０１４０】
第４段階
化合物（ＫＶ４１）の製造
【０１４１】
ｎ−ブチルビニルエーテル２５ｍｌ、クロロホルム５ｍｌを混合した溶媒にジアセト（１，１０−フェナントロリン）パラジウム０．１７ｇを加え室温で１０分かくはんした。そこへ化合物（Ｋ７）１．８ｇを加え６５℃まで温度を上げて１０時間かくはんした。反応溶液を濾過して不溶物を取り除き、濃縮物をシリカゲルカラムクロマトグラフィー、再結晶により精製して０．５ｇの化合物（ＫＶ４１）を得た。融点１１７℃。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）δ１．６０（３Ｈ、ｄ、Ｊ＝７Ｈｚ）、２．１４（２Ｈ、ｍ）、３．８７（２Ｈ、ｔ、Ｊ＝６．０Ｈｚ）、４．１０（２Ｈ、ｔ、Ｊ＝６．０Ｈｚ）、４．１０ ａｎｄ ４．２５ （１Ｈ、２ｓ）、５．３３（１Ｈ、ｍ）、６．４７（１Ｈ、ｑ）、６．８８（２Ｈ、ｄ、Ｊ＝８．８Ｈｚ）、７．２〜７．６（９Ｈ、ｍ）、８．０５（１Ｈ、ｔ、Ｊ＝８Ｈｚ）
【０１４３】
比較例１
一般的なカイラル剤である（ＣＢ−１５）と本発明の化合物のＨＴＰを比較した。
【０１４４】
化合物名 ＨＴＰ
（ＣＢ−１５） ５．７μｍ−１・ｗｔ％−１
（ＫＶ２） ４６．５μｍ−１・ｗｔ％−１
（ＫＶ１３） ３７．７μｍ−１・ｗｔ％−１
本発明の化合物はＣＢ−１５よりも６倍以上大きなＨＴＰを示した。すなわち、本発明の化合物が大きな螺旋誘起力を有していることがこの結果からわかる。
【０１４６】
実施例５
＜共重合体の製造＞
コレステリック液晶共重合体［例えばＭＶＣ１］の製造
【０１４７】
マレイミド（ＭＡ１）０．５ｇ、光学活性ビニルエーテル（ＫＶ１３）０．１２ｇ、ＡＩＢＮ０．００３ｇ、ジメチルスルホキシド２ｍｌをアンプルにとり、−６０℃に冷却し、真空ポンプで十分脱気を行い、そして封管した。封管したアンプルを６０℃で４８時間反応させた。アンプル内の内容物をテトラヒドロフラン１０ｍｌに溶解し、メタノール１００ｍｌに投入して沈殿させた。この操作を３回行った後、メタノールで十分洗浄し、減圧下で乾燥させ、０．４ｇの共重合体［例えばＭＶＣ１、ランダム、ブロック、交互、グラフト共重合体などのいずれでもいい］を得た。
５００ＨｚプロトンＮＭＲの測定により算出した各骨格の共重合体構成割合は、ｘ：ｙ＝７３：２７であった。
重量平均分子量（ＭＷ）：３７，０００
多分散度（Ｍｗ／Ｍｎ）：２．１５
相転移温度：Ｔｍ １５７ Ｃｈ ２８０ Ｉ
重合体［ＭＶＣ１］は、コレステリック相を示す重合体であった。
【０１４９】
実施例６
コレステリック液晶共重合体［例えばＭＶＣ２］の製造
【０１５０】
マレイミド（ＭＡ６）０．５ｇ、光学活性ビニルエーテル（ＫＶ１９）０．１８ｇ、ＡＩＢＮ０．００４１ｇ、テトラヒドロフラン２ｍｌを用い、６０℃で２４時間反応させた以外は実施例３と同様の方法で共重合体［例えばＭＶＣ２、ランダム、ブロック、交互、グラフト共重合体などのいずれでもいい］を０．４８ｇ得た。
５００ＨｚプロトンＮＭＲの測定により算出した各骨格の共重合体構成割合は、ｘ：ｙ＝８３：１７であった。
重量平均分子量（ＭＷ）：２２，０００
多分散度（Ｍｗ／Ｍｎ）：１．８７
相転移温度：Ｔｍ １０５ Ｃｈ １０９ Ｉ
重合体［ＭＶＣ２］は、コレステリック相を示す重合体であった。
【０１５２】
実施例７
コレステリック液晶共重合体［例えばＭＶＣ３］の製造
【０１５３】
マレイミド（ＭＡ１）０．５ｇ、光学活性ビニルエーテル（ＫＶ２）０．１６ｇ、ＡＩＢＮ０．００３５ｇ、ジメチルスルホキシド２ｍｌを用い、６０℃で４８時間反応させた以外は実施例３と同様の方法で共重合体［例えばＭＶＣ３、ランダム、ブロック、交互、グラフト共重合体などのいずれでもいい］を０．５ｇ得た。
５００ＨｚプロトンＮＭＲの測定により算出した各骨格の共重合体構成割合は、ｘ：ｙ＝７４：２６であった。
重量平均分子量（ＭＷ）：３８，０００
多分散度（Ｍｗ／Ｍｎ）：３．１９
相転移温度：Ｔｍ ２７０ Ｃｈ ２９０ Ｉ
重合体［ＭＶＣ３］は、コレステリック相を示す重合体であった。
【０１５５】
実施例８
コレステリック液晶共重合体［例えばＭＶＣ４］の製造
【０１５６】
マレイミド（ＭＡ１１）０．３ｇ、マレイミド（ＭＡ１４）０．２６ｇ、ビニルエーテル（ＫＶ１３）０．１５ｇ、ＡＩＢＮ０．００３７ｇ、ジメチルスルホキシド（２ｍｌ）、テトラヒドロフラン２ｍｌを用い、６０℃で１２時間反応させた以外は実施例３と同様の方法で共重合体［例えばＭＶＣ４、ランダム、ブロック、交互、グラフト共重合体などのいずれでもいい］を０．４ｇ得た。
５００ＨｚプロトンＮＭＲの測定により算出した各骨格の共重合体構成割合は、ｘ＋ｙ：ｗ＝８５：１５であった。
重量平均分子量（ＭＷ）：１２，０００
多分散度（Ｍｗ／Ｍｎ）：２．３９
相転移温度：Ｔｍ １０７ Ｃｈ １３０ Ｉ
重合体［ＭＶＣ４］は、コレステリック相を示す重合体であった。
【０１５８】
実施例９
コレステリック液晶共重合体［例えばＭＶＣ５］の製造
【０１５９】
マレイミド（ＭＡ１）０．２６ｇ、光学活性ビニルエーテル（ＫＶ４１）０．１ｇ、ＡＩＢＮ０．０００２ｇ、テトラヒドロフラン１ｍｌを用い、６０℃で６時間反応させた以外は実施例３と同様の方法で共重合体［例えばＭＶＣ５、ランダム、ブロック、交互、グラフト共重合体などのいずれでもいい］を０．１ｇ得た。
５００ＨｚプロトンＮＭＲの測定により算出した共重合割合は、ｙ：ｗ＝７５：２５であった。
重量平均分子量（ＭＷ）：５，６００
多分散度（Ｍｗ／Ｍｎ）：１．４８
相転移温度：Ｔｍ １３７ Ｃｈ ２５１ Ｉ
重合体［ＭＶＣ５］は、コレステリック相を示す重合体であった。
【０１６１】
実施例１０
＜円偏光フィルムの製造＞
マレイミド（ＭＡ１）０．５ｇ、光学活性ビニルエーテル（ＫＶ１３）０．１２ｇ、ＡＩＢＮ０．００３ｇ、ジメチルスルホキシド２ｍｌをナスフラスコにとり、真空ポンプで十分脱気を行い、ついでアルゴン置換した後、６０℃で３時間反応させた。内容物を水１００ｍｌに投入して沈殿させた。沈殿物を水で十分洗浄し、減圧下で乾燥させ、０．６ｇの固形物［ＭＶＣ３］を得た。重量平均分子量（ＭＷ）は２０００、融点１４０℃、透明点２８０以上であった。厚さ５０μｍのトリアセチルセルロースフィルムに厚さ約０．１μのポリビニルアルコール層を設け、それをレーヨン布でラビング処理し、その処理面に［ＭＶＣ３］のクロロホルム溶液（３０重量％）をスピンコートした。十分乾燥させた後、１２０℃で１５分間配向処理し、つぎに同温度を保持したまま、高圧水銀灯（１２０Ｗ／ｃｍ２）を用い１分間紫外線を照射した。照射後室温に戻しフィルムを得た。
このフィルムの重合体層は厚さ２μｍであり、トリアセチルセルロースフィルムとの一体物からなる光学素子は青色光を反射する円偏光二色性を示し、この反射光は４１２から６９４ｎｍの左円偏光であった。このフィルムを一旦、２８０℃まで加熱して室温にもどしても配向はくずれることなく保持されていた。
【０１６２】
実施例１１
マレイミド（ＭＡ１）０．５ｇ、光学活性ビニルエーテル（ＫＶ１３）０．０９ｇを用いた以外は実施例７および実施例１０に準じて重合と素子の製造を行った。この光学素子は赤色光を反射する円偏光二色性を示し、この反射光は５８１から６９５ｎｍの左円偏光であった。
【０１６３】
実施例１２
実施例７、８で得た共重合体を１：１の比率で混合し、実施例１０に従い素子を製造した。この光学素子は緑色光を反射する円偏光二色性を示し、この反射光は４８０から５８５ｎｍの左円偏光であった。
【０１６４】
実施例１３
実施例１０、１１、１２で得た光学素子を、アクリル系粘着材を介して積層して、４１０から６９０ｎｍの範囲で円偏光二色性を示す光学素子を得た。この光学素子にポリカーボネイトからなる２枚の延伸フィルムの積層体からなる１／４λ板を、アクリル系粘着剤層を介して積層し、自然光を入射したところＮＢＳ方式にもとづく色変化は３で、非常に小さい物であった。また、この１／４λ板を付きの光学素子を８０℃で１０００時間の加熱時間、９０％の湿度、６０℃で１０００時間の湿熱試験においても、光学特性や外観などの変化は殆ど認められず、耐久性に優れたものであった。
【０１６５】
比較例２
実施例７で得た［ＭＶＣ３］をクロロホルムに溶解して、３０重量％の溶液を調製した。この溶液をラビング配向処理した配向膜の付いたガラス基板にスピンコートした後、十分乾燥させ薄膜を得た（膜厚３０ｎｍ）。この基板を１２０℃のオーブンに入れ５分間アニールした。目視で基板が赤色の発色していることを確認した。オーブンから基板を出して室温に戻したところ、赤色のフィルムの発色が消えて白濁したフィルムであり、グランジャン配向がくずれたものであった。このフィルムの透明点は１４０℃であり塗布前の透明点と同じであった。
【０１６６】
【発明の効果】
本発明の光学活性なビニルエーテル誘導体（１）は大きな螺旋誘起力を有しマレイミドとの共重合性に優れたモノマーである。
本発明のマレイミド−ビニルエーテル共重合体は塗布方式に適応でき、配向性に優れている。本発明の共重合体で製造したフィルムは架橋剤を用いることなく、電磁波を照射することで配向の固定化を行うことができ、耐熱性の高いフィルムを簡便に製造できる。本発明の共重合体で作成した配向フィルムは、円偏光性を示すので、液晶表示素子に用いる色補償板、光学位相板、ノッチフィルム等の用途に用いることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The first aspect of the present invention relates to an optically active vinyl ether which maintains a liquid crystallinity even when induced by a copolymer and induces a strong twist required for a cholesteric film having a short selective reflection band near visible light. Second, a maleimide-vinyl ether copolymer having a cholesteric phase such as a Grandian orientation having excellent orientation and heat resistance, which is applicable to a coating method capable of easily and efficiently producing a large area body, and an optical system using the same. Element. A third method is a method for producing a film in which an oriented copolymer is irradiated with an electromagnetic wave to fix a cholesteric phase.
[0002]
[Prior art]
An optical film in which a cholesteric liquid crystal polymer is oriented exhibits circular dichroism. Therefore, it has been proposed to use the liquid crystal display device for a color compensator, an optical phase plate, a notch filter, and the like.
[0003]
In order to manufacture such a cholesteric liquid crystal film, two substrates having a rubbed alignment film are bonded together with a gap agent or the like so as to keep a uniform interval, and a low-molecular polymerizable cholesteric liquid crystal composition is added thereto. Is injected into the cholesteric phase to form a monodomain state, and then polymerized by ultraviolet rays or the like to produce an oriented film (for example, see Patent Document 1). The film obtained by this method has almost no change in the orientation due to heat, and as a result, a film excellent in heat resistance with little optical change due to heat can be produced. However, since the film thickness depends on the substrate on which the monomer is oriented, a large substrate is required to produce a large-screen oriented film, and it is difficult to control the uniform spacing of the substrates when the area is large. Therefore, it was difficult to produce a film having a uniform thickness. That is, the method was excellent as a method for producing a film having high heat resistance, but was inferior in production efficiency.
[0004]
On the other hand, as a method of efficiently producing a cholesteric liquid crystal film having a uniform thickness on a large screen, a solution of a cholesteric liquid crystal polymer is uniformly applied to a substrate on which an alignment film is formed, dried, and then subjected to a glass transition temperature. A method of heating and then cooling and orienting has been proposed (for example, see Patent Document 2). However, the cholesteric liquid crystal polymer film thus produced is fixed when the orientation is lower than the glass transition point temperature, but is subjected to stress such as tensile and torsion applied to the film when the temperature is higher than the glass transition temperature. Therefore, there was a problem that the orientation was disturbed. That is, although this method is excellent in production efficiency, the heat resistance of the film was poor.
[0005]
For the purpose of improving the heat resistance of the film, a copolymer containing a cross-linking group in a monomer unit constituting the polymer has also been proposed (for example, see Patent Document 3). However, the composition of the material was complicated, for example, a crosslinkable monomer having a bifunctional group such as a diacrylic compound had to be added, and it was not industrial.
[0006]
[Patent Document 1]
JP-A-6-281814
[Patent Document 2]
JP-A-9-133810
[Patent Document 3]
JP 2000-336362 A
[0007]
[Problems to be solved by the invention]
The present invention is an optically active vinyl ether that induces a strong twist without deteriorating the liquid crystallinity even when induced into a liquid crystal polymer.
In addition, the cholesteric liquid crystal can be applied to a cholesteric liquid crystal polymer coating method, so that a large area body can be easily and efficiently manufactured, and further, does not require cross-linking and can form an oriented film having excellent heat resistance by irradiation with ultraviolet rays. It is a polymer.
Further, the present invention provides a method for producing a cholesteric liquid crystal polymer oriented film.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned object, the present inventor has conducted intensive studies on the structure of the cholesteric liquid crystal polymer, the structure of the monomer as a raw material of the polymer, the method for producing the film, and the like. The cholesteric liquid crystal polymer obtained by the copolymerization reaction of vinyl ether having is suitable for uniform coating of a large screen, and further, after coating, drying, and heat treatment, can easily be subjected to Grandian alignment, and furthermore, can be obtained. By irradiating the oriented film with electromagnetic waves, it was found that the orientation of the film was fixed and the heat resistance was improved, and the present invention was completed.
[0009]
The present invention has the following configurations.
1.光学 An optically active compound represented by the formula (1).
2.化合物 The compound according to item 1, wherein in formula (1), o is 0.
3.化合物 The compound according to item 1, wherein in formula (1), o is 1.
4.化合物 The compound according to any one of Items 1 to 3, wherein p is 3 to 6 in Formula (1).
[0011]
5.共 A copolymer of the compound represented by formula (2) and the compound according to any one of items 1 to 4.
[0012]
6.共 A copolymer of the compound represented by any one of formulas (a) to (f) and the compound according to any one of items 1 to 4.
[0013]
7. (4) A copolymer comprising a skeleton of a monomer unit represented by the formula (3) and a skeleton represented by a monomer unit represented by the formula (4).
8.共 The copolymer according to item 7, wherein in formula (4), o is 0.
9.共 The copolymer according to item 7, wherein in formula (4), o is 1.
10.に お い て In the formula (4), the copolymer according to any one of items 7 to 9, wherein p is 3 to 6.
[0015]
11.共 In the formula (3), the copolymer according to any one of items 7 to 10, wherein m is 0.
12.共 In the formula (3), the copolymer according to any one of items 7 to 10, wherein m is 1.
13. Any one of items 7 to 12, comprising 60 to 95 mol% of the monomer unit represented by the formula (3) described in the item 7 and 5 to 40 mol% of the monomer unit represented by the formula (4) described in the item 7; A copolymer having a weight average molecular weight of 2,000 to 50,000, comprising the copolymer according to item 1 as a component.
[0016]
14．光学 An optical element comprising the copolymer according to any one of Items 7 to 13.
15. Item 15. The optical element according to item 14, which exhibits a cholesteric phase and has a circular dichroism characteristic in which the copolymer is oriented in a Grand Jean.
16. Item 14. The optical element according to item 14 or 15, which exhibits circular dichroism in the visible light region.
[0017]
17. Item 17: The optical element according to any one of Items 14 to 16, comprising two or more layers of polymers having different wavelength regions exhibiting circular dichroism.
18.光学 An optical member comprising the optical element according to any one of items 14 to 17, further comprising a retardation layer capable of changing circularly polarized light into linearly polarized light.
19.光学 An optical compensation film containing the polymer according to any one of Items 7 to 13.
[0018]
20. [14] An optical writing recording material containing the polymer according to any one of [7] to [13].
21.液晶 A liquid crystal alignment film containing the polymer according to any one of Items 7 to 13.
22. [4] A method for producing an oriented film, comprising: subjecting the copolymer according to any one of items 7 to 13 to an orientation treatment, and then fixing the orientation by irradiation with an electromagnetic wave.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
A first aspect of the present invention is a vinyl ether represented by the formula (1), which is an optically active substance. A second aspect of the present invention is a side-chain cholesteric liquid crystal copolymer having a monomer unit represented by the formula (3) and a monomer unit represented by the formula (4) as constituent units. In the following description, the cholesteric liquid crystal copolymer of the present invention may be referred to as a copolymer. The following group which is a partial structure of the formula (3) may be referred to as a liquid crystal skeleton (MSG).
[0020]
The copolymer is produced by a copolymerization reaction of at least two kinds of monomers. Each monomer has the following effects on the function expression of the copolymer.
1) The optically active vinyl ether represented by the formula (1) has excellent copolymerizability with maleimide, and has a large twist-inducing force. Therefore, with a composition of 40 mol% or less based on maleimide, the pitch can be adjusted to a short pitch such that the selective reflection band is near the wavelength of visible light. Further, since the mixing ratio with maleimide can be reduced, the liquid crystallinity of the copolymer is not easily impaired.
[0022]
2) In the maleimide represented by the formula (2), the liquid crystal skeleton (MSG) is N-substituted with respect to the maleimide or phenylmaleimide using a spacer such as a methylene chain in order to enhance liquid crystallinity. Can adjust the liquid crystal temperature range of the copolymer.
[0024]
In the formula (2) which is a raw material maleimide and the formula (3) which is a monomer unit, R1Is hydrogen, fluorine, chlorine, -NCO, -CN or alkyl having 1 to 20 carbons.2-May be replaced by -O-, -S-, -COO-, -OCO-, or -CO-, and any hydrogen may be replaced by halogen;1, A2And A3Independently of 1,4-cyclohexylene, 1,4-cyclohexylene wherein at least one hydrogen is replaced by fluorine, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen is 1,4-phenylene substituted with halogen, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4 -Tetrahydronaphthalene-2,6-diyl, 5,6,7,8-tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl or 1,3-dioxane-2,5-diyl; A4Is a single bond, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by methyl or halogen; Z1And Z2Is independently a single bond, -COO-, -OCO-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CH = CH-, -CH2CH2-Or -C≡C-; Z3Is a single bond, -COO-, -OCO-, or -O-; m is 1 or 0; and n is an integer of 1-20.
[0026]
Preferred R1Are hydrogen, fluorine, chlorine, -NCO, -CN, fluorinated alkyl having 1 to 3 carbons, fluorinated alkyloxy having 1 to 3 carbons, linear alkyl having 1 to 12 carbons, and 1 carbon -12 straight-chain alkoxy. Preferred fluorinated alkyls and fluorinated alkyloxys are -CF3, -CF2H, -OCF3, And -OCF2H. Preferred alkyls and alkoxys are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, and Decyloxy. R1Is -CF3, -OCF3, -NCO, fluorine or chlorine has a structure in which the compound (2) tends to have a positive dielectric anisotropy. The properties of compound (2) correlate with the properties of the copolymer.
[0027]
A in equation (2)1~ A4Is a divalent group having a ring structure. Preferred A1, A2Or A3The following is an example.
[0028]
A4Is a single bond, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by methyl or halogen. Preferred A4Is shown below as a more specific structure other than a single bond.
[0030]
Z in the formulas (2) and (3)1And Z2Is a linking group. Preferred Z1Or Z2Is a single bond, -COO-, -OCO-, -C≡C-, -CH2O-, -OCH2-, And -CH2CH2-. In the compound (1), Z1And Z2Is a single bond, -COO-, -OCO-, or -C≡C-, a polymer having a large optical anisotropy tends to be obtained. Z1And Z2At least one of -CH2O-, -OCH2-Or -CH2CH2In the case of-, the intermolecular force of the liquid crystal skeleton tends to decrease, so that a copolymer having a relatively small viscosity can be obtained.
[0032]
A1~ A3And Z1And Z2Will be described. In order for the copolymer to have a liquid crystal phase in a relatively low temperature range at room temperature, m is preferably 0 in the liquid crystal skeleton. Preferred liquid crystal skeletons are shown below.
[0033]
R in these formulas1, A1, And A2Has the same meaning as described above.
[0035]
The liquid crystal skeleton in which m is 1 has three rings. A copolymer having a three-ring liquid crystal skeleton generally has a high maximum temperature of a liquid crystal phase. A when it has a three-ring structure1~ A3And Z1And Z2Preferred combinations of are shown below.
[0036]
R in these formulas1, A1, A2And A3Has the same meaning as described above.
[0039]
In the formulas (1) and (4), n or p is preferably an integer of 1 to 20 because the copolymer has a cholesteric phase. More preferred n or p is 3-11. When the copolymer has 1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, the steric configuration is preferably a trans type rather than a cis type. Since there is no significant difference in the physical properties of the compounds, the copolymer is2H (deuterium),ThirteenIsotopes such as C may be included in an amount greater than the natural abundance ratio.
[0040]
In the formulas (2) and (3), n is preferably an integer of 1 to 20 because the copolymer has a liquid crystal phase. More preferably, n is 3-11. When the compound (2) has 1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, its steric configuration is preferably a trans type rather than a cis type. Since there is no significant difference in the properties of the compounds, compound (2)2H (deuterium),ThirteenIsotopes such as C may be contained in a proportion higher than the natural abundance ratio.
[0041]
Preferred examples of the compound (2) are the compounds (2-1) to (2-29).
[0044]
Further preferred examples of the compound (2) include compounds A-2 to A-29 in the compounds (2-1) to (1-29).1Is 1,4-cyclohexylene or 1,4-phenylene;2Is 1,4-phenylene or 1,4-phenylene in which at least one hydrogen is replaced by fluorine. A2Is preferably 1,4-phenylene in terms of compatibility. A2Is preferably 1,4-phenylene in which at least one hydrogen is replaced by fluorine, from the viewpoint of large dielectric anisotropy.
[0045]
In the formula (1) in the optically active vinyl ether and the formula (4) which is a monomer unit having an optically active group, R*Is a group represented by the formula (Ph1), (Ph2), (Ph3), (Ph4), (Ph5), or (Ph6), wherein * is an asymmetric carbon;4Is a single bond, -COO-, -OCO-, -CH2O-, -OCH2-, -CH = CH-, -CH2CH2-Or -C≡C-; G1, G2, G3, G4, G5Or G6Is independently hydrogen, halogen or methyl; o is 1 or 0; and p is an integer from 1 to 20.
[0046]
In the formulas (1) and (4), Z4Is a single bond, -COO-, -OCO-, -CH2O-, -OCH2-, -CH = CH-, -CH2CH2-Or -C≡C- is preferable, but -COO-, -OCO-, -CH2CH2-Or -C≡C- is more preferable because the effect of increasing the upper limit of the liquid crystal phase temperature range of the copolymer can be expected.
[0047]
G1, G2, G3, G4, G5Or G6Is each independently hydrogen, halogen or methyl. Particularly preferred examples in which phenylene is substituted are shown below.
[0048]
The copolymer of the present invention may contain a compound to be another copolymer component or another copolymer skeleton.
[0050]
The method for producing the optically active vinyl ether derivative represented by the formula (1) will be described.
<In the formula (1), R*= (Ph1), Z4= Production of -COO- Compound>
First, an ω-hydroxyalkoxybenzoic acid derivative [a] is obtained by etherifying ω-bromoalkanol and 4-hydroxybenzoic acid with a base such as potassium carbonate, sodium hydroxide, or potassium hydroxide.
[0051]
The 4-acetoxybenzoic acid derivative is converted to the corresponding acid chloride with a chlorinating agent such as thionyl chloride or oxalyl chloride, and amidated in the presence of an optically active R- or S-form phenethylamine [OP1] and a base such as pyridine or triethylamine. And solvolysis with ammonia and diethylamine to produce the phenol derivative [b]. The ω-hydroxyalkoxybenzoic acid derivative [a] and the phenol derivative [b] are esterified with a condensing agent such as dicyclohexylcarbodiimide or 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride to give the alcohol derivative [c]. ] Is obtained. Compound (1-1) is produced by vinyl etherification of [c] using a palladium catalyst.
[0053]
<In the general formula (1), R*= (Ph1), Z4= Preparation of compound of -≡->
The p-bromobenzoic acid chloride derivative and [OP1] are amidated in the presence of a base such as pyridine or triethylamine to give the corresponding amide [d]. [F] is obtained by cross-coupling reaction with trimethylsilylacetylene, detrimethylsilylation reaction, cross-coupling reaction with [e], and deprotection. Next, [f] is vinyl etherified using a palladium catalyst to produce an optically active vinyl ether derivative (1-2).
[0055]
<In the formula (1), R*= (Ph1), Z4= -CH2CH2Production of Compound of->
Compound (1-3) is produced by hydrogenating [f] using palladium carbon or the like as a catalyst and then vinyl etherifying the compound.
[0057]
<In the formula (1), R*= (Ph1), Z4= Production of single bond compound>
(1-4) is produced by a cross-coupling reaction using an amide [d], a boric acid derivative [g], and a palladium catalyst.
[0059]
<In the formula (1), R*= (Ph1), Production of Compound with n = 0>
The alcohol derivative [h] is obtained by etherifying the phenol derivative [b] and ω-bromoalkanol with a base such as potassium carbonate, sodium hydroxide or potassium hydroxide. [H] is vinyl etherified with a palladium catalyst to produce an optically active vinyl ether derivative (1-5).
[0061]
R*= (Ph2) to produce a compound of (R)-(+)-1- (naphthyl) ethylamine or (S)-(-)-1- (naphthyl) ethylamine
R*= (Ph3) to produce a compound of (R)-(-)-2-phenylglycine methyl ester or (S)-(+)-2-phenylglycine methyl ester
R*= (Ph4) to produce a compound of (R)-(+)-1-phenylethanol or (S)-(-)-1-phenylethanol
R*= (Ph5) to produce a compound of (R) -1-biphenylethanol or (S) -1-biphenylethanol
R*= (Ph6) To prepare the compound of (1R, 2S, 5R)-(-)-menthol or (1S, 2R, 5S)-(-)-menthol is used instead of [OP1]. Thus, compounds (KV1) to (KV55) are produced.
[0063]
<Production of maleimide derivative monomer>
The method for producing the maleimide derivative represented by the formula (2) will be described.
<Z in the formula (2)3= Single bond, A4= Production of single bond compound>
A Maleimide furan adduct [i] is produced by a Diels-Alder reaction between maleimide and furan. An alcohol derivative [j] is produced by etherifying a compound having a liquid crystal skeleton (MSG) and having a hydroxyl group at the end with ω-bromoalkanol using a base. Examples of bases are potassium hydroxide, sodium hydroxide, potassium carbonate, sodium hydride and the like. The compound (2-A) is produced by N-alkylation of a maleimide furan adduct [i] and an alcohol derivative [j] by a Mitsunobu reaction, followed by thermal decomposition by a retro-Diels-Alder reaction.
[0070]
<Z in the formula (2)3= -OCO-, A4= Production of 1,4-phenylene compound>
[K] is prepared by the reaction of maleic anhydride with a para-substituted aniline derivative. Subsequently, N-4-hydroxy or N-4-carboxyphenylmaleimide [l] is produced by the intramolecular condensation reaction of [k]. A compound (2-B) is produced by subjecting phenylmaleimide [l] in which Y = COOH and an alcohol derivative [j] to an esterification reaction.
[0072]
<Z in the formula (2)3= -O-, A4= Production of 1,4-phenylene compound>
The compound (2-C) can be produced by etherifying phenylmaleimide [1] and [j] in which Y = OH by the Mitsunobu reaction.
[0074]
<Z in the formula (2)3= -COO-, A4= Production of 1,4-phenylene compound>
A carboxylic acid derivative is produced by etherifying a compound having a liquid crystal skeleton (MSG) and having a hydroxyl group at the end with ω-bromoalkanoic acid using a base. Compound (5-D) is produced by esterification with phenylmaleimide [1] in which Y = OH.
[0076]
<Production of maleimide-vinyl ether copolymer>
Next, the maleimide-vinyl ether copolymer of the present invention will be described. When a composition of an optically active vinyl ether (formula (1)) and a maleimide (formula (2)) is polymerized, a copolymer is obtained. The copolymer is composed of a monomer unit (3) having a liquid crystal skeleton in a side chain and an optically active monomer unit (4) for adjusting the helical pitch of the cholesteric phase. In order to maintain the liquid crystallinity of the copolymer, the content of the monomer unit of the formula (3) is preferably set to 40% or more. In order to sufficiently reduce the helical pitch of the cholesteric liquid crystal phase, it is preferable that the monomer unit of the formula (4) be 40 mol% or less. Therefore, the copolymer of the present invention contains, as a component, a copolymer composed of 60 to 95 mol% of monomer units represented by the formula (3) and 5 to 40 mol% of monomer units represented by the formula (4). Is preferred.
[0078]
The arrangement of the constituent units in the copolymer may be random, block, alternating, graft, or the like. If the molecular weight of the copolymer is too small, the film formability is poor, and if the molecular weight is too large, the alignment as a liquid crystal, especially the monodomain formation by the rubbing alignment film is poor, and it is difficult to form a uniform alignment state. A molecular weight of 2,000 to 50,000 is preferred.
[0079]
The copolymer is produced by polymerizing with heat or light. The reaction temperature of the thermal polymerization is 0 to 150 ° C., the reaction time is 1 to 100 hours, and a radical polymerization initiator is usually used. Examples of the radical polymerization initiator include benzoyl peroxide, diisopropylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxydiisobutyrate, and peroxide. Lauroyl, dimethyl 2,2'-azobisisobutyrate (MAIB), di-t-butyl peroxide (DTBPO), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN) and the like.
[0080]
In polymerization by irradiation with light or an electron beam, a photoradical polymerization initiator is usually used. Examples of the photo-radical polymerization initiator include Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one) and Irgacure 184 (1) among products of Ciba Specialty Chemical Co., Ltd. -Hydroxycyclohexyl phenyl ketone), Irgacure 651 (2,2-dimethoxy-1,2-diphenylethan-1-one), Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgac Cure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Darocure 4265, Irgacure 784, and the like.
[0081]
Other examples of the photoradical polymerization initiator include p-methoxyphenyl-2,4-bis (trichloromethyl) triazine and 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole. 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, and the like.
[0082]
The copolymer can also be produced by an anionic polymerization method, a coordination polymerization method, or a living polymerization method. Preferred catalysts used in these polymerization methods include n-butyllithium, sec-butyllithium, t-butyllithium, alkali metal alkyls such as t-butyllithium-trialkylaluminum, aluminum compounds, transition metal compounds and the like.
[0083]
A solvent may be used for the polymerization reaction. Preferred solvents are benzene, toluene, xylene, mesitylene, pentane, hexane, heptane, octane, nonane, decane, tetrahydrofuran, 1,4-dioxane, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide and the like. A solvent in which at least two of these are mixed may be used.
[0084]
<Manufacture of optical elements>
In the method for producing an oriented film of the present invention, after the copolymer is oriented, the orientation is fixed by irradiation with ultraviolet rays. The formation of such an oriented film was performed by applying a copolymer dissolved in an organic solvent to an oriented substrate, heating the glass to a temperature equal to or higher than the glass transition point, and then allowing it to cool to uniformly align. The polymer is produced by forming a polymer thin film (optically anisotropic thin film), and further performing an alignment fixing treatment by irradiation with ultraviolet rays.
[0085]
Solvents used for preparing the copolymer solution include N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide dimethyl acetal, tetrahydrofuran, Chloroform, 1,4-dioxane, bis (methoxyethyl) ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol and the like. However, usable solvents are not limited to these. A mixture of these solvents or a mixture of these solvents with a common organic solvent such as acetone, benzene, toluene, heptane, and methylene chloride can also be used.
[0086]
In the case of forming an oriented film composed of a superimposed product with a substrate, a stretched film such as a glass plate or a plastic film, a retardation plate, or an optical film such as a polarizing plate is used. Examples of the plastic film include triacetyl cellulose, polyvinyl alcohol, polyimide, polyester, polyarylate, polyetherimide, and polyethylene terephthalate. As other specific trade names, "Arton" manufactured by JSR Corporation, "Zeonex" and "Zeonor" manufactured by Zeon Corporation, "Apel" manufactured by Mitsui Chemicals, Inc. and the like can be used.
[0087]
Coating methods for the copolymer solution include spin coating, roll coating, flow coating, printing, microgravure coating, gravure coating, wire barcode, dip coating, spray coating, and meniscus coating. It can be performed by a method of developing a thin film by a method such as a casting method or a casting film forming method, and drying it to remove the solvent.
[0088]
As the alignment-treated surface, for example, a thin film made of a generally used polyimide or polyvinyl alcohol is formed, and a rubbing treatment with a rayon cloth or the like, an obliquely deposited silicon oxide, or a stretched film is used. Can be
[0089]
After applying and drying the solution of the copolymer on the substrate, a heat treatment is performed for orientation. The heat treatment is performed by heating for a certain time in a temperature range from a glass transition point of the copolymer to a state exhibiting an isotropic phase. The developing layer after the orientation treatment is fixed in the orientation by irradiating an electromagnetic wave such as an ultraviolet ray or an electron beam. At this time, it is not necessary to add a photopolymerization initiator or the like. To use ultraviolet light, a wavelength longer than 300 nm, which does not absorb the copolymer, is preferable. When an electron beam is used, if the irradiation amount is too large, the copolymer will collapse, so 1 to 200 Mrad is preferable. The temperature at the time of electromagnetic wave irradiation is preferably the same as the temperature of the alignment treatment.
[0090]
The thickness of the thin film whose orientation is fixed varies depending on the desired retardation value, and the retardation value varies depending on the birefringence of the optically anisotropic thin film. Preferred retardation values are in the range of about 0.05 to 50 μm, and more preferred retardation values are in the range of about 0.1 to 20 μm. Further, a more preferable retardation value is in a range of about 0.5 to 10 μm. The haze value of the optically anisotropic thin film is 1.5% or less, more preferably 1.0% or less, and the transmittance is 80% or more, more preferably 85% or more. It is preferable that the transmittance satisfies these ratios in the visible light region. A haze value range of 1.5% or less is a preferable condition so as not to cause a problem in polarization performance. A transmittance range of 80% or more is a preferable condition for maintaining brightness when the optically anisotropic thin film is used for a liquid crystal display device.
[0091]
A preferred circularly polarized light separating plate according to the present invention is an adhesive superimposed body of two or more cholesteric liquid crystal polymer layers having different helical pitches in upper and lower layers, and the upper and lower layers are formed of cholesteric liquid crystal polymers having different helical pitches, The helical pitch changes in multiple steps in the thickness direction. As a result, a circularly polarized light separating plate capable of reflecting light in a wide wavelength range can be manufactured. The wavelength range of the reflected light is 150 nm or more in the visible region, preferably 180 nm or more, and more preferably 220 nm to the entire visible light range.
[0092]
By providing the circularly polarized light separating plate of the present invention with a layer that converts linearly polarized light such as a quarter-wave plate, the phase of circularly polarized light emitted from the circularly polarized light separating plate is changed to convert it into linearly polarized light. Thereby, the absorption loss of light by the polarizing plate can be reduced and the luminance of the liquid crystal display device can be improved.
[0093]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. At the phase transition temperatures described in the examples, C is a crystal, N is a nematic phase, Ch is a cholesteric phase, SmA is a smectic A phase, SmX is an unidentified smectic phase, I is an isotropic liquid, and Tm is a polymer. Is shown. The weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw / Mn) of the polymer were measured by GPC (gel permeation chromatography) using a column with an exclusion limit of 10 million, (Converted from known standard polystyrene). Note that the unit symbol L indicates liter. HTP (helical twist power) was calculated using the formula p = 1 / HTP · 1 / c (where p is the pitch and c is the weight concentration of the compound in the host liquid crystal). The pitch was measured by dissolving 1% by weight of a sample in a liquid crystal composition ZLI-1132 manufactured by Merck and using a wedge-shaped cell.
[0094]
Example 1
<Diels-Alder reaction of maleimide and furan>
1 L of furan was added to a solution of 275 g of maleimide dissolved in 3.5 L of diethyl ether, and the mixture was refluxed for 48 hours. During this time, crystals were deposited around the reactor as the reaction proceeded. When the reflux was stopped and the mixture was allowed to stand at room temperature (20 ° C.) for 1 day, crystals were further precipitated. The crystals were filtered and dried under reduced pressure to obtain 434 g of a maleimide furan adduct [i].
Melting point: 130-132 ° C
[0095]
<Production of N- (4-carboxyphenyl) maleimide>
First stage
To a solution of 196 g of maleic anhydride in 640 mL of dimethylformamide was added 274 g of 4-aminobenzoic acid, and the mixture was stirred at room temperature for 6 hours. White crystals precipitated by pouring the reaction solution into 2 L of water were separated by filtration. The crystals were dried under reduced pressure to obtain 449 g of N- (4-carboxyphenyl) maleic acid.
Melting point: 217-220 ° C
[0096]
Second stage
405 g of N- (4-carboxyphenyl) maleic acid and 23 g of sodium acetate were added to 930 ml of acetic anhydride, followed by stirring at 60 ° C. for 2 hours. White crystals precipitated by pouring the reaction solution into 3 L of ice water were separated by filtration. The obtained crystals were thoroughly washed with water, dried, and recrystallized from methanol / water (2/1) to obtain 259 g of N- (4-carboxyphenyl) maleimide.
Melting point: 208-210 ° C
[0097]
<Manufacture of liquid crystal skeleton 1>
30 g of 4- (trans-4-n-propylcyclohexyl) phenol, 27.3 g of 6-bromohexanol and 39 g of potassium carbonate were added to 300 ml of dimethylformamide, and the mixture was stirred at 90 ° C. for 3 hours. White crystals precipitated by pouring the reaction solution into 1 L of 3N hydrochloric acid were separated by filtration. The obtained crystals were thoroughly washed with water and then dried to obtain 25 g of a compound (LC1).
[0098]
The following compounds were produced in the same manner as described above.
[0100]
<Production of liquid crystal skeleton 2>
A solution of 12.3 g of 4-cyano-4'-hydroxybiphenyl, 15 g of 4- (6-hydroxyhexyloxy) benzoic acid and 0.02 g of dimethylaminopyridine in 250 ml of methylene chloride was cooled to 5 ° C. 14 g of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added in several portions, and the mixture was stirred at room temperature for 12 hours. The reaction solution was washed sequentially with water, 5% aqueous sodium hydroxide, 5% hydrochloric acid, and saturated aqueous sodium carbonate, and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was recrystallized twice from ethanol to obtain 14 g of a compound (LC13).
[0101]
The following compounds were produced in the same manner as described above.
[0103]
<Production of maleimide derivative>
To a solution consisting of 5.2 g of maleimide furan adduct [i], 13 g of compound (LC13), 8.9 g of triphenylphosphine and 200 ml of tetrahydrofuran, 11 ml of a 40% toluene solution of diethyl azodicarboxylate was added at 0 ° C. Stirred for hours. 50 ml of water and 200 ml of ethyl acetate were added to carry out liquid separation, and the organic layer was dried over anhydrous magnesium sulfate. 200 ml of toluene was added to the residue obtained by distilling off the solvent, and the mixture was refluxed for 12 hours. The residue obtained by distilling off toluene was purified by silica gel chromatography and recrystallized from ethanol to obtain 7.5 g of compound (MA1).
[0105]
1H-NMR (CDCl3) Δ 1.2-1.9 (8H, m), 3.54 (2H, t, J = 7 Hz), 4.04 (2H, t, J = 6.1 Hz) 6.68 (2H, s) 6 0.97 (2H, d, J = 9 Hz), 7.31 (2H, d, J = 9 Hz), 7.60 (2H, d, J = 9 Hz), 7.70 (4H, s), 8.15 (2H, d, J = 9Hz)
[0107]
<Production of phenylmaleimide derivative>
To a solution consisting of 3 g of N- (4-carboxyphenyl) maleimide, 134.54 g of LC and 100 ml of dichloromethane, 3.14 g of DCC and 0.02 g of DMAP were added at 0 ° C., and the mixture was stirred for 12 hours at room temperature. 100 ml of water was added for liquid separation, and the organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography (toluene / ethyl acetate = 9/1), and recrystallized from heptane to obtain 4.8 g of compound (MA2).
[0108]
The following compounds were produced in the same manner as described above.
Example 2
<Production of optically active vinyl ether derivatives>
First stage
Production of compound (K1)
[0112]
A solution of 260 g of 4-acetoxybenzoic acid and 500 ml of thionyl chloride with a few drops of dimethylformamide was refluxed for 5 hours, and then thionyl chloride was distilled off under reduced pressure to obtain 4-acetoxybenzoic acid chloride. To a solution of 168 g of L-(-)-phenethylamine, 300 ml of pyridine and 800 ml of chloroform, a solution prepared by dissolving the previously synthesized 4-acetoxybenzoic acid chloride in 500 ml of chloroform was added dropwise at room temperature, and after the addition, reflux was further continued for 4 hours. did. Water was added to the reaction solution, and the mixture was separated. The chloroform layer was washed with 5% hydrochloric acid until it became acidic, washed with saturated aqueous sodium carbonate and water in that order, and dried over anhydrous magnesium sulfate. The crystals obtained by distilling off chloroform were recrystallized from ethanol to obtain 287 g of compound (K1). Melting point 155 [deg.] C.
1H-NMR (CDCl3) Δ 1.57 (3H, d, J = 7 Hz), 2.29 (3H, s), 5.30 (1H, m), 6.44 (1H, d, J = 7.2 Hz), 7.11 (2H, d, J = 8.8 Hz), 7.36 (5H, s), 7.77 (2H, d, J = 8.8 Hz)
[0114]
Second stage
Production of Compound (K2)
[0115]
A solution of 287 g of the compound (K1) in 2 L of methanol was added with 100 ml of 28% aqueous ammonia and stirred for 1 hour. 6N hydrochloric acid was added to the reaction solution until neutral, and the reaction was terminated, and the solution was poured into 3 L of water. The precipitated crystals were separated by filtration, dried under reduced pressure, and recrystallized from chloroform to obtain 250 g of a compound (K2). Melting point 192-194 [deg.] C.
1H-NMR (CD3OD) δ 1.55 (3H, d, J = 7 Hz), 5.23 (1H, m), 6.82 (2H, d, J = 8.5 Hz), 7.33 (5H, s), 7. 73 (2H, d, J = 8.5 Hz)
Third stage
Production of compound (K3)
[0117]
50 g of the compound (K2) and 47.6 g of 4- (6-hydroxyhexyloxy) benzoic acid were dissolved in 1.3 L of methylene chloride and cooled to 5 ° C., and 1.5 g of dimethylaminopyridine and 1-ethyl-3- ( 42 g of (3-dimethylaminopropyl) carbodiimide hydrochloride was added, and the mixture was stirred at room temperature for 12 hours. 300 ml of water was added, the layers were separated, and the organic layer was washed with 6N hydrochloric acid, saturated aqueous sodium carbonate and water in that order, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was recrystallized from ethanol to obtain 57 g of a compound (K3). 170 ° C.
1H-NMR (CDCl3) Δ 1.30-1.90 (8H), 1.60 (3H, d, J = 7 Hz), 3.66 (2H, d, J = 6.2 Hz), 4.04 (2H, d, J = 6.2Hz) 5.33 (1H, m), 6.40 (1H, d, J = 7.8Hz), 6.96 (2H, d, J = 8.8Hz), 7.23 (2H, d) , J = 8.8 Hz), 7.35 (5H, s), 7.82 (2H, d, J = 8.8 Hz), 8.12 (2H, d, J = 8.8 Hz)
[0119]
4th stage
Production of Compound (KV13)
[0120]
2 g of diacet (1,10-phenanthroline) palladium was added to a solvent obtained by mixing 500 ml of n-butyl vinyl ether and 120 ml of chloroform, and the mixture was stirred at room temperature for 10 minutes. Thereto was added 22.8 g of the compound (K3), and the mixture was heated to 65 ° C. and stirred for 24 hours. The reaction solution was filtered to remove insolubles, and the concentrated residue was purified by silica gel column chromatography and recrystallization to obtain 10.2 g of a compound (KV13). 151-152 ° C.
1H-NMR (CDCl3) Δ 1.30-1.90 (8H), 1.60 (3H, d, J = 7 Hz), 3.66 (2H, d, J = 6.2 Hz), 4.04 (2H, d, J = 6.2 Hz), 4.10 and 4.25 (1H, 2s), 5.33 (1H, m), 6.40 (1H, d, J = 7.8 Hz), 6.47 (1H, q) , 6.96 (2H, d, J = 8.8 Hz), 7.23 (2H, d, J = 8.8 Hz), 7.35 (5H, s), 7.82 (2H, d, J = 8.8 Hz), 8.12 (2H, d, J = 8.8 Hz)
[0122]
Compound (KV19) was produced by the same production method as in Example 2 except that (S)-(−)-1- (naphthyl) ethylamine was used as a raw material. Melting point: 89 ° C
[0123]
Example 3
First stage
Production of Compound (K4)
[0125]
26.5 g of the compound (K2), 25 g of 6-bromohexanol and 31 g of potassium carbonate were refluxed for 5 hours while stirring in 200 ml of dimethylformamide. The reaction solution was poured into 200 ml of water, extracted with ethyl acetate, and the ethyl acetate layer was washed several times with water and dried over anhydrous magnesium sulfate. The solid obtained by distilling off the solvent was recrystallized from chloroform to obtain 23 g of compound (K4). 105-106 ° C
1H-NMR (CDCl3) Δ 1.30-1.90 (8H), 1.60 (3H, d, J = 7 Hz), 3.62 (2H, d, J = 6.2 Hz), 3.98 (2H, d, J = 6.2 Hz) 5.31 (1H, m), 6.28 (1H, d, J = 7.7 Hz), 6.88 (2H, d, J = 8.8 Hz), 7.34 (5H, s) ), 7.72 (2H, d, J = 8.8 Hz)
[0127]
Second stage
Production of Compound (KV2)
[0128]
1.8 g of diacet (1,10-phenanthroline) palladium was added to a solvent obtained by mixing 300 ml of n-butyl vinyl ether and 80 ml of chloroform, and the mixture was stirred at room temperature for 10 minutes. Thereto was added 15 g of the compound (K4), and the mixture was heated to 65 ° C. and stirred for 24 hours. The reaction solution was filtered to remove insolubles, and the concentrated residue was purified by silica gel column chromatography and recrystallization to obtain 10.2 g of a compound (KV2). Melting point 85 [deg.] C.
1H-NMR (CDCl3) Δ 1.30-1.90 (8H), 1.60 (3H, d, J = 7 Hz), 3.62 (2H, d, J = 6.2 Hz), 3.98 (2H, d, J = 6.2 Hz) 4.10 {and 4.25} (1H, 2s), 5.31 (1H, m), 6.28 (1H, d, J = 7.7 Hz), 6.47 (1H, q), 6.88 (2H, d, J = 8.8 Hz), 7.34 (5H, s), 7.72 (2H, d, J = 8.8 Hz)
[0130]
Example 4
First stage
[0131]
First stage
Production of Compound (K5)
[0132]
A solution obtained by dissolving 4-bromo-2-fluorobenzoic acid chloride in chloroform (200 ml) was added dropwise to a mixture of L-(-)-phenethylamine (78 g), pyridine (180 ml) and chloroform (400 ml) at room temperature. After the addition, the mixture was further refluxed for 4 hours. Water was added to the reaction solution, and the mixture was separated. The chloroform layer was washed with 5% hydrochloric acid until it became acidic, washed with saturated aqueous sodium carbonate and water in that order, and dried over anhydrous magnesium sulfate. The crystals obtained by distilling off chloroform were recrystallized from cyclohexane to obtain 131 g of compound (K5). Melting point 91 ° C
1H-NMR (CDCl3) Δ 1.59 (3H, d, J = 8 Hz), 5.33 (1H, m), 7.2-7.5 (7H, m), 7.97 (1H, t, J = 8 Hz)
[0134]
Second stage
Production of Compound (K6)
[0135]
Compound (K5) (50 g), trimethylsilylacetylene (38 g), PdCl2(PPh3)2(1.16 g), a solution of copper iodide (0.3 g) and triphenylphosphine (0.84 g) dissolved in triethylamine (400 L) were refluxed for 3 hours. The insolubles in the reaction solution were removed by filtration under reduced pressure, the solvent was distilled off, and the concentrate obtained was dissolved in toluene, washed with 6N hydrochloric acid until neutral, then washed with saturated aqueous sodium carbonate, and sulfuric anhydride was added. After drying with magnesium, the solvent was distilled off to obtain an oil. This oil was purified by silica gel column chromatography (toluene: ethyl acetate = 95: 5). The purified oil was dissolved in 300 ml of tetrahydrofuran and cooled to -50 ° C once. A 1 mol / l solution (180 ml) of tetrabutylammonium fluoride was added dropwise thereto. After stirring at −50 ° C. for 1 hour, the temperature was raised to 0 ° C., water (50 ml) was added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was extracted with 400 ml of ethyl acetate, and the organic layer was dried over 6N hydrochloric acid, saturated aqueous sodium carbonate, and anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was recrystallized from cyclohexane to obtain 26 g of (K6). Melting point 94 ° C
1H-NMR (CDCl3) Δ 1.60 (3H, d, J = 7 Hz), 3.22 (1H, s), 5.33 (1H, m), 7.2-7.5 (7H, m), 8.04 (1H) , T, J = 8 Hz)
[0137]
Third stage
Production of Compound (K7)
[0138]
Compound (K6) (13 g), tetrahydropyranyl ether of {4- (3-hydroxypropyloxy) bromobenzene (15 g), PdCl2(PPh3)2(0.34 g), a solution of copper iodide (0.09 g) and triphenylphosphine (0.25 g) dissolved in triethylamine (100 L) were refluxed for 6 hours. The insolubles in the reaction solution were removed by filtration under reduced pressure, and the residue obtained by evaporating the solvent was dissolved in toluene, washed with 6N hydrochloric acid until it became acidic, then washed with saturated aqueous sodium carbonate, and anhydrous magnesium sulfate. And the solvent was distilled off to obtain a solid. The oily substance was subjected to silica gel column chromatography (chloroform: methanol = 97: 3) to remove the catalyst, and the concentrate was recrystallized from cyclohexane to obtain 4 g of (K7). 133-135 ° C.
1H-NMR (CDCl3) Δ 1.60 (3H, d, J = 7 Hz), 2.14 (2H, m), 3.87 (2H, t, J = 6.0 Hz), 4.14 (2H, t, J = 6. Hz). 0 Hz), 5.33 (1H, m), 6.88 (2H, d, J = 8.8 Hz), 7.2 to 7.6 (9H, m), 8.05 (1H, t, J = 8Hz)
[0140]
4th stage
Production of Compound (KV41)
[0141]
To a solvent obtained by mixing 25 ml of n-butyl vinyl ether and 5 ml of chloroform was added 0.17 g of diaceto (1,10-phenanthroline) palladium, and the mixture was stirred at room temperature for 10 minutes. Thereto was added 1.8 g of the compound (K7), and the mixture was heated to 65 ° C and stirred for 10 hours. The reaction solution was filtered to remove insolubles, and the concentrate was purified by silica gel column chromatography and recrystallization to obtain 0.5 g of a compound (KV41). 117 ° C.
1H-NMR (CDCl3) Δ 1.60 (3H, d, J = 7 Hz), 2.14 (2H, m), 3.87 (2H, t, J = 6.0 Hz), 4.10 (2H, t, J = 6. Hz). 0 Hz), 4.10 {4.25} (1H, 2s), 5.33 (1H, m), 6.47 (1H, q), 6.88 (2H, d, J = 8.8 Hz), 7 0.2 to 7.6 (9H, m), 8.05 (1H, t, J = 8Hz)
[0143]
Comparative Example 1
The HTP of (CB-15), a general chiral agent, and the compound of the present invention were compared.
[0144]
Compound name @ HTP
(CB-15) 5.7 μm-1・ Wt%-1
(KV2) 46.5 μm-1・ Wt%-1
(KV13) 37.7 μm-1・ Wt%-1
The compounds of the present invention showed HTP more than 6 times larger than CB-15. That is, it can be seen from the results that the compound of the present invention has a large helix inducing force.
[0146]
Example 5
<Production of copolymer>
Production of cholesteric liquid crystal copolymer [eg MVC1]
[0147]
0.5 g of maleimide (MA1), 0.12 g of optically active vinyl ether (KV13), 0.003 g of AIBN, and 2 ml of dimethyl sulfoxide were placed in an ampoule, cooled to -60 ° C, sufficiently degassed by a vacuum pump, and sealed. The sealed ampule was reacted at 60 ° C. for 48 hours. The contents of the ampoule were dissolved in 10 ml of tetrahydrofuran and poured into 100 ml of methanol to precipitate. After performing this operation three times, the resultant is sufficiently washed with methanol and dried under reduced pressure to obtain 0.4 g of a copolymer [for example, any of MVC1, random, block, alternating, and graft copolymers]. Was.
The copolymer constituent ratio of each skeleton calculated by measurement at 500 Hz proton NMR was x: y = 73: 27.
Weight average molecular weight (MW): 37,000
Polydispersity (Mw / Mn): 2.15
Phase transition temperature: Tm 157 Ch 280 I
The polymer [MVC1] was a polymer showing a cholesteric phase.
[0149]
Example 6
Production of cholesteric liquid crystal copolymer [eg MVC2]
[0150]
Using 0.5 g of maleimide (MA6), 0.18 g of optically active vinyl ether (KV19), 0.0041 g of AIBN, and 2 ml of tetrahydrofuran, a copolymer was prepared in the same manner as in Example 3 except that the reaction was carried out at 60 ° C. for 24 hours. MVC2, any of random, block, alternating, and graft copolymers].
The copolymer constituent ratio of each skeleton calculated by measurement at 500 Hz proton NMR was x: y = 83: 17.
Weight average molecular weight (MW): 22,000
Polydispersity (Mw / Mn): 1.87
Phase transition temperature: Tm 105 Ch 109 I
The polymer [MVC2] was a polymer showing a cholesteric phase.
[0152]
Example 7
Production of cholesteric liquid crystal copolymer [eg MVC3]
[0153]
Using 0.5 g of maleimide (MA1), 0.16 g of optically active vinyl ether (KV2), 0.0035 g of AIBN, and 2 ml of dimethyl sulfoxide, the copolymer was prepared in the same manner as in Example 3 except that the reaction was carried out at 60 ° C. for 48 hours. For example, any of MVC3, random, block, alternating, and graft copolymers may be used].
The copolymer composition ratio of each skeleton calculated by measurement at 500 Hz proton NMR was x: y = 74: 26.
Weight average molecular weight (MW): 38,000
Polydispersity (Mw / Mn): 3.19
Phase transition temperature: Tm 270 Ch 290 I
The polymer [MVC3] was a polymer showing a cholesteric phase.
[0155]
Example 8
Production of cholesteric liquid crystal copolymer [eg MVC4]
[0156]
Using maleimide (MA11) 0.3 g, maleimide (MA14) 0.26 g, vinyl ether (KV13) 0.15 g, AIBN 0.0037 g, dimethyl sulfoxide (2 ml), tetrahydrofuran 2 ml, except that the reaction was carried out at 60 ° C. for 12 hours. In the same manner as in Example 3, 0.4 g of a copolymer (for example, any of MVC4, random, block, alternating, and graft copolymers) was obtained.
The copolymer constituent ratio of each skeleton calculated by measurement at 500 Hz proton NMR was x + y: w = 85: 15.
Weight average molecular weight (MW): 12,000
Polydispersity (Mw / Mn): 2.39
Phase transition temperature: Tm 107 Ch 130 I
The polymer [MVC4] was a polymer showing a cholesteric phase.
[0158]
Example 9
Production of cholesteric liquid crystal copolymer [eg MVC5]
[0159]
Using a method similar to that of Example 3 except that 0.26 g of maleimide (MA1), 0.1 g of optically active vinyl ether (KV41), 0.0002 g of AIBN, and 1 ml of tetrahydrofuran were reacted at 60 ° C. for 6 hours [for example, MVC5, random, block, alternating, graft copolymer, etc.].
The copolymerization ratio calculated from the 500 Hz proton NMR measurement was y: w = 75: 25.
Weight average molecular weight (MW): 5,600
Polydispersity (Mw / Mn): 1.48
Phase transition temperature: Tm 137 Ch 251 I
The polymer [MVC5] was a polymer showing a cholesteric phase.
[0161]
Example 10
<Production of circularly polarized film>
0.5 g of maleimide (MA1), 0.12 g of optically active vinyl ether (KV13), 0.003 g of AIBN, and 2 ml of dimethyl sulfoxide were placed in an eggplant-shaped flask, sufficiently degassed with a vacuum pump, and then purged with argon, and then at 60 ° C. for 3 hours. Reacted. The contents were poured into 100 ml of water to precipitate. The precipitate was thoroughly washed with water and dried under reduced pressure to obtain 0.6 g of a solid [MVC3]. Weight average molecular weight (MW) Was 2000, the melting point was 140 ° C., and the clearing point was 280 or more. A polyvinyl alcohol layer having a thickness of about 0.1 μ was provided on a triacetyl cellulose film having a thickness of 50 μm, rubbed with a rayon cloth, and the treated surface was spin-coated with a chloroform solution (30% by weight) of [MVC3]. . After sufficiently drying, the alignment treatment is performed at 120 ° C. for 15 minutes. Then, while maintaining the same temperature, a high-pressure mercury lamp (120 W / cm2) For 1 minute. After irradiation, the temperature was returned to room temperature to obtain a film.
The polymer layer of this film has a thickness of 2 μm, and the optical element formed integrally with the triacetyl cellulose film exhibits circular dichroism reflecting blue light, and this reflected light is left circularly polarized light of 412 to 694 nm. Met. Even if this film was once heated to 280 ° C. and returned to room temperature, the orientation was maintained without breaking.
[0162]
Example 11
Polymerization and element production were carried out according to Examples 7 and 10, except that 0.5 g of maleimide (MA1) and 0.09 g of optically active vinyl ether (KV13) were used. This optical element exhibited circular dichroism reflecting red light, and the reflected light was left circularly polarized light at 581 to 695 nm.
[0163]
Example 12
The copolymers obtained in Examples 7 and 8 were mixed at a ratio of 1: 1 to produce a device according to Example 10. This optical element exhibited circular dichroism reflecting green light, and the reflected light was left circularly polarized light at 480 to 585 nm.
[0164]
Example 13
The optical elements obtained in Examples 10, 11, and 12 were laminated via an acrylic adhesive to obtain an optical element exhibiting circular dichroism in the range of 410 to 690 nm. A ４λ plate composed of a laminate of two stretched films made of polycarbonate was laminated on this optical element via an acrylic pressure-sensitive adhesive layer, and when natural light was incident thereon, the color change based on the NBS method was 3, and the color change was 3. Was small. In addition, even when the optical element with the ４λ plate was heated at 80 ° C. for 1000 hours, 90% humidity and 60 ° C. for 1000 hours, almost no change in the optical characteristics and appearance was recognized. And excellent durability.
[0165]
Comparative Example 2
[MVC3] obtained in Example 7 was dissolved in chloroform to prepare a 30% by weight solution. This solution was spin-coated on a glass substrate provided with an alignment film subjected to a rubbing alignment treatment, and then sufficiently dried to obtain a thin film (thickness: 30 nm). This substrate was placed in an oven at 120 ° C. and annealed for 5 minutes. It was visually confirmed that the substrate had developed a red color. When the substrate was taken out of the oven and returned to room temperature, the color of the red film disappeared and the film became cloudy, and the Grandian orientation was lost. The clearing point of this film was 140 ° C., which was the same as the clearing point before coating.
[0166]
【The invention's effect】
The optically active vinyl ether derivative (1) of the present invention is a monomer having a large helical inducing force and having excellent copolymerizability with maleimide.
The maleimide-vinyl ether copolymer of the present invention can be applied to a coating method and has excellent orientation. The film produced by using the copolymer of the present invention can fix the orientation by irradiating an electromagnetic wave without using a crosslinking agent, and can easily produce a film having high heat resistance. Since the oriented film made of the copolymer of the present invention exhibits circular polarization, it can be used for applications such as a color compensator, an optical phase plate, and a notch film used for a liquid crystal display device.
Claims (22)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004204190A (en) * | 2002-12-26 | 2004-07-22 | Chisso Corp | Photopolymerizable liquid crystal composition and liquid crystal film |
| TWI411617B (en) * | 2004-09-29 | 2013-10-11 | Fujifilm Corp | Cellulose derivative composition, cellulose derivative film and trialkoxybenzoic acid deriv ative compound |
| WO2018168721A1 (en) * | 2017-03-17 | 2018-09-20 | Jnc株式会社 | Liquid-crystal composition and liquid-crystal display element |
| JPWO2017199778A1 (en) * | 2016-05-19 | 2019-02-14 | Jnc株式会社 | Polymerizable compound and composition, liquid crystal composite, optical anisotropic body, liquid crystal display element and use thereof |
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2002
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004204190A (en) * | 2002-12-26 | 2004-07-22 | Chisso Corp | Photopolymerizable liquid crystal composition and liquid crystal film |
| JP4507490B2 (en) * | 2002-12-26 | 2010-07-21 | チッソ株式会社 | Photopolymerizable liquid crystal composition and liquid crystal film |
| TWI411617B (en) * | 2004-09-29 | 2013-10-11 | Fujifilm Corp | Cellulose derivative composition, cellulose derivative film and trialkoxybenzoic acid deriv ative compound |
| JPWO2017199778A1 (en) * | 2016-05-19 | 2019-02-14 | Jnc株式会社 | Polymerizable compound and composition, liquid crystal composite, optical anisotropic body, liquid crystal display element and use thereof |
| JP2020011987A (en) * | 2016-05-19 | 2020-01-23 | Jnc株式会社 | Polymerizable compound and composition, liquid crystal composite, optical anisotropic body, liquid crystal display element and use thereof |
| JP2020011988A (en) * | 2016-05-19 | 2020-01-23 | Jnc株式会社 | Polymerizable compound and composition, liquid crystal composite, optical anisotropic body, liquid crystal display element and use thereof |
| WO2018168721A1 (en) * | 2017-03-17 | 2018-09-20 | Jnc株式会社 | Liquid-crystal composition and liquid-crystal display element |
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