JP2013087109A - Polymerizable chiral compound - Google Patents
Polymerizable chiral compound Download PDFInfo
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- JP2013087109A JP2013087109A JP2011231702A JP2011231702A JP2013087109A JP 2013087109 A JP2013087109 A JP 2013087109A JP 2011231702 A JP2011231702 A JP 2011231702A JP 2011231702 A JP2011231702 A JP 2011231702A JP 2013087109 A JP2013087109 A JP 2013087109A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 113
- 239000000203 mixture Substances 0.000 claims abstract description 70
- 230000003287 optical effect Effects 0.000 claims abstract description 31
- -1 naphthalene-2,6-diyl group Chemical group 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 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 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 60
- 230000008018 melting Effects 0.000 abstract description 16
- 238000002844 melting Methods 0.000 abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- 238000006243 chemical reaction Methods 0.000 description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- 239000002904 solvent Substances 0.000 description 26
- 239000000758 substrate Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 238000005886 esterification reaction Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000010409 thin film Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 125000004430 oxygen atom Chemical group O* 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 8
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 229960002479 isosorbide Drugs 0.000 description 8
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 5
- 239000004988 Nematic liquid crystal Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RZZZQPNSNIVWAU-UHFFFAOYSA-N 4-prop-2-enoyloxybenzoic acid Chemical compound OC(=O)C1=CC=C(OC(=O)C=C)C=C1 RZZZQPNSNIVWAU-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000005419 hydroxybenzoic acid derivatives Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- KLDXJTOLSGUMSJ-KVTDHHQDSA-N (3r,3ar,6r,6ar)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@@H]1CO[C@@H]2[C@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-KVTDHHQDSA-N 0.000 description 2
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-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
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 2
- YSAVZVORKRDODB-UHFFFAOYSA-N Diethyl tartrate Chemical compound CCOC(=O)C(O)C(O)C(=O)OCC YSAVZVORKRDODB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 238000001953 recrystallisation Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
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- ZPLLNXMJMCTLOE-UHFFFAOYSA-N 2-(4-phenylmethoxyphenyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(C=C1)=CC=C1OCC1=CC=CC=C1 ZPLLNXMJMCTLOE-UHFFFAOYSA-N 0.000 description 1
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- GAXUWNPJYOWVDR-UHFFFAOYSA-N 3-(4-hydroxyphenyl)-2-phenylprop-2-enoic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)=CC1=CC=C(O)C=C1 GAXUWNPJYOWVDR-UHFFFAOYSA-N 0.000 description 1
- WINNQOZTIDYENK-UHFFFAOYSA-N 3-(4-hydroxyphenyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC(O)=CC=2)=C1 WINNQOZTIDYENK-UHFFFAOYSA-N 0.000 description 1
- MQUAYIQAPMFLCC-UHFFFAOYSA-N 3-chloro-4-phenylmethoxybenzoic acid Chemical compound ClC1=CC(C(=O)O)=CC=C1OCC1=CC=CC=C1 MQUAYIQAPMFLCC-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical class CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- JTGCXYYDAVPSFD-UHFFFAOYSA-N 4-(4-hydroxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(O)C=C1 JTGCXYYDAVPSFD-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
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- QRMYFOOFOAGDGE-UHFFFAOYSA-N 6-prop-2-enoyloxynaphthalene-2-carboxylic acid Chemical compound C1=C(OC(=O)C=C)C=CC2=CC(C(=O)O)=CC=C21 QRMYFOOFOAGDGE-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は重合性キラル化合物および当該化合物を含有する重合性液晶組成物、さらに当該重合性液晶組成物の硬化物である光学異方体に関する。 The present invention relates to a polymerizable chiral compound, a polymerizable liquid crystal composition containing the compound, and an optical anisotropic body which is a cured product of the polymerizable liquid crystal composition.
近年、情報化社会の進展に伴い表示ディスプレイに必須な偏向板、位相差板などに用いられる光学異方体の重要性は益々高まっている。光学異方体に必要な光学特性は目的により異なるので目的にあった特性を有する化合物が必要である。また、光学特性だけでなく化合物の重合速度、溶解性、融点、ガラス転移点、重合物の透明性、重合物の機械的強度なども重要な因子となる。 In recent years, with the progress of the information society, the importance of optical anisotropic bodies used for deflecting plates, retardation plates and the like essential for display displays has been increasing. Since the optical properties necessary for the optical anisotropic body vary depending on the purpose, a compound having the properties suitable for the purpose is required. In addition to the optical properties, the polymerization rate, solubility, melting point, glass transition point, transparency of the polymer, mechanical strength of the polymer, and the like are important factors.
近年、重合性コレステリック液晶を用いた円偏光分離機能素子が、輝度向上フィルムとして活用されている。コレステリック液晶は通常、ネマチック液晶に光学活性化合物（以下、キラル化合物）を添加することにより調製できる。液晶デバイスの光学補償フィルムとして、紫外線領域から可視光領域までの円偏光分離機能を得るためには、非常にピッチ(p)の短いらせん構造を必要とする。分子らせんのピッチｐは、式(a)に従い、液晶組成物におけるキラル化合物の濃度ｃに反比例する。比例定数はキラル化合物のらせんねじれ力（ＨＴＰ）である。短いピッチを得るためには、キラル化合物の濃度を増やすか、ねじれ力を強くすれば得られる。 In recent years, circularly polarized light separating functional elements using polymerizable cholesteric liquid crystals have been utilized as brightness enhancement films. A cholesteric liquid crystal can be usually prepared by adding an optically active compound (hereinafter referred to as a chiral compound) to a nematic liquid crystal. As an optical compensation film for liquid crystal devices, a helical structure with a very short pitch (p) is required to obtain a circularly polarized light separating function from the ultraviolet region to the visible light region. The pitch p of the molecular helix is inversely proportional to the concentration c of the chiral compound in the liquid crystal composition according to the formula (a). The proportionality constant is the helical twisting power (HTP) of the chiral compound. In order to obtain a short pitch, it can be obtained by increasing the concentration of the chiral compound or increasing the twisting force.
しかしながらキラル化合物を多く配合してしまうと液晶性、溶解性、重合物の透明性などの光学特性の低下や、高価なキラル化合物による高コスト化のため好ましくない。そこでＨＴＰの強いキラル化合物を用いた液晶組成物が望ましい。このような強いＨＴＰを示す化合物として環構造の光学活性部位を有するキラル化合物が提案されている（引用文献１および２参照）。これらの引用文献には１，４：３，６−ジアンヒドロ−Ｄ−マンニトール（イソマンニド）、ジアンヒドロ−Ｄ−グルシトール（イソソルビド）、ビナフトール等の光学活性化合物に基づく強いＨＴＰを有する重合性キラル化合物が開示されている。しかしながら、これらの光学活性化合物は融点が高く溶解性が悪い、一部の液晶化合物との相溶性が低い等の問題があった（引用文献１）。また、溶解性を向上させるために構造を非対称とした化合物は、溶解性の点ではある程度の改善が見られるものの、製造が煩雑であることから製造コストが高く、光学異方性体の高価格化の要因となる問題があった（引用文献２）。 However, if a large amount of chiral compound is added, it is not preferable because of deterioration of optical properties such as liquid crystallinity, solubility, and transparency of the polymer, and high cost due to expensive chiral compounds. Therefore, a liquid crystal composition using a chiral compound having strong HTP is desirable. As compounds showing such strong HTP, chiral compounds having an optically active site of a ring structure have been proposed (see References 1 and 2). These references disclose polymerizable chiral compounds having strong HTP based on optically active compounds such as 1,4: 3,6-dianhydro-D-mannitol (isomannide), dianhydro-D-glucitol (isosorbide), binaphthol and the like. Has been. However, these optically active compounds have problems such as high melting point and poor solubility and low compatibility with some liquid crystal compounds (Cited document 1). In addition, a compound having an asymmetric structure for improving the solubility is somewhat improved in terms of solubility, but is expensive to manufacture due to the complexity of manufacturing and the high cost of the optically anisotropic material. There was a problem that became a factor of the conversion (Cited document 2).
本発明が解決しようとする課題は、強いＨＴＰを有する溶解性に優れた重合性キラル化合物を提供することである。 The problem to be solved by the present invention is to provide a polymerizable chiral compound having strong HTP and excellent solubility.
本願発明者らは重合性化合物における種々の置換基の検討を行った結果、特定の構造を有する重合性化合物が前述の課題を解決できることを見出し、本願発明を完成するに至った。 As a result of studying various substituents in the polymerizable compound, the present inventors have found that a polymerizable compound having a specific structure can solve the above-mentioned problems, and have completed the present invention.
本願発明は、一般式（Ｉ） The present invention relates to the general formula (I)
（ただし、Ｒ１及びＲ２はお互い独立して以下の式（Ｒ−１）から式（Ｒ−１５）の何れか (However, R 1 and R 2 are each independently any of the following formulas (R-1) to (R-15):
を表し、Ａ１、Ａ２、Ａ３及びＡ４はお互い独立して１，４−フェニレン基、ナフタレン−２，６−ジイル基，１，４−シクロヘキシレン基又はピリジン−２，５−ジイル基を表し、Ａ１、Ａ２、Ａ３及びＡ４に含まれる水素原子はお互い独立してアルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲン、シアノ基又はニトロ基により置換されていても良く、Ｂ１及びＢ２はお互い独立して、−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＯ−ＮＲ１１−、−ＮＲ１１−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＯＯ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＯＣＯ−ＣＨ２ＣＨ２−、−Ｃ≡Ｃ−又は単結合を表し（ただし、Ｒ１１は水素原子又は炭素数１〜４のアルキル基を表す。）、Ｚ１は、−ＣＯＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２Ｏ−又は−ＣＦ２Ｏ−を表し、Ｚ２は、−ＯＣＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＯＣＨ２−又は−ＯＣＦ２−を表し、Ｚは以下の一般式（Ｚ−１）から（Ｚ−３）で表される２価の置換基の何れかを表し、 A 1 , A 2 , A 3 and A 4 are each independently 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group or pyridine-2,5-diyl. A hydrogen atom contained in A 1 , A 2 , A 3 and A 4 may be independently substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen, a cyano group or a nitro group. , B 1 and B 2 are independently of each other —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —OCOO—, —CO—. NR 11 -, - NR 11 -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - OCO-CH = CH -, - COO-CH = CH -, - CH = CH -OCO -, - CH 2 CH 2 -COO -, - CO -CH 2 CH 2 -, - CH 2 CH 2 -OCO -, - OCO-CH 2 CH 2 -, - C≡C- or a single bond (provided that, R 11 is C1-4 hydrogen or C Represents an alkyl group.), Z 1 represents —COO—, —CH═CH—COO—, —CH 2 CH 2 —COO—, —CH 2 O— or —CF 2 O—, and Z 2 represents —OCO—, —OCO—CH═CH—, —OCO—CH 2 CH 2 —, —OCH 2 — or —OCF 2 — is represented, and Z represents the following general formulas (Z-1) to (Z-3) Any one of the divalent substituents represented by
（式中、各置換基は点線で表される結合の一方でＺ１に他方でＺ２と結合することを表しており、Ｙ１、Ｙ２、Ｙ３、Ｙ４、Ｙ５及びＹ６は、それぞれ独立して炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基及び水素原子を表し、式中の一般式（Ｚ−１）から（Ｚ−３）で表される２価の置換基は単一の立体構造を表す。）ｍ及びｎはお互い独立して、０、１又は２を表すが、Ａ１、Ａ２、Ｂ１又は／及びＢ２が複数存在する場合それらはお互い独立して同一であっても異なっていてもよい。）で重合性キラル化合物を提供し、当該化合物を構成部材とする重合性組成物、更に、当該重合性組成物を用いた光学異方体を提供する。 (In the formula, each of the substituents represents that one of the bonds represented by a dotted line is bonded to Z 1 and the other is bonded to Z 2, and Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are represented. Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and a hydrogen atom, and represented by general formulas (Z-1) to (Z-3) in the formula: A valent substituent represents a single steric structure.) M and n independently of one another represent 0, 1 or 2, but there are a plurality of A 1 , A 2 , B 1 or / and B 2 They may be the same or different independently of each other. ) To provide a polymerizable chiral compound, a polymerizable composition comprising the compound as a constituent member, and an optical anisotropic body using the polymerizable composition.
本願発明の重合性キラル化合物は、強いＨＴＰ及び低い融点を有し、低融点であることから他の液晶化合物との優れた溶解性を有し重合性液晶組成物の構成部材として有用である。又、製造方法も簡便なため安価に製造できるメリットもある。本願発明の重合性キラル化合物はねじれ力が強いために優れた光学特性を有する光学異方体を作製することができる。本願発明の光学異方体は、偏向板、位相差板、選択反射板等の用途に有用である。 The polymerizable chiral compound of the present invention has a strong HTP, a low melting point, and has a low melting point, so that it has excellent solubility with other liquid crystal compounds and is useful as a constituent member of a polymerizable liquid crystal composition. In addition, since the manufacturing method is simple, there is an advantage that it can be manufactured at low cost. Since the polymerizable chiral compound of the present invention has a strong twisting power, an optical anisotropic body having excellent optical properties can be produced. The optical anisotropic body of the present invention is useful for applications such as a deflection plate, a phase difference plate, and a selective reflection plate.
一般式（Ｉ）において、Ｒ１及びＲ２はお互い独立して重合性基を表すが、重合性基の具体的な例としては、下記に示す構造が挙げられる。 In General Formula (I), R 1 and R 2 each independently represent a polymerizable group, and specific examples of the polymerizable group include the structures shown below.
これらの重合基はラジカル重合、ラジカル付加重合、カチオン重合、及びアニオン重合により硬化する。特に重合方法として紫外線重合を行う場合には、式（Ｒ−１）、式（Ｒ−２）、式（Ｒ−４）、式（Ｒ−５）、式（Ｒ−７）、式（Ｒ−１１）、式（Ｒ−１３）又は式（Ｒ−１５）が好ましく、式（Ｒ−１）、式（Ｒ−２）、式（Ｒ−７）、式（Ｒ−１１）又は式（Ｒ−１３）がより好ましく、式（Ｒ−１）又は式（Ｒ−２）がより好ましい。 These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when performing ultraviolet polymerization as a polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R -11), formula (R-13) or formula (R-15) are preferred, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferred, and formula (R-1) or formula (R-2) is more preferred.
Ａ１、Ａ２、Ａ３及びＡ４は独立して１，４−フェニレン基およびナフタレン−２，６−ジイル基，１，４−シクロヘキシレン基又はピリジン−２，５−ジイル基を表し、Ａ１、Ａ２、Ａ３及びＡ４はお互い独立してアルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲン、シアノ基又はニトロ基により置換されていても良いが、強いＨＴＰ、溶解性の面で、１，４−フェニレン基、ナフタレン−２，６−ジイル基又はピリジン−２，５−ジイル基が好ましく、１，４−フェニレン基又はナフタレン−２，６−ジイル基がより好ましく、置換基としては、ハロゲン、炭素数１〜４のアルキル基及びアルコキシ基が好ましい。 A 1 , A 2 , A 3 and A 4 independently represent 1,4-phenylene group and naphthalene-2,6-diyl group, 1,4-cyclohexylene group or pyridine-2,5-diyl group, A 1 , A 2 , A 3 and A 4 may be each independently substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen, a cyano group or a nitro group, but have strong HTP and solubility. 1,4-phenylene group, naphthalene-2,6-diyl group or pyridine-2,5-diyl group is preferable, 1,4-phenylene group or naphthalene-2,6-diyl group is more preferable, substituent group Are preferably halogen, an alkyl group having 1 to 4 carbon atoms and an alkoxy group.
Ｂ１及びＢ２はお互い独立して、−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＯ−ＮＲ１１−、−ＮＲ１１−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、―ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＯＯＣ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＯＣＯ−ＣＨ２ＣＨ２−、−Ｃ≡Ｃ−又は単結合を表すが、−ＯＣＨ２−、−ＣＨ２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、―ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＯＯＣ−ＣＨ２ＣＨ２−、−ＣＨ２ＣＨ２−ＯＣＯ−、−ＯＣＯ−ＣＨ２ＣＨ２−、−Ｃ≡Ｃ−又は単結合が好ましく、−ＯＣＨ２−、−ＣＨ２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、―ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−又は単結合がより好ましい。 B 1 and B 2 are, independently of each other, —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —OCOO—, —CO—NR. 11 −, —NR 11 —CO—, —SCH 2 —, —CH 2 S—, —CH═CH—COO—, —OCO—CH═CH—, —CH 2 CH 2 —COO—, —OOC—CH 2 CH 2 —, —CH 2 CH 2 —OCO—, —OCO—CH 2 CH 2 —, —C≡C— or a single bond, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —CH 2 CH 2 —COO—, —OOC—CH 2 CH 2 —, —CH 2 CH 2 —OCO—, —OCO— CH 2 CH 2 -, - C≡C- or a single bond are preferred, -OCH 2 -, - CH 2 -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH- or a single bond is more preferable.
Ｚ１は、−ＣＯＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＨ２ＣＨ２−ＣＯＯ−、−ＣＨ２Ｏ−又は−ＣＦ２Ｏ−を表し、Ｚ２は、−ＯＣＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ２ＣＨ２−、−ＯＣＨ２−又は−ＯＣＦ２−を表すが、分子の剛直性を高め、ＨＴＰを強くするには、Ｚ１は−ＣＯＯ−又は−ＣＨ＝ＣＨ−ＣＯＯ−が好ましく、Ｚ２は−ＯＣＯ−又は−ＯＣＯ−ＣＨ＝ＣＨ−が好ましい。Ｚ１及びＺ２は同一であっても異なっていてもよいが、同一である方が製造工程が簡略であり好ましい。 Z 1 represents —COO—, —CH═CH—COO—, —CH 2 CH 2 —COO—, —CH 2 O— or —CF 2 O—, and Z 2 represents —OCO—, —OCO—. CH = CH—, —OCO—CH 2 CH 2 —, —OCH 2 — or —OCF 2 —, but in order to increase molecular rigidity and strengthen HTP, Z 1 is —COO— or —CH ═CH—COO— is preferable, and Z 2 is preferably —OCO— or —OCO—CH═CH—. Z 1 and Z 2 may be the same or different, but the same is preferable because the manufacturing process is simple.
Ｚは以下の一般式（Ｚ−１）から式（Ｚ−３）で表される２価の置換基の何れかを表すが、一般式（Ｚ−１）又は（Ｚ−３）で表される２価の置換基がより好ましい。 Z represents any of the divalent substituents represented by the following general formulas (Z-1) to (Z-3), and is represented by the general formula (Z-1) or (Z-3). More preferred are divalent substituents.
なお、一般式（Ｚ−３）で表される２価の置換基は軸不斉の化合物である。また、一般式（Ｚ−１）又は（Ｚ−３）で表される２価の置換基は実質的に単一の異性体を示す。 Note that the divalent substituent represented by the general formula (Z-3) is an axially asymmetric compound. Moreover, the bivalent substituent represented by general formula (Z-1) or (Z-3) shows a single isomer substantially.
ｍおよびｎは０、１又は２を表すが、ｍ及びｎは０又は１が好ましい。 m and n represent 0, 1 or 2, and m and n are preferably 0 or 1.
Ａ１、Ａ２、Ｂ１又は／及びＢ２が複数存在する場合それらはお互い独立して同一であっても異なっていてもよい。 When a plurality of A 1 , A 2 , B 1 and / or B 2 are present, they may be the same or different independently of each other.
また本発明の一般式（Ｉ）で表される重合性キラル化合物は環骨格と重合性基が直接結合しているため、メソゲン部位の剛直性が増加し高ＨＴＰが得られる。また、溶解性も改善され当該液晶組成物による光学異方体は優れた反射特性を有する。本発明は、当該化合物、及び構成部材とする液晶組成物、更に当該液晶組成物を用いた光学異方体を提供する。 In the polymerizable chiral compound represented by the general formula (I) of the present invention, since the ring skeleton and the polymerizable group are directly bonded to each other, the rigidity of the mesogen moiety is increased and high HTP is obtained. Further, the solubility is improved, and the optical anisotropic body of the liquid crystal composition has excellent reflection characteristics. The present invention provides the compound, a liquid crystal composition as a constituent member, and an optical anisotropic body using the liquid crystal composition.
一般式（Ｉ）で表される化合物は、より具体的には、下記の式（Ｉ−１）〜一般式（Ｉ−３８）で表される化合物が好ましい。 More specifically, the compound represented by the general formula (I) is preferably a compound represented by the following formula (I-1) to general formula (I-38).
式（Ｉ−２１）〜（Ｉ−２４）及び（Ｉ−３７）にはＲ体及びＳ体があるがねじれ力は同一であるので、特定の用途以外ではどちらでも構わない。本発明の化合物は以下に記載する合成方法で合成することができる。
（製法１） 一般式（Ｉ−３）で表される化合物の製造
4-ベンジルオキシ-3-クロロ安息香酸とイソソルビド（（３Ｓ，３ａα，６ａα）−ヘキサヒドロフロ［３，２−ｂ］フラン−３α，６β−ジオール）とのジシクロヘキシルカルボジイミド（ＤＣＣ）等の脱水縮合剤及び触媒としてＮ，Ｎ−ジメチル−４−アミノピリジン（ＤＭＡＰ）等を用いたエステル化反応により得られる式（Ｓ−１）で表される化合物を、パラジウムカーボンによる接触水素還元によりベンジル基を脱離させて式（Ｓ−２）で表されるイソソルビド誘導体を得る。更にメタクリル酸クロリドとのエステル化反応により、式（Ｉ−３）で表される目的化合物を得ることができる。
The formulas (I-21) to (I-24) and (I-37) include an R body and an S body, but the torsional force is the same. The compound of the present invention can be synthesized by the synthesis method described below.
(Production Method 1) Production of Compound Represented by General Formula (I-3)
Dehydration condensation of 4-benzyloxy-3-chlorobenzoic acid and isosorbide ((3S, 3aα, 6aα) -hexahydrofuro [3,2-b] furan-3α, 6β-diol) such as dicyclohexylcarbodiimide (DCC) The compound represented by the formula (S-1) obtained by esterification reaction using N, N-dimethyl-4-aminopyridine (DMAP) or the like as an agent and catalyst is converted into a benzyl group by catalytic hydrogen reduction with palladium carbon. The isosorbide derivative represented by the formula (S-2) is obtained by desorption. Furthermore, the target compound represented by the formula (I-3) can be obtained by an esterification reaction with methacrylic acid chloride.
（製法２） 一般式（Ｉ−８）で表される化合物の製造
４’−ベンジルオキシビフェニルカルボン酸とイソソルビドとのＤＣＣ等の脱水縮合剤を用いたエステル化反応により得られる式（Ｓ−３）で表される化合物を、パラジウムカーボン（Ｐｄ／Ｃ）による接触水素還元によりベンジル基を脱離させて式（Ｓ−４）で表されるイソソルビド誘導体を得る。更にメタクリル酸クロリドとのエステル化反応により、式（Ｉ−８）で表される目的化合物を得ることができる。
(Production Method 2) Production of Compound Represented by General Formula (I-8) Formula (S-3) obtained by esterification reaction of 4′-benzyloxybiphenylcarboxylic acid and isosorbide using a dehydration condensing agent such as DCC ) To remove the benzyl group by catalytic hydrogen reduction with palladium carbon (Pd / C) to obtain an isosorbide derivative represented by the formula (S-4). Furthermore, the target compound represented by the formula (I-8) can be obtained by an esterification reaction with methacrylic acid chloride.
（製法３） 一般式（Ｉ−１４）で表される化合物の製造
４−ベンジルオキシ安息香酸とイソソルビドとのＤＣＣ等の脱水縮合剤を用いたエステル化反応により得られる式（Ｓ−５）で表される化合物を、Ｐｄ／Ｃによる接触水素還元によりベンジル基を脱離させて式（Ｓ−６）で表されるイソソルビド誘導体を得る。
(Production Method 3) Production of Compound Represented by General Formula (I-14) In Formula (S-5) obtained by an esterification reaction using 4-benzyloxybenzoic acid and isosorbide using a dehydration condensing agent such as DCC The benzyl group is eliminated from the compound represented by catalytic hydrogen reduction with Pd / C to obtain an isosorbide derivative represented by the formula (S-6).
次いで、４−ヒドロキシ桂皮酸のテトラヒドロピラニルエーテル化合物と式（Ｓ−６）で表される化合物とのＤＣＣ等の脱水縮合剤を用いたエステル化反応によりイソソルビド誘導体を得る。更にイソソルビド誘導体をテトラヒドロフラン（ＴＨＦ）／塩酸で脱保護を行い式（Ｓ−７）で表されるイソソルビド誘導体を得て、アクリル酸クロリドとのエステル化反応により、式（Ｉ−１４）で表される目的化合物を得ることができる。 Next, an isosorbide derivative is obtained by an esterification reaction of 4-hydroxycinnamic acid tetrahydropyranyl ether compound with a compound represented by the formula (S-6) using a dehydration condensing agent such as DCC. Further, the isosorbide derivative was deprotected with tetrahydrofuran (THF) / hydrochloric acid to obtain an isosorbide derivative represented by the formula (S-7), which was then represented by the formula (I-14) by esterification with acrylic acid chloride. Target compound can be obtained.
（製法４） 一般式（Ｉ−１７）で表される化合物の製造
４−ブロモ安息香酸メチルとトリメチルシリルアセチレンとの園頭反応により式（Ｓ−７）で表されるトリメチルシリルアセチレン誘導体を合成した後、テトラブチルアンモニウムフロリドによりトリメチルシリル基（ＴＭＳ）を脱離させて、式（Ｓ−８）で表されるアセチレン誘導体を得る。更に、４−ブロモ−２−フルオロフェノールのテトラヒドロピラニルエーテル化合物との園頭反応により式（Ｓ−９）で表されるトラン誘導体を得て、次いで水酸化ナトリウムによる加水分解によりトラン骨格を有する式（Ｓ−１０）で表される安息香酸誘導体を得る。
(Production Method 4) Production of Compound Represented by General Formula (I-17) After Synthesis of Trimethylsilyl Acetylene Derivative Represented by Formula (S-7) by Sonogashira Reaction of Methyl 4-Bromobenzoate and Trimethylsilylacetylene The trimethylsilyl group (TMS) is eliminated with tetrabutylammonium fluoride to obtain an acetylene derivative represented by the formula (S-8). Furthermore, a Tran derivative represented by the formula (S-9) is obtained by Sonogashira reaction of 4-bromo-2-fluorophenol with a tetrahydropyranyl ether compound, and then a formula having a Tran skeleton by hydrolysis with sodium hydroxide. A benzoic acid derivative represented by (S-10) is obtained.
トラン骨格を有する式（Ｓ−１０）で表される安息香酸誘導体とイソソルビドとをＤＣＣ等の脱水縮合剤を用いたエステル化反応によりイソソルビド誘導体を得て、更にイソソルビド誘導体をＴＨＦ／塩酸で脱保護を行い式（Ｓ−１１）で表されるイソソルビド誘導体を得る。 An isosorbide derivative is obtained by esterification using a benzoic acid derivative having a tolan skeleton represented by the formula (S-10) and isosorbide using a dehydration condensing agent such as DCC, and the isosorbide derivative is further deprotected with THF / hydrochloric acid. To obtain an isosorbide derivative represented by the formula (S-11).
次いでメタクリル酸クロリドとのエステル化反応により、式（Ｉ−１７）で表される目的化合物を得ることができる。 Subsequently, the target compound represented by the formula (I-17) can be obtained by an esterification reaction with methacrylic acid chloride.
（製法５） 一般式（Ｉ−２３）で表される化合物の製造
ビナフトールとアセトキシ安息香酸とのジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応によりビナフチル誘導体（Ｓ−１２）を得た後、ブチルアミンによりアセチル基を脱離させてヒドロキシ安息香酸誘導体（Ｓ−１３）を得る。次いで,ヒドロキシ安息香酸誘導体（Ｓ−１４）と4-アクリロイルオキシ安息香酸とのジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応により目的物化合物（Ｉ−２３）を得ることができる。
(Production Method 5) Production of Compound Represented by General Formula (I-23) After obtaining binaphthyl derivative (S-12) by esterification reaction of binaphthol and acetoxybenzoic acid using a dehydration condensing agent such as dicyclohexylcarbodiimide. The acetyl group is eliminated with butylamine to obtain a hydroxybenzoic acid derivative (S-13). Subsequently, the target compound (I-23) can be obtained by an esterification reaction of a hydroxybenzoic acid derivative (S-14) and 4-acryloyloxybenzoic acid using a dehydration condensing agent such as dicyclohexylcarbodiimide.
（製法６） 一般式（Ｉ−２５）で表される化合物の製造
酒石酸エチルと4-アクリロイルオキシ安息香酸とをジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応により目的物化合物（Ｉ−２５）を得ることができる。
(Manufacturing method 6) Manufacture of the compound represented by general formula (I-25) The target compound (I-25) is obtained by esterification of ethyl tartrate and 4-acryloyloxybenzoic acid using a dehydration condensing agent such as dicyclohexylcarbodiimide. ) Can be obtained.
（製法７） 一般式（Ｉ−３８）で表される化合物の製造
酒石酸エチルとアセトキシナフトエ酸とのジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応、更にブチルアミンを用いた脱アセチル基反応により、ナフトエ酸誘導体（Ｓ−１４）を得る。次いで、マレイミド酢酸とのジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応により目的化合物（Ｉ−３８）を得ることができる。
(Production Method 7) Production of Compound Represented by General Formula (I-38) By an esterification reaction of ethyl tartrate and acetoxynaphthoic acid using a dehydration condensing agent such as dicyclohexylcarbodiimide, and further a deacetylation reaction using butylamine To obtain a naphthoic acid derivative (S-14). Subsequently, the target compound (I-38) can be obtained by esterification reaction with maleimidoacetic acid using a dehydration condensing agent such as dicyclohexylcarbodiimide.
本願発明の重合性化合物は、キラルネマチック、キラルスメクチック及びコレステリック液晶組成物に好適に使用できる。本願発明の化合物を構成部材とする液晶組成物において、重合性キラル化合物の添加量は、０．１〜４０質量％が好ましく３〜２５質量％がより好ましい。 The polymerizable compound of the present invention can be suitably used for chiral nematic, chiral smectic and cholesteric liquid crystal compositions. In the liquid crystal composition comprising the compound of the present invention as a constituent member, the addition amount of the polymerizable chiral compound is preferably 0.1 to 40% by mass, and more preferably 3 to 25% by mass.
本願発明の重合性キラル化合物を含有する重合性組成物は液晶性を示しても示さなくてもよいが、液晶性を示すものが好ましく、その構成としては、一般式（Ｉ）で表される化合物を含有する以外に制限はないが、組み合わせて使用する重合性化合物としては、化合物中にアクリロイルオキシ基（Ｒ−１）又はメタアクリロイルオキシ基（Ｒ−２）を有するものが好ましく、重合性官能基を分子内に２つ以上持つものがより好ましい。 The polymerizable composition containing the polymerizable chiral compound of the present invention may or may not exhibit liquid crystallinity, but preferably exhibits liquid crystallinity, and the constitution thereof is represented by the general formula (I). Although there is no restriction | limiting except containing a compound, As a polymeric compound used combining, what has an acryloyloxy group (R-1) or a methacryloyloxy group (R-2) in a compound is preferable, and it is polymerizable. Those having two or more functional groups in the molecule are more preferred.
組み合わせて使用する重合性化合物は液晶性を示すことが好ましいが、具体的には一般式（II） Although the polymerizable compound used in combination preferably exhibits liquid crystallinity, specifically, the general formula (II)
（ただし、式中Ａは、Ｈ、Ｆ、Ｃｌ、ＣＮ、ＳＣＮ、ＯＣＦ３、１〜１２個の炭素原子を有するアルキル基であり、該アルキル基は酸素原子同士が直接結合しないものとして炭素原子が酸素原子、硫黄原子、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−で置換されて良く、又は−Ｌ６−Ｓ４−Ｒ４であり、Ｒ３及びＲ４はお互い独立して、一般式（Ｉ）におけるＲ１と同じ意味を表し、Ｓ３及びＳ４は、お互い独立して単結合、又は１〜１２個の炭素原子を有するアルキレン基を表し、ここで一つ以上の−ＣＨ２−は、酸素原子同士が直接結合しないものとして−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−に置き換えられても良く、Ｌ４、Ｌ５、及びＬ６はお互い独立して、単結合、−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯＣＨ２−、−ＣＨ２ＯＣＯＯ−、−ＣＯ−ＮＲ１１−、−ＮＲ１１−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＯＣ−ＣＨ＝ＣＨ−、−ＣＯＯＣ２Ｈ４−、−ＯＣＯＣ２Ｈ４−、−Ｃ２Ｈ４ＯＣＯ−、−Ｃ２Ｈ４ＣＯＯ−、−ＯＣＯＣＨ２−、−ＣＨ２ＣＯＯ−、−ＣＨ＝ＣＨ−、−Ｃ２Ｈ４−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−ＣＦ２−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２ＣＨ２−、−ＣＨ２ＣＦ２−、−ＣＦ２ＣＦ２−又は−Ｃ≡Ｃ−を表し（式中、Ｒ１１は炭素原子１〜４のアルキル基を表す。）、Ｍ３及びＭ４はお互い独立して、１，４−フェニレン基、１，４−シクロヘキシレン基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ナフタレン−２，６−ジイル基、テトラヒドロナフタレン−２，６−ジイル基又は１，３−ジオキサン−２，５−ジイル基を表すが、Ｍ３及びＭ４はお互い独立して無置換であるか又はアルキル基、ハロゲン化アルキル基、アルコキシ基、ハロゲン化アルコキシ基、ハロゲン基、シアノ基又はニトロ基に置換されていても良く、ｐは０、１、２又は３を表す。ｐが２又は３を表す場合、２個あるいは３個存在するＬ５及びＭ４はお互い独立して同一であっても異なっていても良い。）で表される化合物が好ましい。 (In the formula, A is H, F, Cl, CN, SCN, OCF 3 , an alkyl group having 1 to 12 carbon atoms, and the alkyl group is a carbon atom on the assumption that oxygen atoms are not directly bonded to each other. May be substituted with an oxygen atom, a sulfur atom, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, —C≡C—, or —L 6 —S 4 —R 4. R 3 and R 4 each independently represent the same meaning as R 1 in the general formula (I), and S 3 and S 4 each independently represent a single bond or 1 to 12 carbon atoms. Wherein one or more —CH 2 — may be replaced with —O—, —COO—, —OCO—, —OCOO—, in which oxygen atoms are not directly bonded to each other, L 4 , L 5 , and L 6 are each independently a single bond, O -, - S -, - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NR 11 -, - NR 11 -CO -, - SCH 2 - , - CH 2 S -, - CH = CH-COO -, - OOC-CH = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - OCOCH 2 -, - CH 2 COO -, - CH = CH -, - C 2 H 4 -, - CF = CH -, - CH = CF -, - CF 2- , —CF 2 O—, —OCF 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 — or —C≡C— (wherein R 11 represents carbon Represents an alkyl group of atoms 1 to 4, and M 3 and M 4 are each independently 1,4-phenylene group. 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, tetrahydronaphthalene-2,6-diyl group, or 1,3- A dioxane-2,5-diyl group, wherein M 3 and M 4 are each independently unsubstituted, an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen group, a cyano group or It may be substituted with a nitro group, and p represents 0, 1, 2, or 3. When p represents 2 or 3, two or three L 5 and M 4 are independently the same. Or may be different.) Is preferred.
特にＬ４、Ｌ５及びＬ６がお互い独立して、単結合、−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を表し、Ｍ３及びＭ４がお互い独立して、１，４−フェニレン基、１，４−シクロヘキシレン基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基又はナフタレン−２，６−ジイル基で表される重合性化合物が好ましい。 In particular, L 4 , L 5 and L 6 each independently represent a single bond, —O—, —COO— or —OCO—, and M 3 and M 4 each independently represent a 1,4-phenylene group, A polymerizable compound represented by a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group or a naphthalene-2,6-diyl group is preferred.
一般式（ＩＩ）で表される重合性化合物は具体的には、一般式（ＩＩ−１）〜一般式（ＩＩ−２２）で表される化合物が好ましい。 Specifically, the polymerizable compound represented by formula (II) is preferably a compound represented by formula (II-1) to formula (II-22).
（式中、ｐ及びｑはお互い独立して０〜１２の整数を表すが、ｐ及び／又はｑが０の場合は２個の酸素原子直接結合することはなく、一方の酸素原子を除去する。）
また本願発明の重合性組成物に使用する重合性液晶化合物としては、液晶温度範囲や複屈折率の調節、粘度低減を目的として一般式（ＩＩＩ−１）〜一般式（ＩＩＩ−１１）を配合することが好ましい。
(In the formula, p and q independently represent an integer of 0 to 12, but when p and / or q is 0, two oxygen atoms are not directly bonded, and one oxygen atom is removed. .)
In addition, as the polymerizable liquid crystal compound used in the polymerizable composition of the present invention, the general formula (III-1) to the general formula (III-11) are blended for the purpose of adjusting the liquid crystal temperature range, the birefringence, and reducing the viscosity. It is preferable to do.
（式中、ｐ及びｑはお互い独立して０〜１２の整数を表すが、ｐが０の場合は２個の酸素原子直接結合することはなく、一方の酸素原子を除去する。）
また本願発明の化合物以外のキラル化合物も添加しても良い、具体的な化合物としては一般式（ＩＶ−１）〜一般式（ＩＶ−７）に示される。キラル化合物の配合量は、液晶組成物に対して、０．５〜３０質量％が好ましく、２〜２０質量％がより好ましい。
(In the formula, p and q independently represent an integer of 0 to 12, but when p is 0, two oxygen atoms are not directly bonded, and one oxygen atom is removed.)
In addition, chiral compounds other than the compound of the present invention may be added. Specific compounds are represented by general formula (IV-1) to general formula (IV-7). 0.5-30 mass% is preferable with respect to a liquid crystal composition, and, as for the compounding quantity of a chiral compound, 2-20 mass% is more preferable.
（式中、ｐ及びｑはお互い独立して０〜１２の整数を表すが、ｐ及び／又はｑが０の場合は２個の酸素原子直接結合することはなく、一方の酸素原子を除去する。）
さらに本発明の液晶組成物に、重合性基を有しない液晶組成物に添加してもよく、通常の液晶デバイス、例えばＳＴＮ（スーパー・ツイステッド・ネマチック）液晶や、ＴＮ（ツイステッド・ネマチック）液晶、ＴＦＴ（薄膜トランジスター）液晶等に使用されるネマチック液晶組成物、強誘電液晶組成物等が挙げられる。
(In the formula, p and q independently represent an integer of 0 to 12, but when p and / or q is 0, two oxygen atoms are not directly bonded, and one oxygen atom is removed. .)
Furthermore, the liquid crystal composition of the present invention may be added to a liquid crystal composition having no polymerizable group, and is a normal liquid crystal device such as STN (super twisted nematic) liquid crystal, TN (twisted nematic) liquid crystal, Examples thereof include nematic liquid crystal compositions and ferroelectric liquid crystal compositions used for TFT (thin film transistor) liquid crystals.
また、重合性官能基を有する化合物であって、液晶性を示さない化合物を添加することもできる。このような化合物としては、通常、この技術分野で高分子形成性モノマーあるいは高分子形成性オリゴマーとして認識されるものであれば特に制限なく使用することができるが、組成物が液晶相を呈することが求められる場合には、その添加量は組成物として液晶性を呈するように調整する必要がある。 Moreover, it is a compound which has a polymerizable functional group, Comprising: The compound which does not show liquid crystallinity can also be added. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field, but the composition exhibits a liquid crystal phase. Is required to be adjusted so that the composition exhibits liquid crystallinity.
本発明の液晶組成物は、重合開始剤を添加しなくても熱及び光による重合が可能であるが、光重合開始剤の添加が好ましい。添加する光重合開始剤の濃度は、０．１〜１０質量%が好ましく、０．２〜１０質量%がさらに好ましく、０．４〜５質量%が特に好ましい。光開始剤としては、ベンゾインエーテル類、ベンゾフェノン類、アセトフェノン類、ベンジルケタール類、アシルフォスフィンオキサイド類等が挙げられる。 The liquid crystal composition of the present invention can be polymerized by heat and light without adding a polymerization initiator, but the addition of a photopolymerization initiator is preferred. The concentration of the photopolymerization initiator to be added is preferably 0.1 to 10% by mass, more preferably 0.2 to 10% by mass, and particularly preferably 0.4 to 5% by mass. Examples of the photoinitiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides.
また、本発明の液晶組成物には、その保存安定性を向上させるために、安定剤を添加することもできる。使用できる安定剤としては、例えば、ヒドロキノン類、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、β−ナフチルアミン類、β−ナフトール類、ニトロソ化合物等が挙げられる。安定剤を使用する場合の添加量は、液晶組成物に対して０．００５〜１質量％の範囲が好ましく、０．０２〜０．５質量％がさらに好ましく、０．０３〜０．１質量％が特に好ましい。 In addition, a stabilizer can be added to the liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the amount added is preferably 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0.1% by mass with respect to the liquid crystal composition. % Is particularly preferred.
また、本発明の液晶組成物を位相差フィルム、偏光フィルムや配向膜の原料、又は印刷インキ及び塗料、保護膜等の用途に利用する場合には、その目的に応じて金属、金属錯体、染料、顔料、色素、蛍光材料、燐光材料、界面活性剤、レベリング剤、チキソ剤、ゲル化剤、多糖類、紫外線吸収剤、赤外線吸収剤、抗酸化剤、イオン交換樹脂、酸化チタン等の金属酸化物等を添加することもできる。 In addition, when the liquid crystal composition of the present invention is used for a retardation film, a material for a polarizing film or an alignment film, a printing ink, a paint, a protective film or the like, a metal, a metal complex, or a dye is used depending on the purpose. , Pigments, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, titanium oxide, etc. A thing etc. can also be added.
次に本発明の光学異方体について説明する。本発明の液晶組成物を重合させることによって製造される光学異方体は種々の用途に利用できる。例えば、本発明の重合性液晶組成物を、配向させない状態で重合させた場合、光散乱板、偏光解消板、モアレ縞防止板として利用可能である。また、本発明の重合性液晶組成物を配向させた状態において、重合させることにより製造された光学異方体は、物理的性質に光学異方性を有しており、有用である。このような光学異方体は、例えば、本発明の重合性液晶組成物表面を、布等でラビング処理した基板、もしくは有機薄膜を形成した基板表面を布等でラビング処理した基板、あるいはＳｉＯ２を斜方蒸着した配向膜を有する基板上に担持させるか、基板間に挟持させた後、本発明の液晶を重合させることによって製造することができる。 Next, the optical anisotropic body of the present invention will be described. The optical anisotropic body produced by polymerizing the liquid crystal composition of the present invention can be used for various applications. For example, when the polymerizable liquid crystal composition of the present invention is polymerized without being oriented, it can be used as a light scattering plate, a depolarizing plate, or a moire fringe prevention plate. Moreover, the optically anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention in an aligned state has optical anisotropy in physical properties and is useful. Such an optical anisotropic body is, for example, a substrate obtained by rubbing the surface of the polymerizable liquid crystal composition of the present invention with a cloth or the like, a substrate obtained by rubbing a substrate surface on which an organic thin film is formed with a cloth, or SiO 2. Can be produced by polymerizing the liquid crystal of the present invention after it is supported on a substrate having an orientation film deposited obliquely or sandwiched between the substrates.
重合性液晶組成物を基板上に担持させる際の方法としては、スピンコーティング、ダイコーティング、エクストルージョンコーティング、ロールコーティング、ワイヤーバーコーティング、グラビアコーティング、スプレーコーティング、ディッピング、プリント法等を挙げることができる。またコーティングの際、重合性液晶組成物をそのまま使用しても、有機溶媒を添加しても良い。有機溶媒としては、酢酸エチル、テトラヒドロフラン、トルエン、ヘキサン、メタノール、エタノール、ジメチルホルムアミド、ジクロロメタン、イソプロパノール、アセトン、メチルエチルケトン、アセトニトリル、セロソルブ、シクロヘキサノン、γ−ブチルラクトン、アセトキシ−２−エトキシエタン、プロピレングリコールモノメチルアセタート、Ｎ−メチルピロリジノン類を挙げることができる。これらは単独でも、組み合わせて用いても良く、その蒸気圧と重合性液晶組成物の溶解性を考慮し、適宜選択すれば良い。また、その添加量は９０質量％以下が好ましい。添加した有機溶媒を揮発させる方法としては、自然乾燥、加熱乾燥、減圧乾燥、減圧加熱乾燥を用いることができる。重合性液晶材料の塗布性をさらに向上させるためには、基板上にポリイミド薄膜等の中間層を設けることや、重合性液晶材料にレベリング剤を添加するのも有効である。基板上にポリイミド薄膜等の中間層を設けるのは、重合性液晶材料を重合させて得られる光学異方体と基板の密着性が良くない場合に、密着性を向上させる手段としても有効である。 Examples of the method for supporting the polymerizable liquid crystal composition on the substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing. . In coating, the polymerizable liquid crystal composition may be used as it is, or an organic solvent may be added. Organic solvents include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, dichloromethane, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolve, cyclohexanone, γ-butyllactone, acetoxy-2-ethoxyethane, propylene glycol monomethyl Examples include acetate and N-methylpyrrolidinones. These may be used alone or in combination, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. Moreover, the addition amount is preferably 90% by mass or less. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. Providing an intermediate layer such as a polyimide thin film on the substrate is also effective as a means for improving the adhesion when the adhesion between the optically anisotropic substance obtained by polymerizing the polymerizable liquid crystal material and the substrate is not good. .
液晶組成物を基板間に挟持させる方法としては、毛細管現象を利用した注入法が挙げられる。基板間に形成された空間を減圧し、その後液晶材料を注入する手段も有効である。 Examples of a method for sandwiching the liquid crystal composition between the substrates include an injection method using a capillary phenomenon. It is also effective to depressurize the space formed between the substrates and then inject a liquid crystal material.
ラビング処理、あるいはＳｉＯ２の斜方蒸着以外の配向処理としては、液晶材料の流動配向の利用や、電場又は磁場の利用を挙げることができる。これらの配向手段は単独で用いても、また組み合わせて用いても良い。さらに、ラビングに代わる配向処理方法として、光配向法を用いることもできる。この方法は、例えば、ポリビニルシンナメート等の分子内に光二量化反応する官能基を有する有機薄膜、光で異性化する官能基を有する有機薄膜又はポリイミド等の有機薄膜に、偏光した光、好ましくは偏光した紫外線を照射することによって、配向膜を形成するものである。この光配向法に光マスクを適用することにより配向のパターン化が容易に達成できるので、光学異方体内部の分子配向も精密に制御することが可能となる。 Examples of the alignment treatment other than the rubbing treatment or the oblique deposition of SiO 2 include the use of fluid orientation of a liquid crystal material and the use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. This method can be applied to, for example, an organic thin film having a functional group that undergoes photodimerization reaction in a molecule such as polyvinyl cinnamate, an organic thin film having a functional group that is isomerized by light, or an organic thin film such as polyimide. An alignment film is formed by irradiating polarized ultraviolet rays. By applying an optical mask to this photo-alignment method, patterning of the alignment can be easily achieved, so that the molecular orientation inside the optical anisotropic body can be precisely controlled.
基板の形状としては、平板の他に、曲面を構成部分として有していても良い。基板を構成する材料は、有機材料、無機材料を問わずに用いることができる。基板の材料となる有機材料としては、例えば、ポリエチレンテレフタレート、ポリカーボネート、ポリイミド、ポリアミド、ポリメタクリル酸メチル、ポリスチレン、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリアリレート、ポリスルホン、トリアセチルセルロース、セルロース、ポリエーテルエーテルケトン等が挙げられ、また、無機材料としては、例えば、シリコン、ガラス、方解石等が挙げられる。 As a shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.
これらの基板を布等でラビングすることによって適当な配向性を得られない場合、公知の方法に従ってポリイミド薄膜又はポリビニルアルコール薄膜等の有機薄膜を基板表面に形成し、これを布等でラビングしても良い。また、通常のＴＮ液晶デバイス又はＳＴＮ液晶デバイスで使用されているプレチルト角を与えるポリイミド薄膜は、光学異方体内部の分子配向構造を更に精密に制御することができることから、特に好ましい。 When appropriate orientation cannot be obtained by rubbing these substrates with a cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the substrate surface according to a known method, and this is rubbed with a cloth or the like. Also good. Moreover, the polyimide thin film which gives the pretilt angle used in the normal TN liquid crystal device or STN liquid crystal device is particularly preferable because the molecular orientation structure inside the optical anisotropic body can be controlled more precisely.
また、電場によって配向状態を制御する場合には、電極層を有する基板を使用する。この場合、電極上に前述のポリイミド薄膜等の有機薄膜を形成するのが好ましい。 In the case where the alignment state is controlled by an electric field, a substrate having an electrode layer is used. In this case, it is preferable to form an organic thin film such as the aforementioned polyimide thin film on the electrode.
本発明の液晶組成物を重合させる方法としては、迅速な重合の進行が望ましいので、紫外線又は電子線等の活性エネルギー線を照射することによって重合させる方法が好ましい。紫外線を使用する場合、偏光光源を用いても良いし、非偏光光源を用いても良い。また、液晶組成物を２枚の基板間に挟持させて状態で重合を行う場合には、少なくとも照射面側の基板は活性エネルギー線に対して適当な透明性が与えられていなければならない。また、光照射時にマスクを用いて特定の部分のみを重合させた後、電場や磁場又は温度等の条件を変化させることにより、未重合部分の配向状態を変化させて、さらに活性エネルギー線を照射して重合させるという手段を用いても良い。また、照射時の温度は、本発明の液晶組成物の液晶状態が保持される温度範囲内であることが好ましい。特に、光重合によって光学異方体を製造しようとする場合には、意図しない熱重合の誘起を避ける意味からも可能な限り室温に近い温度、即ち、典型的には２５℃での温度で重合させることが好ましい。活性エネルギー線の強度は、０．１ｍＷ／ｃｍ２〜２Ｗ／ｃｍ２が好ましい。強度が０．１ｍＷ／ｃｍ２以下の場合、光重合を完了させるのに多大な時間が必要になり生産性が悪化してしまい、２Ｗ／ｃｍ２以上の場合、重合性液晶化合物又は重合性液晶組成物が劣化してしまう危険がある。 As a method of polymerizing the liquid crystal composition of the present invention, since rapid progress of polymerization is desirable, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. Moreover, it is preferable that the temperature at the time of irradiation is in the temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. In particular, when an optical anisotropic body is to be produced by photopolymerization, the polymerization is carried out at a temperature as close to room temperature as possible from the viewpoint of avoiding unintentional induction of thermal polymerization, that is, typically at a temperature of 25 ° C. It is preferable to make it. The intensity of the active energy ray is preferably 0.1 mW / cm 2 to 2 W / cm 2 . When the intensity is 0.1 mW / cm 2 or less, a great amount of time is required to complete the photopolymerization and the productivity is deteriorated. When the intensity is 2 W / cm 2 or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal is used. There is a risk that the composition will deteriorate.
重合によって得られた本発明の光学異方体は、初期の特性変化を軽減し、安定的な特性発現を図ることを目的として熱処理を施すこともできる。熱処理の温度は５０〜２５０℃の範囲で、また熱処理時間は３０秒〜１２時間の範囲が好ましい。 The optical anisotropic body of the present invention obtained by polymerization can be subjected to heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.
このような方法によって製造される本発明の光学異方体は、基板から剥離して単体で用いても、剥離せずに用いても良い。また、得られた光学異方体を積層しても、他の基板に貼り合わせて用いてもよい。 The optical anisotropic body of the present invention produced by such a method may be peeled off from the substrate and used alone or without peeling. Further, the obtained optical anisotropic bodies may be laminated or bonded to another substrate for use.
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。各種分析は以下の方法により行った。
・相転移温度：温度調節ステージを備えた偏光顕微鏡で測定
・化合物の構造：核磁気共鳴スペクトル(NMR)、質量スペクトル(MS)等により確認
以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。
EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Various analyzes were performed by the following methods.
-Phase transition temperature: measured with a polarizing microscope equipped with a temperature control stage-Compound structure: Confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS), etc. "%" in the compositions of the following examples and comparative examples Means “mass%”.
Ｔｎ−ｉはネマチック相−等方相の転移温度を表す。 T n−i represents a transition temperature between a nematic phase and an isotropic phase.
ＨＴＰ（ねじれ力）の測定方法：重合性キラル化合物をネマチック液晶（ＤＯＮ−１０３，ＤＩＣ社製）に２重量％添加した組成物を市販の一軸配向処理を行ったクサビ型セルに注入し、偏光顕微鏡を用いて室温でらせんピッチを測定した。この値を上記式（ａ）に代入しＨＴＰを求めた。 Measurement method of HTP (twisting force): A composition obtained by adding 2% by weight of a polymerizable chiral compound to a nematic liquid crystal (DON-103, manufactured by DIC) was injected into a commercially available wedge-shaped cell subjected to uniaxial alignment treatment, and polarized light. The helical pitch was measured at room temperature using a microscope. This value was substituted into the above formula (a) to obtain HTP.
円偏光特性：紫外可視分光光度計 Ｕ−４１００（日立製作所製）で４５０ｎｍ〜６５０ｎｍのスペクトルを測定
化合物記載に下記の略号を使用する。
（実施例１）
撹拌装置、冷却器及び温度計を備えた反応容器に３−（ｐ−ヒドロキシフェニル）安息香酸 ３３．２ｇ（２４０ミリモル）、ヨウ化カリウム ４ｇ、テトラブチルアンモニウムブロミド １ｇ、エタノール ４００ｍｌを仕込み室温で攪拌した。水酸化ナトリウム ２４ｇの２５％水溶液をゆっくり滴下した。滴下終了後、反応容器を５０℃に保ち、ベンジルブロミド ５０ｇ（２８８ミリモル）をゆっくり滴下した。滴下終了後、反応容器を更に７０℃に加温して更に３時間反応させた。反応終了後、１０％塩酸で中和して酢酸エチルで抽出を行い、硫酸ナトリウムで乾燥後、溶媒を濃縮して式（１）で表す化合物を３８ｇ合成した。
Circularly polarized light characteristics: UV-visible spectrophotometer U-4100 (manufactured by Hitachi, Ltd.) Measures a spectrum of 450 nm to 650 nm The following abbreviations are used in the compound description.
Example 1
A reaction vessel equipped with a stirrer, a cooler and a thermometer was charged with 33.2 g (240 mmol) of 3- (p-hydroxyphenyl) benzoic acid, 4 g of potassium iodide, 1 g of tetrabutylammonium bromide, and 400 ml of ethanol and stirred at room temperature. did. A 25% aqueous solution of 24 g of sodium hydroxide was slowly added dropwise. After completion of the dropping, the reaction vessel was kept at 50 ° C., and 50 g (288 mmol) of benzyl bromide was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further heated to 70 ° C. and further reacted for 3 hours. After completion of the reaction, the mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was concentrated to synthesize 38 g of the compound represented by formula (1).
次いで、撹拌装置、冷却器及び温度計を備えた反応容器に、上記で合成した式（１）で表す化合物２８ｇ（１２３ミリモル）、イソソルビド ７．７ｇ（５５ミリモル）、ジメチルアミノピリジン １．８ｇ、ジクロロメタン ５００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド １９ｇ（１５０ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液にジクロロメタン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（２）で表す化合物２３ｇを得た。 Next, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 28 g (123 mmol) of the compound represented by the formula (1) synthesized above, 7.7 g (55 mmol) of isosorbide, 1.8 g of dimethylaminopyridine, Charge 500 ml of dichloromethane and keep the reaction vessel at 5 ° C or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 19 g (150 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was performed with a 5 times amount (weight ratio) silica gel column to obtain 23 g of a compound represented by the formula (2).
次いで、撹拌装置備えたオートクレーブ容器に、上記で合成した式（２）で表す化合物２３ｇ（４０．５ミリモル）、パラジウムカーボン １ｇ、エタノール１５０ｍｌを仕込み、０．１ＭＰａの水素にて還元反応（反応温度５０℃、３時間）を行った。反応液をろ過した後、反応溶媒を留去して式（３）で表す化合物１４ｇを得た。 Subsequently, 23 g (40.5 mmol) of the compound represented by the formula (2) synthesized above, 1 g of palladium carbon, and 150 ml of ethanol were charged in an autoclave container equipped with a stirrer, and a reduction reaction (reaction temperature) with 0.1 MPa of hydrogen. (50 ° C., 3 hours). After filtering the reaction solution, the reaction solvent was distilled off to obtain 14 g of a compound represented by the formula (3).
次いで、撹拌装置、冷却器及び温度計を備えた反応容器に、上記の式（３）で表す化合物４ｇ（１０．３ミリモル）、アクリル酸クロリド ２．２６ｇ（２５ミリモル）、ジクロロメタン５０ｍｌを仕込み、窒素ガス雰囲気下で反応器を５℃以下に冷却した。次いでトリエチルアミン ２．５ｇ（２５ミリモル）をゆっくり滴下した。滴下終了後、２０℃以下で３時間反応させた。反応終了後、ジクロロメタンを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（４）で表す目的の化合物 ４．２ｇを得た。 Then, 4 g (10.3 mmol) of the compound represented by the above formula (3), 2.26 g (25 mmol) of acrylic acid chloride, and 50 ml of dichloromethane were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer. The reactor was cooled to 5 ° C. or lower under a nitrogen gas atmosphere. Then 2.5 g (25 mmol) of triethylamine was slowly added dropwise. After completion of the dropping, the reaction was carried out at 20 ° C. or lower for 3 hours. After completion of the reaction, dichloromethane was added, and the organic layer was washed with a 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 4.2 g of the desired compound represented by the formula (4).
（物性値）
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：４．０５−４．１１（ｍ，４Ｈ），４．６７（ｍ，１Ｈ），５．０６（ｍ，１Ｈ），５．４２（ｍ，１Ｈ），５．４９（ｓ，１Ｈ），６．０４（ｄ，２Ｈ），６．２９（ｍ，２Ｈ），６．６５（ｄ，２Ｈ），７．２１−７．２６（ｍ，４Ｈ），８．０６（ｄｄ，４Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：７０．７，７３．４，７４．５，７８．５，８１．１，８６．１，１２１．７，１２６．９，１２７．０，１２７．５，１３１．３，１３３．３，１５４．５，１６３．８，１６４．７，１６５．１
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９
（融点）１２５℃
下記で表すネマチック液晶組成物に式（４）で示される化合物を５．０％添加して光学顕微鏡より求めるピッチよりＨＴＰを算出した結果、ＨＴＰ＝３１と高い値を示した。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 4.05-4.11 (m, 4H), 4.67 (m, 1H), 5.06 (m, 1H), 5.42 (m, 1H), 5.49 (s, 1H), 6.04 (d, 2H), 6.29 (m, 2H), 6.65 (d, 2H), 7.21-7.26 (m, 4H) ), 8.06 (dd, 4H)
13 C-NMR (solvent: deuterated chloroform): δ: 70.7, 73.4, 74.5, 78.5, 81.1, 86.1, 121.7, 126.9, 127.0, 127 5, 131.3, 133.3, 154.5, 163.8, 164.7, 165.1
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
(Melting point) 125 ° C
As a result of calculating HTP from the pitch obtained from an optical microscope by adding 5.0% of the compound represented by the formula (4) to the nematic liquid crystal composition represented below, it showed a high value of HTP = 31.
（実施例２）
撹拌装置、冷却器及び温度計を備えた反応容器に、実施例１で合成した式（３）で表す化合物４ｇ（１０．３ミリモル）、４−アクリロイルオキシ安息香酸 ４．６ｇ（２４ミリモル）、ジメチルアミノピリジン ２００ｍｇ、ジクロロメタン ５００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド ３．６ｇ（２８ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液にジクロロメタン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（５）で表す目的の化合物 ５．２ｇを得た。
(Example 2)
In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 4 g (10.3 mmol) of the compound represented by the formula (3) synthesized in Example 1, 4.6 g (24 mmol) of 4-acryloyloxybenzoic acid, Charge 200 mg of dimethylaminopyridine and 500 ml of dichloromethane, and keep the reaction vessel at 5 ° C or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 3.6 g (28 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a 5 times amount (weight ratio) silica gel column to obtain 5.2 g of the desired compound represented by the formula (5).
（物性値）
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：４．０５−４．１１（ｍ，４Ｈ），４．６７（ｍ，１Ｈ），５．０６（ｍ，１Ｈ），５．４２（ｍ，１Ｈ），５．４９（ｓ，１Ｈ），６．０４（ｄ，２Ｈ），６．２９（ｍ，２Ｈ），６．６５（ｄ，２Ｈ），７．２６−７．３７（ｍ，８Ｈ），８．１０（ｄ，２Ｈ），８．１７（ｄ，２Ｈ），８．２４−８．２７（ｍ，４Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：７０．７，７３．４，７４．６，７８．５，８１．１，８６．１，１２１．８，１２１．９，１２６．５，１２７．０，１２７．１，１２７．４，１３１．４，１３１．８，１３３．４，１５４．５，１６３．７，１６４．７，１６５．１
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９
（融点）１７７℃
実施例１と同様にしてＨＴＰを算出した結果、ＨＴＰ＝４２と高い値を示した。
（実施例３）
撹拌装置、冷却器及び温度計を備えた反応容器に、実施例１で合成した式（３）で表す化合物４ｇ（１０．３ミリモル）、４−（４−メタアクリロイルオキシ）フェニル桂皮酸 ７．４ｇ（２４ミリモル）、ジメチルアミノピリジン ２００ｍｇ、ジクロロメタン ５００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド ３．６ｇ（２８ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液にジクロロメタン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（６）で表す目的の化合物 ６．４ｇを得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 4.05-4.11 (m, 4H), 4.67 (m, 1H), 5.06 (m, 1H), 5.42 (m, 1H), 5.49 (s, 1H), 6.04 (d, 2H), 6.29 (m, 2H), 6.65 (d, 2H), 7.26-7.37 (m, 8H) ), 8.10 (d, 2H), 8.17 (d, 2H), 8.24-8.27 (m, 4H)
13 C-NMR (solvent: deuterated chloroform): δ: 70.7, 73.4, 74.6, 78.5, 81.1, 86.1, 121.8, 121.9, 126.5, 127 0.0, 127.1, 127.4, 131.4, 131.8, 133.4, 154.5, 163.7, 164.7, 165.1
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
(Melting point) 177 ° C
As a result of calculating HTP in the same manner as in Example 1, it showed a high value of HTP = 42.
(Example 3)
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 4 g (10.3 mmol) of the compound represented by the formula (3) synthesized in Example 1 and 4- (4-methacryloyloxy) phenylcinnamic acid7. Charge 4 g (24 mmol), 200 mg of dimethylaminopyridine, and 500 ml of dichloromethane, and keep the reaction vessel at 5 ° C. or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 3.6 g (28 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a 5-fold amount (weight ratio) silica gel column to obtain 6.4 g of the desired compound represented by the formula (6).
（物性値）
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１．９２（ｓ，６Ｈ），３．９１−３．９５（ｍ，２Ｈ），４．０５−４．１５（ｍ，２Ｈ），４．６３（ｍ，１Ｈ），４．９８（ｍ，１Ｈ），５．３１−５．３９（ｍ，２Ｈ），５．７７（ｓ，１Ｈ），６．４１（ｓ，２Ｈ），６．４４−６．６５（ｍ，４Ｈ），７．２２（ｄ，２Ｈ），７．４０−７．７０（ｍ，１２Ｈ），７．７６−７．８５（ｍ，２Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：７０．３，７３．６，７４．１，７６．７，８１．０，８６．０，１１６．９，１１７．０，１２２．０，１２７．４，１２７．１，１２８．０，１２８．７，１３３．０，１３３．２，１３５．７，１３７．６，１４２．３，１４２．４，１４５．３，１５０．８，１６５．７，１６５．８，１６６．２
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９
（融点）２４８℃
実施例１で用いたネマチック液晶組成物に式（６）で示される化合物を２．０％添加して光学顕微鏡より求めるピッチよりＨＴＰを算出した結果、ＨＴＰ＝５６と高い値を示した。
（実施例４）
撹拌装置、冷却器及び温度計を備えた反応容器に、実施例１で合成した式（３）で表す化合物４ｇ（１０．３ミリモル）、６−アクリロイルオキシ−２−ナフトエ酸 ５．８ｇ（２４ミリモル）、ジメチルアミノピリジン ２００ｍｇ、ジクロロメタン ５００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド ３．６ｇ（２８ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液にジクロロメタン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（７）で表す目的の化合物 ５．７ｇを得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 1.92 (s, 6H), 3.91-3.95 (m, 2H), 4.05-4.15 (m, 2H), 4. 63 (m, 1H), 4.98 (m, 1H), 5.31-5.39 (m, 2H), 5.77 (s, 1H), 6.41 (s, 2H), 6.44 -6.65 (m, 4H), 7.22 (d, 2H), 7.40-7.70 (m, 12H), 7.76-7.85 (m, 2H)
13 C-NMR (solvent: deuterated chloroform): δ: 70.3, 73.6, 74.1, 76.7, 81.0, 86.0, 116.9, 117.0, 122.0, 127 4, 127.1, 128.0, 128.7, 133.0, 133.2, 135.7, 137.6, 142.3, 142.4, 145.3, 150.8, 165.7 , 165.8, 166.2
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
(Melting point) 248 ° C
As a result of calculating HTP from the pitch obtained from an optical microscope by adding 2.0% of the compound represented by formula (6) to the nematic liquid crystal composition used in Example 1, it showed a high value of HTP = 56.
Example 4
In a reaction vessel equipped with a stirrer, a cooler and a thermometer, 4 g (10.3 mmol) of the compound represented by the formula (3) synthesized in Example 1 and 5.8 g of 6-acryloyloxy-2-naphthoic acid (24 Millimoles), 200 mg of dimethylaminopyridine, and 500 ml of dichloromethane were charged, and the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 3.6 g (28 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a 5-fold amount (weight ratio) silica gel column to obtain 5.7 g of the desired compound represented by the formula (7).
（物性値）
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：４．１３−４．１９（ｍ，４Ｈ），４．７７（ｍ，１Ｈ），５．１６（ｍ，１Ｈ），５．５０（ｍ，１Ｈ），５．５２（ｓ，１Ｈ），６．０４（ｄ，２Ｈ），６．２９（ｍ，２Ｈ），６．６５（ｄ，２Ｈ），７．２６−７．３７（ｍ，８Ｈ），８．１０（ｄ，２Ｈ），８．１７（ｄ，２Ｈ），８．２４−８．２７（ｍ，４Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：７０．７，７３．５，７４．７，７８．５，８１．２，８６．１，１１８．５，１２２．１，１２５．８，１２６．５，１２７．６，１２８．０，１３０．３，１３０．９，１３１．１，１３３．１，１３６．２，１５０．２，１６４．３，１６５．５，１６５．９
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９
（融点）１７９℃
実施例１と同様にしてＨＴＰを算出した結果、ＨＴＰ＝３４と高い値を示した。
（実施例５）
次いで、撹拌装置、冷却器及び温度計を備えた反応容器に、（Ｒ）−１，１‘−２−ビナフトール １５．７ｇ（５５ミリモル）、４−（４’−アクリロイルオキシ）ビフェニルカルボン酸 ３５．３ｇ（１３０ミリモル）ジメチルアミノピリジン １．８ｇ、ジクロロメタン ５００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド １９ｇ（１５０ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液にジクロロメタン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い式（８）で表す目的の化合物（Ｒ体） ３５ｇを得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 4.13-4.19 (m, 4H), 4.77 (m, 1H), 5.16 (m, 1H), 5.50 (m, 1H), 5.52 (s, 1H), 6.04 (d, 2H), 6.29 (m, 2H), 6.65 (d, 2H), 7.26-7.37 (m, 8H) ), 8.10 (d, 2H), 8.17 (d, 2H), 8.24-8.27 (m, 4H)
13 C-NMR (solvent: deuterated chloroform): δ: 70.7, 73.5, 74.7, 78.5, 81.2, 86.1, 118.5, 122.1, 125.8, 126 5, 127.6, 128.0, 130.3, 130.9, 131.1, 133.1, 136.2, 150.2, 164.3, 165.5, 165.9
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
(Melting point) 179 ° C
As a result of calculating HTP in the same manner as in Example 1, it showed a high value of HTP = 34.
(Example 5)
Then, (R) -1,1′-2-binaphthol 15.7 g (55 mmol), 4- (4′-acryloyloxy) biphenylcarboxylic acid 35 was added to a reaction vessel equipped with a stirrer, a cooler and a thermometer. .3 g (130 mmol) of dimethylaminopyridine (1.8 g) and dichloromethane (500 ml) were charged, and the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 19 g (150 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a 5-fold amount (weight ratio) silica gel column to obtain 35 g of the desired compound (R-form) represented by the formula (8).
（物性値）
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：４．０５−４．１１（ｍ，４Ｈ），４．６７（ｍ，１Ｈ），５．０６（ｍ，１Ｈ），５．４２（ｍ，１Ｈ），５．４９（ｓ，１Ｈ），６．０４（ｄ，２Ｈ），６．２９（ｍ，２Ｈ），６．６５（ｄ，２Ｈ），７．２６−７．３７（ｍ，８Ｈ），８．１０（ｄ，２Ｈ），８．１７（ｄ，２Ｈ），８．２４−８．２７（ｍ，４Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１２１．７，１２１．９，１２３．６，１２５．７，１２６．１，１２６．８，１２７．７，１２８．０，１２８．２，１２９．６，１３０．４，１３１．５，１３２．３，１３３．３，１３７．６，１４４．９，１４６．９，１５０．６，１６４．４，１６４．５
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：１７６０，１６５２−１６２２，８０９
（融点）１０７℃
実施例１と同様にしてＨＴＰを算出した結果、ＨＴＰ＝６５と高い値を示した。
（比較例１）
撹拌装置、冷却器、及び温度計を備えた反応容器に４−（４−ヒドロキシフェニル）安息香酸 ２１．４ｇ（１００ミリモル）、ヨウ化カリウム ２．５ｇ、テトラブチルアンモニウムブロミド ０．７ｇ、エタノール ４００ｍｌを仕込み室温で攪拌した。水酸化ナトリウム １２ｇの２５％水溶液をゆっくり滴下した。滴下終了後、反応容器を５０℃に保ち、６−クロロプロパノール ２０ｇ（１５０ミリモル）をゆっくり滴下した。滴下終了後、反応容器を更に７０℃に加温して更に３時間反応させた。反応終了後、１０％塩酸で中和して酢酸エチルで抽出を行い、硫酸ナトリウムで乾燥後、溶媒を濃縮して式（９）で表す化合物を２２ｇ合成した。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 4.05-4.11 (m, 4H), 4.67 (m, 1H), 5.06 (m, 1H), 5.42 (m, 1H), 5.49 (s, 1H), 6.04 (d, 2H), 6.29 (m, 2H), 6.65 (d, 2H), 7.26-7.37 (m, 8H) ), 8.10 (d, 2H), 8.17 (d, 2H), 8.24-8.27 (m, 4H)
13 C-NMR (solvent: deuterated chloroform): δ: 121.7, 121.9, 123.6, 125.7, 126.1, 126.8, 127.7, 128.0, 128.2, 129 6, 130.4, 131.5, 132.3, 133.3, 137.6, 144.9, 146.9, 150.6, 164.4, 164.5
Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622, 809
(Melting point) 107 ° C
As a result of calculating HTP in the same manner as in Example 1, it showed a high value of HTP = 65.
(Comparative Example 1)
In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 21.4 g (100 mmol) of 4- (4-hydroxyphenyl) benzoic acid, 2.5 g of potassium iodide, 0.7 g of tetrabutylammonium bromide, 400 ml of ethanol Was stirred at room temperature. A 25% aqueous solution of 12 g of sodium hydroxide was slowly added dropwise. After completion of the dropping, the reaction vessel was kept at 50 ° C., and 20 g (150 mmol) of 6-chloropropanol was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further heated to 70 ° C. and further reacted for 3 hours. After completion of the reaction, the mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was concentrated to synthesize 22 g of the compound represented by formula (9).
次いで、撹拌装置、冷却器及びディーンスタークを備えた反応容器に、上記で合成した式（９）で表す化合物２２ｇ（７１ミリモル）、アクリル酸 １０ｇ（１４０ミリモル）、ｐ−トルエンスルホン酸 １ｇ、トルエン１００ｍｌを仕込んだ。反応容器を加熱してトルエン還流させそのまま４時間反応させた。反応終了後、反応液を飽和炭酸水素ナトリウムで洗浄した後、１０％塩酸水溶液で中和、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去して、式（１０）で表す化合物１９ｇを得た。 Next, in a reaction vessel equipped with a stirrer, a cooler, and Dean Stark, 22 g (71 mmol) of the compound represented by the formula (9) synthesized above, 10 g (140 mmol) of acrylic acid, 1 g of p-toluenesulfonic acid, toluene 100 ml was charged. The reaction vessel was heated to reflux with toluene and allowed to react for 4 hours. After completion of the reaction, the reaction solution was washed with saturated sodium hydrogen carbonate, neutralized with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 19 g of a compound represented by the formula (10).
更に、撹拌装置、冷却器及び温度計を備えた反応容器に、上記で合成した式（１０）で表す化合物１９ｇ（５１ミリモル）、イソソルビド ３．８ｇ（２７ミリモル）、ジメチルアミノピリジン ０．９ｇ、ジクロロメタン ２００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド ９ｇ（６．３ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液にジクロロメタン１００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、シリカゲルカラムおよび再結晶により精製を行い式（１１）で表す目的の化合物１４ｇを得た。この化合物の融点は１５０℃以上であり測定できなかった。 Furthermore, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 19 g (51 mmol) of the compound represented by the formula (10) synthesized above, 3.8 g (27 mmol) of isosorbide, 0.9 g of dimethylaminopyridine, Charge 200 ml of dichloromethane and keep the reaction vessel at 5 ° C or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 9 g (6.3 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 100 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was performed by a silica gel column and recrystallization to obtain 14 g of the desired compound represented by the formula (11). The melting point of this compound was 150 ° C. or higher and could not be measured.
（物性値）
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１．５５−１．４５（ｍ，８Ｈ），１．７１（ｍ，４Ｈ），１．８３（ｍ，４Ｈ），２．６６（ｍ，４Ｈ），２．９６（ｍ，４Ｈ），
３．９３（ｍ，２Ｈ），３．９８（ｍ，２Ｈ），４．０３（ｓ，４Ｈ），４．３０（ｔ，４Ｈ），４．５０（ｔ，４Ｈ），５．３５（ｓ，２Ｈ），５．６５（ｄｄ，２Ｈ），５．８５（ｄ，２Ｈ），５．８５（ｄ，２Ｈ），６．１５（ｑ，２Ｈ），６．５５（ｄ，２Ｈ），７．１０（ｄ，４Ｈ），７．５０（ｍ，４Ｈ），８．１２（ｄ，４Ｈ），８．１３（ｄ，４Ｈ）
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９
（融点）＞１５０℃
比較例１記載の式（１１）で表される化合物は、融点が高く他の化合物との溶解性にも問題があった。実施例１と同様の液晶組成物でＨＴＰを算出した結果、ＨＴＰ＝３３と高い値を示したが、溶解性が悪いため下記の組成に０．５％しか添加できなかった。
（比較例２）
撹拌装置、冷却器及び温度計を備えた反応容器にｐ−ヒドロキシフェニル桂皮酸 １９．６ｇ（１２０ミリモル）、ヨウ化カリウム ２ｇ、テトラブチルアンモニウムブロミド ０．５ｇ、エタノール ４００ｍｌを仕込み室温で攪拌した。水酸化ナトリウム １２ｇの２５％水溶液をゆっくり滴下した。滴下終了後、反応容器を５０℃に保ち、ベンジルブロミド ２５ｇ（１４４ミリモル）をゆっくり滴下した。滴下終了後、反応容器を更に７０℃に加温して更に３時間反応させた。反応終了後、１０％塩酸で中和して酢酸エチルで抽出を行い、硫酸ナトリウムで乾燥後、溶媒を濃縮して式（１２）で表す化合物を２１ｇ合成した。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 1.55-1.45 (m, 8H), 1.71 (m, 4H), 1.83 (m, 4H), 2.66 (m, 4H), 2.96 (m, 4H),
3.93 (m, 2H), 3.98 (m, 2H), 4.03 (s, 4H), 4.30 (t, 4H), 4.50 (t, 4H), 5.35 (s , 2H), 5.65 (dd, 2H), 5.85 (d, 2H), 5.85 (d, 2H), 6.15 (q, 2H), 6.55 (d, 2H), 7 .10 (d, 4H), 7.50 (m, 4H), 8.12 (d, 4H), 8.13 (d, 4H)
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
(Melting point)> 150 ° C.
The compound represented by the formula (11) described in Comparative Example 1 had a high melting point and had a problem in solubility with other compounds. As a result of calculating HTP with the same liquid crystal composition as in Example 1, it showed a high value of HTP = 33, but because of poor solubility, only 0.5% could be added to the following composition.
(Comparative Example 2)
In a reaction vessel equipped with a stirrer, a cooler and a thermometer, 19.6 g (120 mmol) of p-hydroxyphenylcinnamic acid, 2 g of potassium iodide, 0.5 g of tetrabutylammonium bromide, and 400 ml of ethanol were charged and stirred at room temperature. A 25% aqueous solution of 12 g of sodium hydroxide was slowly added dropwise. After completion of the dropping, the reaction vessel was kept at 50 ° C., and 25 g (144 mmol) of benzyl bromide was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further heated to 70 ° C. and further reacted for 3 hours. After completion of the reaction, the mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was concentrated to synthesize 21 g of the compound represented by formula (12).
次いで、撹拌装置、冷却器及び温度計を備えた反応容器に、上記で合成した式（１２）で表す化合物２１ｇ（８２ミリモル）、イソソルビド ６ｇ（４１ミリモル）、ジメチルアミノピリジン １ｇ、ジクロロメタン ５００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド １２．４ｇ（１００ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液にジクロロメタン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、５倍量（重量比）のシリカゲルカラムにより精製を行い１９ｇを得た。 Next, 21 g (82 mmol) of the compound represented by the formula (12) synthesized above, 6 g (41 mmol) of isosorbide, 1 g of dimethylaminopyridine, and 500 ml of dichloromethane were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer. Keep the reaction vessel at 5 ° C or less with a trash ice bath. In an atmosphere of nitrogen gas, 12.4 g (100 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out with a 5 times amount (weight ratio) silica gel column to obtain 19 g.
次いで、撹拌装置備えたオートクレーブ容器に、上記で合成した中間体１９ｇ、パラジウムカーボン １ｇ、エタノール１５０ｍｌ、テトラヒドロフラン１００ｍｌを仕込み、1気圧の水素にて還元反応（反応温度５０℃、３時間）を行った。反応液をろ過した後、反応溶媒を留去して式（１３）で表す化合物１１．５ｇを得た。 Next, 19 g of the intermediate synthesized above, 1 g of palladium carbon, 150 ml of ethanol and 100 ml of tetrahydrofuran were charged into an autoclave container equipped with a stirrer, and a reduction reaction (reaction temperature 50 ° C., 3 hours) was performed with 1 atmosphere of hydrogen. . After the reaction solution was filtered, the reaction solvent was distilled off to obtain 11.5 g of a compound represented by formula (13).
次いで撹拌装置、冷却器及び温度計を備えた反応容器に、上記で合成した式（１３）で示す化合物１１．５ｇ（２６ミリモル）、４−（４−アクリロイルオキシヘキシルオキシ）安息香酸１５．２ｇ（５２ミリモル）、ジメチルアミノピリジン ０．８ｇ、ジクロロメタン ３００ｍｌを仕込こみ、氷冷バスにて５℃以下に反応容器を保ち。窒素ガスの雰囲気下でジイソプロピルカルボジイミド ７．８ｇ（６４ミリモル）をゆっくり滴下した。滴下終了後、反応容器を室温に戻し５時間反応させた。反応液をろ過した後、ろ液にジクロロメタン１００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、シリカゲルカラムおよび再結晶により精製を行い式（１４）で表す目的の化合物 １８ｇを得た。 Then, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 11.5 g (26 mmol) of the compound represented by the formula (13) synthesized above, 15.2 g of 4- (4-acryloyloxyhexyloxy) benzoic acid. (52 mmol), 0.8 g of dimethylaminopyridine, and 300 ml of dichloromethane were charged, and the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath. In an atmosphere of nitrogen gas, 7.8 g (64 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 100 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was performed by a silica gel column and recrystallization to obtain 18 g of the desired compound represented by formula (14).
（物性値）
1Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１．５５−１．４５（ｍ，８Ｈ），１．７１（ｍ，４Ｈ），１．８３（ｍ，４Ｈ），２．６６（ｍ，４Ｈ），２．９６（ｍ，４Ｈ），３．７６（ｍ，２Ｈ），３．９０（ｓ，４Ｈ），４．０３（ｔ，４Ｈ），４．１７（ｔ，４Ｈ），４．２９（ｔ，１Ｈ），４．７６（ｔ，１Ｈ），５．１８（ｄ，２Ｈ），５．７８（ｄ，２Ｈ），６．１５（ｑ，２Ｈ），６．３７（ｄ，２Ｈ），６．９６（ｄ，４Ｈ）７．２３（ｄ，４Ｈ），７．２５（ｍ，４Ｈ），８．１２（ｄ，４Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：２５．６，２８．４，２８．８，３０．１，３０．２，３５．３，３５．５，６４．３，６７．９，７３．０，７３．８，８０．６，８５．７，１１４．０，１２１．３，１２１．５，１２８．３，１２９．０，１３０．２，１３１．９，１３７．１，１３７．４，１４９．２，１６３．０，１６４．５，１６５．９，１７１．３，１７１．６
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９
（融点）７９℃
式（１４）で表される化合物は、融点が７９℃と低く、他の液晶性化合物との溶解性に優れるが、実施例１と同様にしてＨＴＰを算出した結果、ＨＴＰ＝１２と低い値であった。
（実施例６） 重合性液晶組成物の調製
以下で表す組成の重合性液晶組成物（組成物１）を調製した。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 1.55-1.45 (m, 8H), 1.71 (m, 4H), 1.83 (m, 4H), 2.66 (m, 4H), 2.96 (m, 4H), 3.76 (m, 2H), 3.90 (s, 4H), 4.03 (t, 4H), 4.17 (t, 4H), 4. 29 (t, 1H), 4.76 (t, 1H), 5.18 (d, 2H), 5.78 (d, 2H), 6.15 (q, 2H), 6.37 (d, 2H) ), 6.96 (d, 4H) 7.23 (d, 4H), 7.25 (m, 4H), 8.12 (d, 4H)
13 C-NMR (solvent: deuterated chloroform): δ: 25.6, 28.4, 28.8, 30.1, 30.2, 35.3, 35.5, 64.3, 67.9, 73 0.0, 73.8, 80.6, 85.7, 114.0, 121.3, 121.5, 128.3, 129.0, 130.2, 131.9, 137.1, 137.4 , 149.2, 163.0, 164.5, 165.9, 171.3, 171.6
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809
(Melting point) 79 ° C
The compound represented by the formula (14) has a melting point as low as 79 ° C. and is excellent in solubility with other liquid crystal compounds. As a result of calculating HTP in the same manner as in Example 1, it was as low as HTP = 12. Met.
(Example 6) Preparation of polymerizable liquid crystal composition A polymerizable liquid crystal composition (composition 1) having the following composition was prepared.
重合性液晶組成物は、良好な相溶安定性を有し、コレステリック液晶相を示した。この組成物に光重合開始剤 ベンジルジメチルケタール（商品名イルガキュアー６５１チバスペシャリティーケミカル社製）を組成物１の１００ｇに対し１ｇ添加して重合性液晶組成物（組成物２）を調製した。この組成物２を、真空注入法により、縦５ｃｍ、横５ｃｍ、ギャップ５μｍのポリイミド付きセルに注入した。これに高圧水銀ランプを用いて４ｍＷ／ｃｍ２の紫外線を１２０秒間照射したところ、組成物２が均一な配向状態を保ったまま重合し、光学異方体が得られた。この光学異方体は良好な円偏光特性を有していた。
（比較例３） 重合性液晶組成物の調製
以下に示す組成の重合性液晶組成物（組成物５）を調製した。
The polymerizable liquid crystal composition had good compatibility stability and exhibited a cholesteric liquid crystal phase. 1 g of a photopolymerization initiator benzyl dimethyl ketal (trade name: Irgacure 651 manufactured by Ciba Specialty Chemicals) was added to 100 g of the composition 1 to prepare a polymerizable liquid crystal composition (composition 2). This composition 2 was injected into a cell with polyimide having a length of 5 cm, a width of 5 cm, and a gap of 5 μm by a vacuum injection method. When this was irradiated with ultraviolet rays of 4 mW / cm 2 for 120 seconds using a high-pressure mercury lamp, the composition 2 polymerized while maintaining a uniform orientation, and an optically anisotropic body was obtained. This optical anisotropic body had good circular polarization characteristics.
(Comparative Example 3) Preparation of polymerizable liquid crystal composition A polymerizable liquid crystal composition (composition 5) having the following composition was prepared.
重合性液晶組成物は、コレステリック液晶相を示したが、配向性が悪く不均一であった。この組成物に光重合開始剤 ベンジルジメチルケタール（商品名イルガキュアー６５１チバスペシャリティーケミカル社製）を組成物５の１００ｇに対し１ｇ添加して重合性液晶組成物（組成物６）を調製した。この組成物６を、真空注入法により、縦５ｃｍ、横５ｃｍ、ギャップ５μｍのポリイミド付きセルに注入した。これに高圧水銀ランプを用いて４ｍＷ／ｃｍ２の紫外線を１２０秒間照射したところ、この光学異方体は円偏光特性を有していたが、白濁しており不均一な光学異方体であった。 The polymerizable liquid crystal composition showed a cholesteric liquid crystal phase, but was poorly oriented and non-uniform. A photopolymerization initiator benzyl dimethyl ketal (trade name Irgacure 651, manufactured by Ciba Specialty Chemicals) was added to this composition in an amount of 1 g per 100 g of the composition 5 to prepare a polymerizable liquid crystal composition (composition 6). This composition 6 was injected into a cell with polyimide having a length of 5 cm, a width of 5 cm, and a gap of 5 μm by a vacuum injection method. When this was irradiated with ultraviolet rays of 4 mW / cm 2 for 120 seconds using a high-pressure mercury lamp, this optical anisotropic body had circular polarization characteristics, but it was cloudy and was an uneven optical anisotropic body. It was.
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| JP2022017349A (en) * | 2017-06-29 | 2022-01-25 | Dic株式会社 | Polymerizable liquid crystal composition, optical film using the same and method for producing the same |
| WO2019181247A1 (en) | 2018-03-23 | 2019-09-26 | 富士フイルム株式会社 | Cholesteric liquid crystal layer, laminated body, optically anisotropic body, reflective film, production method for cholesteric liquid crystal layer; forgery prevention medium, and determination method |
| WO2019182052A1 (en) | 2018-03-23 | 2019-09-26 | 富士フイルム株式会社 | Cholesteric liquid crystal layer production method, cholesteric liquid crystal layer, liquid crystal composition, cured product, optically anisotropic body, and reflective layer |
| JPWO2021166802A1 (en) * | 2020-02-18 | 2021-08-26 | ||
| WO2021166802A1 (en) * | 2020-02-18 | 2021-08-26 | 富士フイルム株式会社 | Compound and liquid crystal composition |
Also Published As
| Publication number | Publication date |
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| CN103059036A (en) | 2013-04-24 |
| CN103059036B (en) | 2017-06-06 |
| KR20130044178A (en) | 2013-05-02 |
| JP5962945B2 (en) | 2016-08-03 |
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