JP2013180974A - Polymerizable compound and liquid crystal composition using the same - Google Patents
Polymerizable compound and liquid crystal composition using the same Download PDFInfo
- Publication number
- JP2013180974A JP2013180974A JP2012045324A JP2012045324A JP2013180974A JP 2013180974 A JP2013180974 A JP 2013180974A JP 2012045324 A JP2012045324 A JP 2012045324A JP 2012045324 A JP2012045324 A JP 2012045324A JP 2013180974 A JP2013180974 A JP 2013180974A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- group
- polymerizable
- formula
- crystal composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 132
- 150000001875 compounds Chemical class 0.000 title claims abstract description 110
- 239000000203 mixture Substances 0.000 title claims abstract description 98
- 230000003287 optical effect Effects 0.000 claims description 26
- -1 pyridine-2,5-diyl group Chemical group 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 15
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 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 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 26
- 238000003860 storage Methods 0.000 abstract description 10
- 229920002284 Cellulose triacetate Polymers 0.000 abstract description 5
- 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 abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 81
- 238000006243 chemical reaction Methods 0.000 description 61
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 27
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 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 20
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000012044 organic layer Substances 0.000 description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 17
- 239000010408 film Substances 0.000 description 15
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000010409 thin film Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 9
- 239000004988 Nematic liquid crystal Substances 0.000 description 8
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 238000006266 etherification reaction Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical class C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 210000002858 crystal cell Anatomy 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000001678 irradiating effect Effects 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
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- VVWRJUBEIPHGQF-MDZDMXLPSA-N propan-2-yl (ne)-n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)\N=N\C(=O)OC(C)C VVWRJUBEIPHGQF-MDZDMXLPSA-N 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SCWWDULYYDFWQV-UHFFFAOYSA-N (2-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1O SCWWDULYYDFWQV-UHFFFAOYSA-N 0.000 description 2
- YYXFJSDMOVHLMJ-UHFFFAOYSA-N (4-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(O)C=C1 YYXFJSDMOVHLMJ-UHFFFAOYSA-N 0.000 description 2
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 description 2
- MXLVVOUBPBBRDE-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C=C1 MXLVVOUBPBBRDE-UHFFFAOYSA-N 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
- CCIOBLAYSWKEFP-UHFFFAOYSA-N 3-(4-hydroxyphenyl)propyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCCC1=CC=C(C=C1)O CCIOBLAYSWKEFP-UHFFFAOYSA-N 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000006751 Mitsunobu reaction Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.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 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 1
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- PJMXUSNWBKGQEZ-UHFFFAOYSA-N (4-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(O)C=C1 PJMXUSNWBKGQEZ-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- KTVPMCWZIFNUCO-UHFFFAOYSA-N 1-(4-hydroxyphenyl)ethyl prop-2-enoate Chemical compound C(C=C)(=O)OC(C)C1=CC=C(C=C1)O KTVPMCWZIFNUCO-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- MXDQGXMBJCGRCB-UHFFFAOYSA-N 2-(4-bromophenoxy)oxane Chemical compound C1=CC(Br)=CC=C1OC1OCCCC1 MXDQGXMBJCGRCB-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 150000004786 2-naphthols Chemical class 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical class C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-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
- AQVKHRQMAUJBBP-UHFFFAOYSA-N 4-Bromocatechol Chemical compound OC1=CC=C(Br)C=C1O AQVKHRQMAUJBBP-UHFFFAOYSA-N 0.000 description 1
- RKNBRHXCTBZOCO-UHFFFAOYSA-N 4-[2-[(2-methylpropan-2-yl)oxy]ethoxy]phenol Chemical compound C(C)(C)(C)OCCOC1=CC=C(C=C1)O RKNBRHXCTBZOCO-UHFFFAOYSA-N 0.000 description 1
- YLDFTMJPQJXGSS-UHFFFAOYSA-N 6-bromo-2-naphthol Chemical compound C1=C(Br)C=CC2=CC(O)=CC=C21 YLDFTMJPQJXGSS-UHFFFAOYSA-N 0.000 description 1
- ZAMRNNPFCAMROT-UHFFFAOYSA-N 6-phenylmethoxynaphthalene-2-carboxylic acid Chemical compound C1=CC2=CC(C(=O)O)=CC=C2C=C1OCC1=CC=CC=C1 ZAMRNNPFCAMROT-UHFFFAOYSA-N 0.000 description 1
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101100328110 Arabidopsis thaliana CLC-A gene Proteins 0.000 description 1
- CIPOUSZLSMTYEI-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCCCCC1=C(C=C(C=C1)O)F Chemical compound C(C(=C)C)(=O)OCCCCCCC1=C(C=C(C=C1)O)F CIPOUSZLSMTYEI-UHFFFAOYSA-N 0.000 description 1
- JTVFWAODZCHGMG-UHFFFAOYSA-N C(C=C)(=O)OCC1=CC=C(C=C1)CCC(=O)O Chemical compound C(C=C)(=O)OCC1=CC=C(C=C1)CCC(=O)O JTVFWAODZCHGMG-UHFFFAOYSA-N 0.000 description 1
- BGZLKKANODPFFV-UHFFFAOYSA-N C(C=C)(=O)OCCC1=CC=C(C=C1)CCC(=O)O Chemical compound C(C=C)(=O)OCCC1=CC=C(C=C1)CCC(=O)O BGZLKKANODPFFV-UHFFFAOYSA-N 0.000 description 1
- KBINYCAJIJYSEV-UHFFFAOYSA-N C(C=C)(=O)OCCCOC1=CC=C(C=C1)CCC(=O)O Chemical compound C(C=C)(=O)OCCCOC1=CC=C(C=C1)CCC(=O)O KBINYCAJIJYSEV-UHFFFAOYSA-N 0.000 description 1
- AZCBGLINAIRYAJ-UHFFFAOYSA-N C1(CCCCC1)N=C=NC1CCCCC1.C(C(=C)C)(=O)OC1=CC=C(C=C1)C(C(=O)O)C Chemical compound C1(CCCCC1)N=C=NC1CCCCC1.C(C(=C)C)(=O)OC1=CC=C(C=C1)C(C(=O)O)C AZCBGLINAIRYAJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本願発明は、重合性化合物、及び当該化合物を含有する液晶組成物、更に当該液晶組成物の硬化物である光学異方体又は該液晶分子の配向を制御する硬化物を含有する液晶表示素子に関する。 The present invention relates to a polymerizable compound, a liquid crystal composition containing the compound, an optical anisotropic body that is a cured product of the liquid crystal composition, or a liquid crystal display device containing a cured product that controls the alignment of the liquid crystal molecules. .
近年、情報化社会の進展に伴い液晶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補償フイルムの重要性は益々高まっており、耐久性が高く、高機能化が求められる光学補償フイルムには重合性の液晶組成物を重合させる例が報告されている（特許文献１〜３参照）。光学補償フイルム等に用いる光学異方体は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、機械的強度、表面硬度及び耐熱性なども重要な因子となる。特に近年の３Ｄディスプレイの位相差板として有用であり今後大きく普及するものと思われる。しかしながらよりトリアセチルセルロース（ＴＡＣ）フイルム等のフイルム基板に重合性の液晶組成物を塗布し硬化させた場合は密着性が低く長期信頼性、生産性に問題がおきる懸念があった。 In recent years, with the progress of the information society, the importance of optical compensation films used for deflecting plates and retardation plates, which are essential for liquid crystal displays, has been increasing, and optical compensation films that are required to have high durability and high functionality. Have reported examples of polymerizing a polymerizable liquid crystal composition (see Patent Documents 1 to 3). The optical anisotropy used for the optical compensation film has important factors such as not only the optical properties but also the polymerization rate, solubility, melting point, glass transition point, transparency of the polymer, mechanical strength, surface hardness and heat resistance of the compound. It becomes. In particular, it is useful as a phase difference plate for recent 3D displays and is expected to become widely used in the future. However, when a polymerizable liquid crystal composition is applied to a film substrate such as a triacetyl cellulose (TAC) film and cured, there is a concern that the adhesion is low and long-term reliability and productivity are problematic.
また近年、高速応答性や高いコントラストが得られる液晶表示素子としてＰＳＡ（Ｐｏｌｙｍｅｒ Ｓｕｓｔａｉｎｅｄ Ａｌｉｇｎｍｅｎｔ）型液晶表示装置、ＰＳＶＡ（Ｐｏｌｙｍｅｒ Ｓｔａｂｉｌｉｓｅｄ Ｖｅｒｔｉｃａｌ Ａｌｉｇｎｍｅｎｔ）型液晶表示装置が開発されている。ＰＳＡやＰＳＶＡ型液晶表示素子は、非重合性液晶性組成物及び重合性化合物からなる重合性液晶組成物を基板間に配した状態で、場合により基板間に電圧を印加して液晶分子を配向させ、配向した状態で紫外線等を照射することにより、重合性化合物を重合させて液晶の配向状態を硬化物に記憶させている。またＩＰＳ（インプレーンスイッチング）型液晶表示素子に適用する場合は、無印加状態で硬化させることにより作成できる。 In recent years, PSA (Polymer Sustained Alignment) type liquid crystal display devices and PSVA (Polymer Stabilized Vertical Alignment) type liquid crystal display devices have been developed as liquid crystal display elements capable of obtaining high-speed response and high contrast. A PSA or PSVA type liquid crystal display device aligns liquid crystal molecules by applying a voltage between substrates in a state where a polymerizable liquid crystal composition comprising a non-polymerizable liquid crystal composition and a polymerizable compound is arranged between the substrates. Then, the polymerizable compound is polymerized by irradiating ultraviolet rays or the like in the aligned state, and the alignment state of the liquid crystal is stored in the cured product. Moreover, when applying to an IPS (in-plane switching) type | mold liquid crystal display element, it can produce by hardening in a no-application state.
このような液晶表示素子の課題として、同一の表示を長時間継続した場合に発生する「焼き付き」などの信頼性の問題や保存安定性、及び製造プロセスに起因する生産性に等の課題も残されている。信頼性の問題は、単純なものではなく、幾つかの複合的な要因によって引き起こされるものであるが特に、（１）残存した重合性化合物に起因するもの、（２）液晶分子の傾斜の変化（プレチルト角の変化）に起因するもの、及び（３）紫外線照射による液晶分子等の劣化に起因するものが挙げられる。 As problems with such liquid crystal display elements, there remain problems such as reliability problems such as “burn-in” that occur when the same display is continued for a long time, storage stability, and productivity resulting from the manufacturing process. Has been. The problem of reliability is not simple and is caused by several complex factors, in particular, (1) caused by the remaining polymerizable compound, (2) change in tilt of liquid crystal molecules And (3) those caused by deterioration of liquid crystal molecules and the like due to ultraviolet irradiation.
信頼性に関しては、使用する重合開始剤及びその分解物が、液晶表示素子の電圧保持率が低下や、焼き付けの原因となってしまう。従って、光重合開始剤を用いることなく、低紫外線量で重合が完結するような重合性化合物含有液晶組成物が求められる。また、焼き付きの発生には、重合性化合物を含有する液晶組成物における、液晶分子のプレチルト角の変化に起因するものも知られている。すなわち、重合性化合物の硬化物であるポリマーが柔軟であると、表示素子を構成した場合において同一のパターンを長時間表示し続けるとポリマーの構造が変化し、その結果としてプレチルト角が変化してしまう。プレチルト角の変化は、応答速度に大きく影響を与えるため焼き付きの原因となる。このことから（２）を解決するためには、ポリマー構造が変化しない剛直な構造を持つポリマーを形成する重合性化合物が有効であるが、液晶組成物の低温保存が悪化することから液晶との相溶性も向上させる必要がある。溶解性を向上させるため全ての環構造と重合性官能基の間にスペーサー基を挿入してしまうと分子の剛性が低下し液晶分子の傾斜を制御する能力が低下してしまう。以上のように、従来の重合性液晶組成物を使用した液晶表示素子では、焼き付き特性、溶解性及びプレチルト角の安定性に満足できるものではなかった。 Regarding reliability, the polymerization initiator to be used and the decomposition product thereof cause a decrease in the voltage holding ratio of the liquid crystal display element and cause burn-in. Accordingly, there is a demand for a polymerizable compound-containing liquid crystal composition that can be polymerized with a low amount of ultraviolet light without using a photopolymerization initiator. Further, the occurrence of image sticking is also known to be caused by a change in the pretilt angle of liquid crystal molecules in a liquid crystal composition containing a polymerizable compound. That is, if the polymer, which is a cured product of the polymerizable compound, is flexible, the structure of the polymer will change if the same pattern is displayed for a long time when the display element is configured, and as a result, the pretilt angle will change. End up. The change in the pretilt angle greatly affects the response speed, which causes burn-in. Therefore, in order to solve (2), a polymerizable compound that forms a polymer having a rigid structure in which the polymer structure does not change is effective. However, since the low-temperature storage of the liquid crystal composition deteriorates, It is necessary to improve the compatibility. If a spacer group is inserted between all the ring structures and the polymerizable functional group in order to improve the solubility, the rigidity of the molecule is lowered and the ability to control the tilt of the liquid crystal molecules is lowered. As described above, the liquid crystal display element using the conventional polymerizable liquid crystal composition is not satisfactory in the seizure characteristics, the solubility and the stability of the pretilt angle.
本発明の課題は、トリアセチルセルロース（ＴＡＣ）フイルム等のフイルム基板に重合性の液晶組成物を塗布し硬化させた場合の密着性改善及び、ＰＳＡ表示素子に用いた場合の組成物の保存安定性、及び表示特性の改善した液晶表示素子を提供することである。 An object of the present invention is to improve adhesion when a polymerizable liquid crystal composition is applied to a film substrate such as a triacetyl cellulose (TAC) film and cured, and to preserve the composition when used for a PSA display element. It is to provide a liquid crystal display element having improved properties and display characteristics.
本願発明者らは、上記課題を解決するために鋭意検討した結果、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 intensive studies to solve the above-mentioned problems, 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)
（式中、Ｚは水素原子、炭素原子数１〜８のアルキル基、炭素原子数１〜８のハロゲン化アルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数１〜８のハロゲン化アルコキシ基、ハロゲン、シアノ基、又はニトロ基又は−Ｓ１−Ｒ２を表し、Ｓ１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、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−に置き換えられても良い炭素数１〜１２のアルキレン基、又は単結合を表し、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 (In the formula, Z represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogenated group having 1 to 8 carbon atoms. Represents an alkoxy group, a halogen, a cyano group, or a nitro group, or —S 1 —R 2 , and S 1 represents an oxygen atom, —COO—, —OCO—, —OCOO assuming that the oxygen atoms are not directly bonded to each other. -Represents an alkylene group having 1 to 12 carbon atoms which may be replaced with-or a single bond, and R 1 and R 2 are each independently any of the following formulas (R-1) to (R-15):
を表し、Ｌ１は単結合、−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−Ｃ２Ｈ４−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯＣＨ２−、−ＣＨ２ＯＣＯＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯＣ２Ｈ４−、−ＯＣＯＣ２Ｈ４−、−Ｃ２Ｈ４ＯＣＯ−、−Ｃ２Ｈ４ＣＯＯ−、−ＣＨ＝ＣＨ−、−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。）、Ｌ２は−ＯＣＨ２ＣＨ２Ｏ−、−ＯＣＯＣ２Ｈ４−又は−ＣＯＯＣ２Ｈ４−を表し、Ｍ１、Ｍ２及びＭ３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、ナフタレン−１，４−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、Ｍ１、Ｍ２及びＭ３は、お互い独立して無置換であるか又は炭素原子数１〜８のアルキル基、炭素原子数１〜８のハロゲン化アルキル基、炭素原子数１〜８のアルコキシ基、ハロゲン、シアノ基又はニトロ基で置換されていても良く、更にＭ１はＲ１で置換されていてもよく、Ｒ１が複数存在する場合にはそれらは同一であっても異なっていてもよく、ｎは１，２及び３を表し、ｎが２又は３を表す場合、２個又は３個存在するＬ１及びＭ２は同一であっても異なっていても良いが、Ｌ１の少なくとも一つは単結合を表す。）で表される重合性化合物を提供し、併せて当該重合性化合物を含有する重合性組成物、当該重合性化合物を含有する重合性液晶組成物、当該重合性液晶組成物の重合体により構成される光学異方体、当該重合性化合物及び非重合性液晶化合物を含有する重合性液晶組成物及び重合性液晶組成物を使用し、重合性液晶組成物中の重合性化合物を重合することにより液晶配向能を付与した液晶表示素子を提供する。 L 1 represents a single bond, —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —C 2 H 4 —, —COO—, —OCO—, —OCOOCH 2 —, -CH 2 OCOO -, - CH = CH-COO -, - OCO-CH = CH -, - COO-CH = CH -, - CH = CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 —, —CF 2 CF 2 — or —C≡C— is represented (wherein R 11 represents an alkyl group having 1 to 4 carbon atoms), and L 2 represents —OCH 2 CH 2 O—, —OCOC. 2 H 4 - or -COOC 2 H 4 - represents, M 1, M 2 and M 3 are independently from each other, , 4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, Represents a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, wherein M 1 , M 2 and M 3 are each independently unsubstituted or have 1 carbon atom May be substituted with an alkyl group of ˜8, a halogenated alkyl group of 1 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, a halogen, a cyano group or a nitro group, and M 1 is R 1 They may be substituted, and when there are a plurality of R 1 s , they may be the same or different, n represents 1, 2 and 3, and when n represents 2 or 3, 2 Or three L 1 and M 2 are the same Although it may be present or different, at least one of L 1 represents a single bond. And a polymerizable composition containing the polymerizable compound, a polymerizable liquid crystal composition containing the polymerizable compound, and a polymer of the polymerizable liquid crystal composition. By polymerizing the polymerizable compound in the polymerizable liquid crystal composition using the polymerizable liquid crystal composition and the polymerizable liquid crystal composition containing the optically anisotropic body, the polymerizable compound and the non-polymerizable liquid crystal compound Provided is a liquid crystal display element imparted with liquid crystal alignment ability.
本願発明の重合性化合物を用いた重合性組成物を用いた光学異方体は、基板との密着性が良好で偏向板、位相差板等の用途に有用である。 An optical anisotropic body using a polymerizable composition using the polymerizable compound of the present invention has good adhesion to a substrate and is useful for applications such as a deflection plate and a retardation plate.
また、重合性液晶組成物中の重合性化合物を重合することにより液晶配向能を付与した液晶表示素子に使用した場合は、重合開始剤を添加しないか、ごく少量の添加で当該重合性化合物は光又は熱による重合が可能であり、光開始剤由来の不純物の影響がないかあるいは極めて少ないため信頼性と生産性を両立させることが出来る。また当該重合性化合物を使用することにより、プレチルト角の安定性が従来と比較して大きく改善された液晶表示素子の提供が可能となった。 In addition, when used in a liquid crystal display element having a liquid crystal alignment ability by polymerizing a polymerizable compound in the polymerizable liquid crystal composition, the polymerizable compound is added with a very small amount of addition of a polymerization initiator. Polymerization by light or heat is possible, and there is no influence or very little influence of impurities derived from the photoinitiator, so that both reliability and productivity can be achieved. Further, by using the polymerizable compound, it has become possible to provide a liquid crystal display device in which the stability of the pretilt angle is greatly improved as compared with the conventional one.
更に、本発明の重合性組成物及び重合性液晶組成物は保存時の結晶の析出や分離等によって評価される保存安定性も良好である。 Furthermore, the polymerizable composition and the polymerizable liquid crystal composition of the present invention have good storage stability evaluated by crystal precipitation and separation during storage.
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）、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 preferable, and formula (R-1) and formula (R-2) are more preferable.
Ｚは水素原子、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、シアノ基、又はニトロ基又は−Ｓ１−Ｒ２を表し、Ｓ１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、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−に置き換えられても良い炭素数１〜１２のアルキレン基、又は単結合を表すが、表示素子に使用する場合は、Ｚが−Ｓ１−Ｒ２であることが好ましく、Ｓ１が炭素数１〜１２のアルキレン基、又は単結合がより好ましい。 Z represents a hydrogen atom, an alkyl group, a halogenated alkyl group, alkoxy group, halogenated alkoxy group, a halogen, a cyano group, or a nitro group or a -S 1 -R 2, S 1 is between oxygen atoms are not linked directly The carbon atom represents an alkylene group having 1 to 12 carbon atoms which may be replaced by an oxygen atom, -COO-, -OCO-, -OCOO-, or a single bond. Is preferably -S 1 -R 2 , and S 1 is more preferably a C 1-12 alkylene group or a single bond.
Ｌ１は単結合、−ＯＣＨ２−、−ＣＨ２Ｏ−、−Ｃ２Ｈ４−、―ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯＣ２Ｈ４−、−ＯＣＯＣ２Ｈ４−、−Ｃ２Ｈ４ＯＣＯ−、−Ｃ２Ｈ４ＣＯＯ−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−Ｃ≡Ｃ−が好ましく、安価に製造、液晶配向性の観点から、単結合、―ＣＯＯ−、−ＯＣＯ−、又は−ＯＣＨ２−、−ＣＨ２Ｏ−がより好ましいが、複数あるＬ１の少なくとも一つは単結合を表す。Ｌ２は溶解性、紫外線吸収帯の長波長化の観点から−ＯＣＯＣ２Ｈ４−、−ＣＯＯＣ２Ｈ４−が好ましい。Ｍ１、Ｍ２及びＭ３は、１，４−フェニレン基、１，４−シクロヘキシレン基又はナフタレン−２，６−ジイル基が好ましい。Ｍ１上にＲ１は一般式（Ｉ）に明示したＲ１以外に更に１個又は２個以上存在してもよいが、硬化物の強度を上げるためには１又は２個が好ましく、液晶性に関しては１個又は置換していないことが好ましい。Ｍ１上にＲ１が置換している場合には、一般式（Ｉ）におけるＲ１のオルト位に置換していることが好ましい。ｎは１，２及び３を表すが、ｎは１又は２が好ましい。 L 1 is a single bond, —OCH 2 —, —CH 2 O—, —C 2 H 4 —, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —COO. -CH = CH -, - CH = CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - CF 2 O-, —OCF 2 — and —C≡C— are preferable, and from the viewpoint of inexpensive production and liquid crystal alignment, a single bond, —COO—, —OCO—, or —OCH 2 —, —CH 2 O— are more preferable. And at least one of the plurality of L 1 represents a single bond. L 2 is soluble, -OCOC 2 H 4 in view of the long wavelength UV absorption band -, - COOC 2 H 4 - is preferable. M 1 , M 2 and M 3 are preferably a 1,4-phenylene group, a 1,4-cyclohexylene group or a naphthalene-2,6-diyl group. One or two or more R 1 may be present on M 1 in addition to R 1 explicitly shown in the general formula (I), but one or two are preferable for increasing the strength of the cured product. In terms of sex, it is preferred that one or not be substituted. When R 1 is substituted on M 1 , it is preferably substituted at the ortho position of R 1 in formula (I). n represents 1, 2 and 3, and n is preferably 1 or 2.
一般式（Ｉ）で表される化合物は、より具体的には、下記の一般式（Ｉ−１）〜一般式（Ｉ−４５）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 general formula (I-1) to general formula (I-45).
（式中、ｐは０〜１２の整数を表すが、ｐが０であり酸素原子同士が直接結合してしまう場合には一方の酸素原子を除去する。）
本発明の重合性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−１）で表される化合物の製造
４−（４−ヒドロキシフェニル）安息香酸エチルと４−（２−ヒドロキシエチル）フェノールとの錫触媒によるエステル交換反応によりビフェニル骨格を有するフェノール誘導体（Ｓ−１）を得る。更に塩化アクリロイルとのエステル化反応により目的物（Ｉ−１）を得ることができる。
(In the formula, p represents an integer of 0 to 12, but when p is 0 and oxygen atoms are directly bonded to each other, one oxygen atom is removed.)
The polymerizable 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-1) Biphenyl Skeleton by Transesterification Reaction of Ethyl 4- (4-hydroxyphenyl) benzoate and 4- (2-hydroxyethyl) phenol with a Tin Catalyst A phenol derivative (S-1) having Further, the desired product (I-1) can be obtained by esterification with acryloyl chloride.
（製法２） 一般式（Ｉ−５）で表される化合物の製造
４，４’−ジヒドロキシビフェニルとエチレングリコールモノターシャリーブチルエーテルとのトリフェニルホスフィン、ジイソプロピルアゾジカルボン酸との光延反応により、ビフェノール誘導体（Ｓ−２）を得て、更に塩化メタクリロイルとのエステル化反応によりメタクリル酸誘導体（Ｓ−３）を得る。次いでトリフルオロ酢酸により、ターシャリーブチル基を脱離させてエタノールに変換したメタクリル酸誘導体（Ｓ−４）を得る。
(Production method 2) Production of compound represented by general formula (I-5) Biphenol derivative by Mitsunobu reaction of 4,4'-dihydroxybiphenyl with triphenylphosphine and diisopropylazodicarboxylic acid of ethylene glycol monotertiary butyl ether (S-2) is obtained, and further a methacrylic acid derivative (S-3) is obtained by an esterification reaction with methacryloyl chloride. Next, a methacrylic acid derivative (S-4) obtained by removing the tertiary butyl group and converting it to ethanol with trifluoroacetic acid is obtained.
メタクリル酸誘導体（Ｓ−４）と４−メタクリロイルオキシフェノールとのトリフェニルホスフィン、ジイソプロピルアゾジカルボン酸との光延反応により目的化合物（Ｉ−５）を得ることができる。
（製法３） 一般式（Ｉ−１６）で表される化合物の製造
２−ブロモ−６−オキシテトラヒドロピラニルナフタレンとヒドロキシフェニルホウ酸との鈴木カップリング反応によりフェニルナフタレン誘導体（Ｓ−５）を得て、更に塩化メタクリロイルとのエステル化反応によりメタクリル酸誘導体（Ｓ−６）を得る。次いで塩酸によりフェノール性水酸基の保護基を脱離させてナフトール誘導体（Ｓ−７）を得る。
The target compound (I-5) can be obtained by Mitsunobu reaction of methacrylic acid derivative (S-4) with 4-methacryloyloxyphenol with triphenylphosphine and diisopropyl azodicarboxylic acid.
(Manufacturing method 3) Manufacture of the compound represented by general formula (I-16) A phenyl naphthalene derivative (S-5) is obtained by a Suzuki coupling reaction of 2-bromo-6-oxytetrahydropyranylnaphthalene and hydroxyphenyl boric acid. Further, a methacrylic acid derivative (S-6) is obtained by an esterification reaction with methacryloyl chloride. Next, the protecting group of the phenolic hydroxyl group is eliminated with hydrochloric acid to obtain a naphthol derivative (S-7).
次いで、１−（４−メタクリロイルオキシフェニルプロピオン酸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−１２）を得ることができる。 Subsequently, the target compound (I-12) can be obtained by esterification reaction using a dehydrating condensing agent such as 1- (4-methacryloyloxyphenylpropionic acid dicyclohexylcarbodiimide).
（製法４） 一般式（Ｉ−１９）で表される化合物の製造
２，３−ジフルオロ−４−（４−ヒドロキシフェニル）フェニルホウ酸と１−ブロモ−４−オキシテトラヒドロピラニルベンゼンとの鈴木カップリング反応により水酸基を有するテルフェニル誘導体（Ｓ−８）を得る。次いでエチレングリコールモノターシャリーブチルエーテルとのトリフェニルホスフィン及びジイソプロピルアゾジカルボン酸を用いた光延のエーテル化反応により、テルフェニル誘導体（Ｓ−９）を得て、更に塩酸によりフェノール性水酸基の保護基を脱離させ（Ｓ−１０）とした後、塩化アクリロイルを用いたエステル化反応により、アクリロイル基を有するテルフェニル誘導体（Ｓ−１１）を得る。次いでトリフルオロ酢酸により、ターシャリーブチル基を脱離させてエチレングリコールモノエーテル誘導体（Ｓ−１２）を得る。
(Production Method 4) Production of Compound Represented by General Formula (I-19) Suzuki Cup of 2,3-difluoro-4- (4-hydroxyphenyl) phenylboric acid and 1-bromo-4-oxytetrahydropyranylbenzene A terphenyl derivative (S-8) having a hydroxyl group is obtained by a ring reaction. Next, Mitsunobu etherification reaction with ethylene glycol monotertiary butyl ether using triphenylphosphine and diisopropyl azodicarboxylic acid gave terphenyl derivative (S-9), and further the protecting group of phenolic hydroxyl group was removed with hydrochloric acid. After releasing (S-10), a terphenyl derivative (S-11) having an acryloyl group is obtained by an esterification reaction using acryloyl chloride. Next, the tertiary butyl group is eliminated with trifluoroacetic acid to obtain an ethylene glycol monoether derivative (S-12).
更にエチレングリコールモノエーテル誘導体（Ｓ−１２）と４−（１−アクリロイルオキシエチル）フェノールをトリフェニルホスフィン及びジイソプロピルアゾジカルボン酸を用いた光延のエーテル化反応により目的化合物（Ｓ−１９）を得ることができる。 Furthermore, the target compound (S-19) is obtained by the etherification reaction of Mitsunobu with ethylene glycol monoether derivative (S-12) and 4- (1-acryloyloxyethyl) phenol using triphenylphosphine and diisopropyl azodicarboxylic acid. Can do.
（製法５） 一般式（Ｉ−２９）で表される化合物の製造
２−アクリロイルオキシ−６−ナフトエ酸と製法２で合成したビフェノール誘導体（Ｓ−２）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ナフトエ誘導体（Ｓ−１３）得る。次いでトリフルオロ酢酸により、ターシャリーブチル基を脱離させてエタノールに変換したメタクリル酸誘導体（Ｓ−１４）を得て、更に４−（６−メタクリロイルオキシヘキシル）−３−フルオロフェノールとのトリフェニルホスフィン及びジイソプロピルアゾジカルボン酸を用いた光延のエーテル化反応により目的化合物（Ｉ−２９）を得ることができる。
(Production Method 5) Production of Compound Represented by General Formula (I-29) A dehydration condensing agent such as dicyclohexylcarbodiimide of 2-acryloyloxy-6-naphthoic acid and the biphenol derivative (S-2) synthesized by Production Method 2 The naphtho derivative (S-13) is obtained by the esterification reaction used. Next, a methacrylic acid derivative (S-14) obtained by removing the tertiary butyl group and converting to ethanol with trifluoroacetic acid was obtained, and further triphenyl with 4- (6-methacryloyloxyhexyl) -3-fluorophenol. The target compound (I-29) can be obtained by Mitsunobu etherification reaction using phosphine and diisopropyl azodicarboxylic acid.
（製法６） 一般式（Ｉ−３８）で表される化合物の製造
塩化ベンジルを用いて４−ブロモカテコールに保護基を導入した化合物（Ｓ−１５）と４−ヒドロキシフェニルホウ酸との鈴木カップリング反応によりヒドロキシビフェニル誘導体（Ｓ−１６）を得て、更にエチレングリコールモノターシャリーブチルエーテルとのトリフェニルホスフィン及びジイソプロピルアゾジカルボン酸を用いた光延のエーテル化反応により、ビフェニル誘導体（Ｓ−１７）を得る。次いで、パラジウムカーボンを用いた接触水素還元によりベンジル保護基を脱離させてカテコール誘導体（Ｓ−１８）を得る。
(Manufacturing method 6) Manufacture of the compound represented by general formula (I-38) Suzuki cup of the compound (S-15) which introduce | transduced the protective group into 4-bromocatechol using benzyl chloride, and 4-hydroxyphenyl boric acid A hydroxybiphenyl derivative (S-16) is obtained by a ring reaction, and further a biphenyl derivative (S-17) is obtained by an etherification reaction of Mitsunobu using triphenylphosphine and diisopropyl azodicarboxylic acid with ethylene glycol monotertiary butyl ether. obtain. Next, the benzyl protecting group is eliminated by catalytic hydrogen reduction using palladium carbon to obtain a catechol derivative (S-18).
カテコール誘導体（Ｓ−１８）と塩化メタクリロイルとのエステル化反応によりメタクリル酸誘導体（Ｓ−１９）を得て、更にトリフルオロ酢酸により、ターシャリーブチル基を脱離させてエタノールに変換したメタクリル酸誘導体（Ｓ−２０）を得る。次いで４−（３−メタクリロイルオキプロピル）フェノールとのトリフェニルホスフィン及びジイソプロピルアゾジカルボン酸を用いた光延のエーテル化反応により目的化合物（Ｉ−３８）を得ることができる。 Methacrylic acid derivative obtained by obtaining methacrylic acid derivative (S-19) by esterification reaction of catechol derivative (S-18) and methacryloyl chloride, and then removing tertiary butyl group with trifluoroacetic acid to convert it to ethanol (S-20) is obtained. Subsequently, the target compound (I-38) can be obtained by Mitsunobu etherification reaction using 4- (3-methacryloyloxypropyl) phenol with triphenylphosphine and diisopropyl azodicarboxylic acid.
（製法７） 一般式（Ｉ−４３）で表される化合物の製造
製法６で合成したカテコール誘導体（Ｓ−１８）と３−エチル−３−オキセタンメタノールとのトリフェニルホスフィン及びジイソプロピルアゾジカルボン酸を用いた光延のエーテル化反応によりオキセタン酸誘導体（Ｓ−２１）を得て、更にトリフルオロ酢酸により、ターシャリーブチル基を脱離させてエタノールに変換したオキセタン酸誘導体（Ｓ−２２）を得る。
(Production Method 7) Production of Compound Represented by General Formula (I-43) Triphenylphosphine and diisopropyl azodicarboxylic acid of catechol derivative (S-18) synthesized in Production Method 6 and 3-ethyl-3-oxetanemethanol The oxetanoic acid derivative (S-21) is obtained by the etherification reaction of Mitsunobu used, and the oxetanoic acid derivative (S-22) which is converted to ethanol by removing the tertiary butyl group with trifluoroacetic acid.
次いで４−（３−メタクリロイルオキプロピル）フェノールとのトリフェニルホスフィン及びジイソプロピルアゾジカルボン酸を用いた光延のエーテル化反応により目的化合物（Ｉ−４３）を得る。 Subsequently, Mitsunobu etherification reaction with 4- (3-methacryloyloxypropyl) phenol using triphenylphosphine and diisopropyl azodicarboxylic acid gives the target compound (I-43).
本願発明の重合性組成物及び重合性液晶組成物は、本願発明の重合性化合物を一種以上用いる以外に、任意の範囲で他の重合性化合物を添加しても構わない。本願発明以外の重合性化合物の具体例としては、特に制限はないが、組み合わせて使用する重合性液晶化合物としては、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。 In the polymerizable composition and the polymerizable liquid crystal composition of the present invention, other polymerizable compounds may be added in an arbitrary range other than using one or more polymerizable compounds of the present invention. Specific examples of the polymerizable compound other than the present invention are not particularly limited, but the polymerizable liquid crystal compound used in combination includes an acryloyloxy group (R-1) or a methacryloyloxy group (R-2) in the compound. ) Are preferred, and those having two or more polymerizable functional groups in the molecule are more preferred.
組み合わせて使用する重合性（液晶）化合物として具体的には一般式（ＩＩ） Specifically, the polymerizable (liquid crystal) compound used in combination is represented by the general formula (II)
（式中Ｒ１１は重合性基であり、Ｓ１１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わし、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炭素原子が酸素原子、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−に置き換えられても良く、Ｌ１１及びＬ１２はお互い独立して、単結合、−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯＣＨ２−、−ＣＨ２ＯＣＯＯ−、−ＣＯ−ＮＲ１３−、−ＮＲ１３−ＣＯ−、−ＣＨ＝Ｎ−、−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−を表わすが（式中、Ｒ１３は炭素原子１〜４のアルキル基を表わす。）、Ｍ１１及びＭ１２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−ジイル基を表わすが、Ｍ１、及びＭ１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、ｌ１１は０、１、２又は３を表わす。ｌ１１が２又は３を表す場合、２個あるいは３個存在するＬ１２及びＭ１２は同一であっても異なっていても良い。）で表される化合物を挙げることができる
一般式（ＩＩ）で表される化合物について、Ｌ１、Ｌ１及びＬ１はお互い独立して、単結合、−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−が好ましく、Ｍ１１及びＭ１２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−ジイル基又はナフタレン−２，６−ジイル基が好ましい。
Wherein R 11 is a polymerizable group, and S 11 independently represents a single bond or an alkylene group having 1 to 12 carbon atoms, wherein one or more —CH 2 — represents The carbon atom may be replaced with an oxygen atom, —COO—, —OCO—, —OCOO— as those in which oxygen atoms are not directly bonded to each other, and L 11 and L 12 are each independently a single bond, —O— , -S -, - OCH 2 - , - CH 2 O -, - CO -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CO-NR 13 -, - NR 13 - CO -, - CH = N - , - 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 -, - OC CH 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 represents a -C≡C-, (wherein, R 13 represents an alkyl group having 1 to 4 carbon atoms.) M 11 and M 12 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6- A diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, wherein M 1 and M 1 are each independently unsubstituted or an alkyl group, halogen Alkyl group, alkoxy group, halogenated alkoxy group Halogen group may be substituted with a cyano group, or a nitro group, l 11 if .l 11 representing 0, 1, 2 or 3 is 2 or 3, two or three L 12 and there M 12 may be the same or different.) For the compound represented by the general formula (II), L 1 , L 1 and L 1 are independent of each other. , A single bond, —O—, —COO— or —OCO— is preferable, and M 11 and M 12 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5- A diyl group, a pyrimidine-2,5-diyl group or a naphthalene-2,6-diyl group is preferred.
一般式（ＩＩ）で表される化合物は具体的には、一般式（ＩＩ−１）〜一般式（ＩＩ−４３）で表される化合物が好ましい。 Specifically, the compound represented by General Formula (II) is preferably a compound represented by General Formula (II-1) to General Formula (II-43).
（式中、ａ及びｂは、０〜１２の整数を表わすが、ａ及び／又はｂが０であり酸素原子同士が直接結合してしまう場合には一方の酸素原子を除去する。）
本願発明の重合性化合物は、偏向板、位相差板などに用いられる光学補償フイルムを作成する際の構成成分として有効であり、重合性化合物で液晶分子の配向を制御するＰＳＡ（Ｐｏｌｙｍｅｒ Ｓｕｓｔａｉｎｅｄ Ａｌｉｇｎｍｅｎｔ）型液晶表示装置、ＰＳＶＡ（Ｐｏｌｙｍｅｒ Ｓｔａｂｉｌｉｓｅｄ Ｖｅｒｔｉｃａｌ Ａｌｉｇｎｍｅｎｔ）型液晶表示装置にも有効である。またＯＣＢ（Ｏｐｔｉｃａｌｌｙ Ｃｏｍｐｅｎｓａｔｅｄ Ｂｉｒｅｆｒｉｎｇｅｎｃｅ）−ＬＣＤ及びＩＰＳ−ＬＣＤ（インプレーンスイッチング液晶表示素子）にも使用可能である。当該液晶表示装置の駆動方式としては、アクティブ駆動及びパッシブ駆動が可能であり、ＡＭ−ＬＣＤ（アクティブマトリックス液晶表示素子）、ＴＮ（ネマチック液晶表示素子）及びＳＴＮ−ＬＣＤ（超ねじれネマチック液晶表示素子）に有用であり、ＡＭ−ＬＣＤに特に有用である。
(In the formula, a and b represent an integer of 0 to 12, but when a and / or b is 0 and oxygen atoms are directly bonded to each other, one oxygen atom is removed.)
The polymerizable compound of the present invention is effective as a component for producing an optical compensation film used for a deflecting plate, a retardation plate, and the like, and is a PSA (Polymer Sustained Alignment) that controls the alignment of liquid crystal molecules with the polymerizable compound. The present invention is also effective for a liquid crystal display device of a type and a PSVA (Polymer Stabilized Vertical Alignment) type of liquid crystal display device. It can also be used for OCB (Optically Compensated Birefringence) -LCD and IPS-LCD (In-Plane Switching Liquid Crystal Display Device). As a driving method of the liquid crystal display device, active driving and passive driving are possible, and AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), and STN-LCD (super twisted nematic liquid crystal display element). It is particularly useful for AM-LCDs.
非重合性の液晶組成物としては、一般に知られている誘電率異方性が正又は負のフッ素系ネマチック液晶組成物、誘電率異方性が正又は負のトラン系ネマチック液晶組成物、誘電率異方性が正のシアノ系ネマチック液晶組成物、強誘電液晶組成物、ブルー相液晶組成物、コレステリック液晶組成物等を用いることができる。本願発明の液晶組成物がコレステリック液晶の場合は、通常キラル化合物を添加するが、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重量％が好ましく、２〜２０重量％がより好ましい。 Non-polymerizable liquid crystal compositions include generally known fluorine-based nematic liquid crystal compositions having a positive or negative dielectric anisotropy, tolan-based nematic liquid crystal compositions having a positive or negative dielectric anisotropy, and dielectrics. A cyano nematic liquid crystal composition having a positive rate anisotropy, a ferroelectric liquid crystal composition, a blue phase liquid crystal composition, a cholesteric liquid crystal composition, or the like can be used. When the liquid crystal composition of the present invention is a cholesteric liquid crystal, a chiral compound is usually added. Specific compounds are represented by general formulas (IV-1) to (IV-7). 0.5-30 weight% is preferable with respect to a liquid crystal composition, and, as for the compounding quantity of a chiral compound, 2-20 weight% is more preferable.
（式中、ｍ及びｌは、０〜１２の整数を表わすが、ｍ及び／又はｌが０であり酸素原子同士が直接結合してしまう場合には一方の酸素原子を除去する。）
本発明の重合性化合物を用いたＰＳＡ、ＰＳ−ＶＡ、ＰＳ−ＩＰＳ及びＰＳ−ＯＣＢ液晶組成物の場合は、一般式（Ｉ）で表される重合性化合物を少なくとも１種を含有するが、１種〜５種含有することが好ましく、１種〜３種含有することが特に好ましい。また、一般式（Ｉ）で表される重合性化合物の含有率は、少ないと非重合性液晶化合物に対する配向規制力が弱くなり、多すぎると重合時の必要エネルギーが上昇し、重合せず残存してしまう重合性化合物の量が増してしまうため、下限値は０．０１質量%であることが好ましく、０．０３質量%であることがより好ましく、上限値は５．０質量%であることが好ましく、１．０質量%であることがより好ましい。
(In the formula, m and l represent an integer of 0 to 12, but when m and / or l is 0 and oxygen atoms are directly bonded to each other, one oxygen atom is removed.)
In the case of PSA, PS-VA, PS-IPS and PS-OCB liquid crystal compositions using the polymerizable compound of the present invention, it contains at least one polymerizable compound represented by the general formula (I). 1 to 5 types are preferably contained, and 1 to 3 types are particularly preferably contained. In addition, if the content of the polymerizable compound represented by the general formula (I) is small, the alignment regulating power for the non-polymerizable liquid crystal compound is weak, and if it is too large, the necessary energy during polymerization increases and the polymer does not polymerize. Therefore, the lower limit value is preferably 0.01% by mass, more preferably 0.03% by mass, and the upper limit value is 5.0% by mass. It is preferably 1.0% by mass.
また、本発明の重合性（液晶）組成物には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、その添加量は重合性組成物が液晶相を呈することが求められる場合には、添加後の重合性液晶組成物が液晶性を呈するように調整する必要がある。 Moreover, the compound which does not show liquid crystallinity can also be added to the polymeric (liquid crystal) composition of this invention. 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. Is required to exhibit a liquid crystal phase, it is necessary to adjust so that the polymerizable liquid crystal composition after the addition exhibits liquid crystallinity.
本発明の重合性（液晶）組成物は、π電子が広く共役したビフェニル及びフェニルナフタレン骨格を有するため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、光重合開始剤を添加してもよい。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 polymerizable (liquid crystal) composition of the present invention has a biphenyl and phenylnaphthalene skeleton in which π electrons are widely conjugated, and thus can be polymerized by heat and light without adding a polymerization initiator. May be added. 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、本発明の重合性（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、重合性組成物に対して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 may be added to the polymerizable (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. The addition amount in the case of using a stabilizer is preferably in the range of 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0.1% with respect to the polymerizable composition. Mass% is particularly preferred.
また、本発明の重合性（液晶）組成物を位相差フイルム、偏光フイ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、溶剤、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 polymerizable (liquid crystal) composition of the present invention is used for a retardation film, a raw material for a polarizing film or an alignment film, or a printing ink and paint, a protective film, etc., a metal, Metal complexes, dyes, pigments, solvents, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, Metal oxides such as titanium oxide can also be added.
次に本発明の光学異方体について説明する。本発明の重合性（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を担持した表面を、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 polymerizable (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 on which the surface carrying the polymerizable liquid crystal composition of the present invention is rubbed with a cloth or the like, or a substrate surface on which an organic thin film is formed is rubbed with a cloth or the like, Alternatively, it can be produced by polymerizing the liquid crystal of the present invention after it is supported on a substrate having an orientation film on which SiO 2 is obliquely deposited 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に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重量％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. The amount added is preferably 90% by weight 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. .
重合性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や液晶滴下注入（ＯＤＦ：Ｏｎｅ Ｄｒｏｐ Ｆｉｌｌ）も有効である。 Examples of a method for sandwiching the polymerizable liquid crystal composition between the substrates include an injection method using a capillary phenomenon. Means for reducing the space formed between the substrates and then injecting a liquid crystal material and liquid crystal drop injection (ODF: One Drop Fill) are also effective.
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。
（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６−ブロモ−２−ナフトール ２０ｇ（９０ミリモル）、エチレングリコールモノターシャリーブチルエーテル １２ｇ（１０７ミリモル）、トリフェニルホスフィン ３５ｇ（１３４ミリモル）、ジクロロメタン ３００ｍｌを仕込み、反応容器を５℃に冷却した。その後、ジアゾカルボン酸ジイソプロピル（ＤＩＡＤ）２２ｇ（１０７ミリモル）を滴下した。滴下終了後、室温で５時間撹拌して反応を終了させた。反応終了後、ジクロロメタン ２００ｍｌを加え、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、シリカゲルカラムによる精製により（１）で表される化合物１８ｇを得た。
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%”.
Example 1
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 20 g (90 mmol) of 6-bromo-2-naphthol, 12 g (107 mmol) of ethylene glycol monotertiary butyl ether, 35 g (134 mmol) of triphenylphosphine, dichloromethane 300 ml was charged and the reaction vessel was cooled to 5 ° C. Thereafter, 22 g (107 mmol) of diisopropyl diazocarboxylate (DIAD) was added dropwise. After completion of the dropwise addition, the reaction was terminated by stirring at room temperature for 5 hours. After completion of the reaction, 200 ml of dichloromethane was added, and the organic layer was washed with pure water and saturated brine. After the solvent was distilled off, 18 g of the compound represented by (1) was obtained by purification with a silica gel column.
次いで撹拌装置、冷却器及び温度計を備えた反応容器に、式（１）で表される化合物１０ｇ、ヒドロキシフェニルホウ酸 ４．５ｇ（３２ミリモル）、炭酸カリウム ６．４ｇ（４６ミリモル）、テトラキストリフェニルホスフィンパラジウム ４００ｍｇ、テトラヒドロフラン２００ｍｌ、純水１００ｍｌを仕込み、７０℃で５時間反応させた。反応終了後、冷却し、１０％塩酸を加えた後、酢酸エチルにより目的物を抽出した。有機層を水、飽和食塩水で洗浄し、溶媒を留去した。その後、トルエンによる分散洗浄を行い式（２）で表される化合物 ７ｇを得た。 Next, in a reaction vessel equipped with a stirrer, a condenser and a thermometer, 10 g of the compound represented by the formula (1), 4.5 g (32 mmol) of hydroxyphenylboric acid, 6.4 g (46 mmol) of potassium carbonate, tetrakis 400 mg of triphenylphosphine palladium, 200 ml of tetrahydrofuran, and 100 ml of pure water were charged and reacted at 70 ° C. for 5 hours. After completion of the reaction, the mixture was cooled, 10% hydrochloric acid was added, and the target product was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and the solvent was distilled off. Thereafter, dispersion cleaning with toluene was performed to obtain 7 g of a compound represented by the formula (2).
更に、撹拌装置、冷却器及び温度計を備えた反応容器に、上記式（２）で表される化合物５．５ｇ（１６ミリモル）、メタクリル酸 ２．１ｇ（２４ミリモル）、ジメチルアミノピリジン １１８ｍｇ、ジクロロメタン ５０ｍｌを仕込み、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 ２．４ｇ（２０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１５０ｍｌを加え、５％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、２倍量（重量比）のアルミナカラムにより精製を行い、ジクロロメタンとヘキサンの混合溶液から再結晶により式（３）で表される化合物７．５ｇを得た。 Furthermore, 5.5 g (16 mmol) of the compound represented by the above formula (2), 2.1 g (24 mmol) of methacrylic acid, 118 mg of dimethylaminopyridine, 50 ml of dichloromethane was charged, the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath, and 2.4 g (20 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 150 ml of dichloromethane was added to the filtrate, washed with a 5% 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 with a double amount (weight ratio) alumina column, and 7.5 g of a compound represented by the formula (3) was obtained by recrystallization from a mixed solution of dichloromethane and hexane.
撹拌装置、冷却器及び温度計を備えた反応容器に、上記式（３）で表される化合物７．５ｇ、ジクロロメタン ２０ｍｌを仕込み、氷冷バスにて５℃以下に反応容器を保ち、トリフルオロ酢酸５０ｍｌをゆっくり滴下した。滴下終了後、反応容器を室温に戻し１時間反応させた。反応終了後、反応液を１０℃以下に冷却し純水５０ｍｌをゆっくり加えた。更にジクロロメタン１５０ｍｌを加え、有機層を純水、飽和炭酸水素ナトリウム５％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、式（４）に示す目的の化合物５．５ｇを得た。 A reaction vessel equipped with a stirrer, a cooler, and a thermometer was charged with 7.5 g of the compound represented by the above formula (3) and 20 ml of dichloromethane, and the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath. 50 ml of acetic acid was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 1 hour. After completion of the reaction, the reaction solution was cooled to 10 ° C. or lower and 50 ml of pure water was slowly added. Further, 150 ml of dichloromethane was added, and the organic layer was washed with pure water and saturated aqueous sodium hydrogen carbonate 5% hydrochloric acid, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 5.5 g of the objective compound represented by formula (4).
撹拌装置、冷却器、及び温度計を備えた反応容器に式（４）で表される化合物５ｇ、４−（２−メタクリロイルオキシエチル）フェノール ３．２ｇ（１６ミリモル）、トリフェニルホスフィン ５ｇ（１８ミリモル）、ジクロロメタン ５０ｍｌを仕込み、反応容器を５℃に冷却した。その後、ＤＩＡＤ ３．４ｇ（１７．２ミリモル）を滴下した。滴下終了後、室温で５時間撹拌して反応を終了させた。反応終了後、ジクロロメタン ２００ｍｌを加え、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、シリカゲルカラムクロマトグラフィーによる精製により式（５）で表される化合物４ｇを得た。
In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 5 g of the compound represented by the formula (4), 3.2 g (16 mmol) of 4- (2-methacryloyloxyethyl) phenol, 5 g of triphenylphosphine (18 Mmol) and 50 ml of dichloromethane, and the reaction vessel was cooled to 5 ° C. Thereafter, 3.4 g (17.2 mmol) of DIAD was added dropwise. After completion of the dropwise addition, the reaction was terminated by stirring at room temperature for 5 hours. After completion of the reaction, 200 ml of dichloromethane was added, and the organic layer was washed with pure water and saturated brine. After distilling off the solvent, 4 g of the compound represented by the formula (5) was obtained by purification by silica gel column chromatography.
（物性値）
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ： １．９３（ｓ，３Ｈ），２．１１（ｓ，３Ｈ），２．９２（ｔ，２Ｈ），４．３０−４．３３（ｍ，６Ｈ），５．５４−５．５６（ｍ，１Ｈ），５．８３−５．８４（ｍ，１Ｈ），６．０８（ｓ，１Ｈ），６．４３（ｓ，１Ｈ），６．８９−６．９１（ｍ，２Ｈ），７．００−７．０４（ｍ，２Ｈ），７．１６−７．２６（ｍ，４Ｈ），７．３６−７．３８（ｍ，１Ｈ），７．６８−７．６９（ｍ，１Ｈ），７．８９（ｄ，１Ｈ），８．０２（ｄ，１Ｈ），８．１９−８．２２（ｍ，１Ｈ），８．７８（ｓ，１Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１８．３，１８．４，３４．２，６５．４，６６．５，６７．０，１１４．７，１１５．４，１１８．６，１２２．３，１２２．５，１２５．５，１２６．２，１２６．７，１２７．８，１２８．１，１２９．９，１３０．５，１３１．０，１３１．６，１３５．６，１４４．７，１５０．７，１５６．４，１５７．３，１６５．２，１６５．７
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：１７６０，１６５２−１６２２，８０９ｃｍ−１
融点：１９６℃
（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６−ベンジルオキシ−２−ナフトエ酸 ６．５ｇ（２３．５ミリモル）、４−（２−ターシャリーブトキシエチルオキシ）フェノール４．５ｇ（２１．４ミリモル）、ジメチルアミノピリジン １５０ｍｇ、ジクロロメタン ５０ｍｌを仕込み、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 ３．３ｇ（２６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１５０ｍｌを加え、５％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、２倍量（重量比）のシリカゲルを用いたカラムクロマトグラフィーにより精製を行い式（６）で表される化合物６．５ｇを得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 1.93 (s, 3H), 2.11 (s, 3H), 2.92 (t, 2H), 4.30-4.33 (m, 6H), 5.54-5.56 (m, 1H), 5.83-5.84 (m, 1H), 6.08 (s, 1H), 6.43 (s, 1H), 6.89 -6.91 (m, 2H), 7.00-7.04 (m, 2H), 7.16-7.26 (m, 4H), 7.36-7.38 (m, 1H), 7 68-7.69 (m, 1H), 7.89 (d, 1H), 8.02 (d, 1H), 8.19-8.22 (m, 1H), 8.78 (s, 1H) )
13 C-NMR (solvent: deuterated chloroform): δ: 18.3, 18.4, 34.2, 65.4, 66.5, 67.0, 114.7, 115.4, 118.6, 122 3,122.5,125.5,126.2,126.7,127.8,128.1,129.9,130.5,131.0,131.6,135.6,144.7 , 150.7, 156.4, 157.3, 165.2, 165.7
Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622, 809 cm −1
Melting point: 196 ° C
(Example 2)
In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 6.5 g (23.5 mmol) of 6-benzyloxy-2-naphthoic acid, 4.5 g of 4- (2-tertiarybutoxyethyloxy) phenol ( 21.4 mmol), 150 mg of dimethylaminopyridine, and 50 ml of dichloromethane were kept in an ice-cooled bath at 5 ° C. or lower, and 3.3 g (26 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 150 ml of dichloromethane was added to the filtrate, washed with a 5% 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, the residue was purified by column chromatography using a double amount (weight ratio) of silica gel to obtain 6.5 g of a compound represented by the formula (6).
次いで撹拌器を備えたオートクレーブ容器に、式（６）で表される化合物６．５ｇ、テトラヒドロフラン（ＴＨＦ） １００ｍｌ、パラジウムカーボン １００ｍｇを仕込み、水素で反応容器を加圧し５０℃で５時間反応させた。反応終了後、ろ過によりパラジウムカーボンをろ別したのち、アルミナカラムで精製を行い式（７）で表される化合物５ｇを得た。 Next, an autoclave vessel equipped with a stirrer was charged with 6.5 g of the compound represented by the formula (6), 100 ml of tetrahydrofuran (THF), and 100 mg of palladium carbon, and the reaction vessel was pressurized with hydrogen and reacted at 50 ° C. for 5 hours. . After completion of the reaction, palladium carbon was filtered off and purified with an alumina column to obtain 5 g of a compound represented by the formula (7).
次いで撹拌装置、冷却器、及び温度計を備えた反応容器に式（７）で表される化合物 ５．０ｇ（１３ミリモル）、メタクリル酸１．７ｇ（２０ミリモル）、ジメチルアミノピリジン １００ｍｇ、ジクロロメタン ５０ｍｌを仕込み、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 ２．０ｇ（１６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１５０ｍｌを加え、５％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、２倍量（重量比）のシリカゲルを用いたカラムクロマトグラフィーにより精製を行い式（８）で表される化合物３．５ｇを得た。 Next, 5.0 g (13 mmol) of the compound represented by the formula (7), 1.7 g (20 mmol) of methacrylic acid, 100 mg of dimethylaminopyridine, and 50 ml of dichloromethane in a reaction vessel equipped with a stirrer, a cooler, and a thermometer. The reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath, and 2.0 g (16 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 150 ml of dichloromethane was added to the filtrate, washed with a 5% 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, the residue was purified by column chromatography using a double amount (weight ratio) of silica gel to obtain 3.5 g of a compound represented by the formula (8).
撹拌装置、冷却器及び温度計を備えた反応容器に、上記式（８）で表される化合物３．５ｇ、ジクロロメタン ２０ｍｌを仕込み、氷冷バスにて５℃以下に反応容器を保ち、トリフルオロ酢酸 ２５ｍｌをゆっくり滴下した。滴下終了後、反応容器を室温に戻し１時間反応させた。反応終了後、反応液を１０℃以下に冷却し純水５０ｍｌをゆっくり加えた。更にジクロロメタン１５０ｍｌを加え、有機層を純水、飽和炭酸水素ナトリウム５％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、式（４）で表される化合物３．２ｇを得た。 A reaction vessel equipped with a stirrer, a cooler, and a thermometer was charged with 3.5 g of the compound represented by the above formula (8) and 20 ml of dichloromethane, and the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath. 25 ml of acetic acid was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 1 hour. After completion of the reaction, the reaction solution was cooled to 10 ° C. or lower and 50 ml of pure water was slowly added. Further, 150 ml of dichloromethane was added, and the organic layer was washed with pure water and saturated aqueous sodium hydrogen carbonate 5% hydrochloric acid, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 3.2 g of a compound represented by the formula (4).
次いで、撹拌装置、冷却器、及び温度計を備えた反応容器に式（９）で表される化合物３．２ｇ、４−（２−メタクリロイルオキシエチル）フェノール １．８ｇ（１６ミリモル）、トリフェニルホスフィン ２．５ｇ（１０ミリモル）、ジクロロメタン ５０ｍｌを仕込み、反応容器を５℃に冷却した。その後、ＤＩＡＤ ２．０ｇ（１７．２ミリモル）を滴下した。滴下終了後、室温で５時間撹拌して反応を終了させた。反応終了後、ジクロロメタン ２００ｍｌを加え、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、シリカゲルカラムクロマトグラフィーによる精製により式（１０）で表される化合物４ｇを得た。 Then, 3.2 g of the compound represented by the formula (9), 1.8 g (16 mmol) of 4- (2-methacryloyloxyethyl) phenol, triphenyl in a reaction vessel equipped with a stirrer, a cooler, and a thermometer. 2.5 g (10 mmol) of phosphine and 50 ml of dichloromethane were charged, and the reaction vessel was cooled to 5 ° C. Thereafter, 2.0 g (17.2 mmol) of DIAD was added dropwise. After completion of the dropwise addition, the reaction was terminated by stirring at room temperature for 5 hours. After completion of the reaction, 200 ml of dichloromethane was added, and the organic layer was washed with pure water and saturated brine. After distilling off the solvent, 4 g of the compound represented by the formula (10) was obtained by purification by silica gel column chromatography.
（物性値）
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ： １．７７（ｓ，３Ｈ），２．１１（ｓ，３Ｈ），２．９２（ｔ，２Ｈ），４．３０−４．３６（ｍ，６Ｈ），５．５４−５．５６（ｍ，１Ｈ），５．８３−５．８４（ｍ，１Ｈ），６．０９（ｓ，１Ｈ），６．４３（ｓ，１Ｈ），６．８９−６．９３（ｍ，２Ｈ），７．０１−７．０６（ｍ，２Ｈ），７．１２−７．２１（ｍ，４Ｈ），７．３６−７．３８（ｍ，１Ｈ），７．６８−７．６９（ｍ，１Ｈ），７．８９（ｄ，１Ｈ），８．０２（ｄ，１Ｈ），８．２０−８．２２（ｍ，１Ｈ），８．７８（ｓ，１Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１８．３，１８．４，３４．２，６５．４，６６．４，６６．９，１１４．６，１１５．４，１１８．６，１２２．３，１２２．５，１２５．５，１２６．２，１２６．６，１２７．８，１２８．０，１２９．９，１３０．４，１３１．０，１３１．６，１３５．６，１３６．３，１４４．７，１５０．７，１５６．４，１５７．３，１６５．２，１６５．７
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：１７６０，１６５２−１６２２，８０９ｃｍ−１
融点：１４０℃
（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２−（４−ブロモフェノキシ）テトラヒドロピラン ４０ｇ（１５５ミリモル）、４−ヒドロキシフェニルホウ酸 ２１ｇ（１５５ミリモル）、炭酸カリウム ３２ｇ（２３２ミリモル）、テトラキストリフェニルホスフィンパラジウム １．８ｇ、テトラヒドロフラン２００ｍｌ、純水１００ｍｌを仕込み、７０℃で５時間反応させた。反応終了後、冷却し、１０％塩酸を加えた後、酢酸エチルにより目的物を抽出した。有機層を水、飽和食塩水で洗浄し、溶媒を留去した。その後、トルエンによる分散洗浄、アルミナカラムによる精製を行い式（１１）で表される化合物 ２７ｇを得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 1.77 (s, 3H), 2.11 (s, 3H), 2.92 (t, 2H), 4.30-4.36 (m, 6H), 5.54-5.56 (m, 1H), 5.83-5.84 (m, 1H), 6.09 (s, 1H), 6.43 (s, 1H), 6.89 -6.93 (m, 2H), 7.01-7.06 (m, 2H), 7.12-7.21 (m, 4H), 7.36-7.38 (m, 1H), 7 68-7.69 (m, 1H), 7.89 (d, 1H), 8.02 (d, 1H), 8.20-8.22 (m, 1H), 8.78 (s, 1H) )
13 C-NMR (solvent: deuterated chloroform): δ: 18.3, 18.4, 34.2, 65.4, 66.4, 66.9, 114.6, 115.4, 118.6, 122 .3,122.5,125.5,126.2,126.6,127.8,128.0,129.9,130.4,131.0,131.6,135.6,136.3 , 144.7, 150.7, 156.4, 157.3, 165.2, 165.7
Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622, 809 cm −1
Melting point: 140 ° C
(Example 3)
In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 40 g (155 mmol) of 2- (4-bromophenoxy) tetrahydropyran, 21 g (155 mmol) of 4-hydroxyphenylboric acid, 32 g (232 mmol) of potassium carbonate Then, 1.8 g of tetrakistriphenylphosphine palladium, 200 ml of tetrahydrofuran, and 100 ml of pure water were charged and reacted at 70 ° C. for 5 hours. After completion of the reaction, the mixture was cooled, 10% hydrochloric acid was added, and the target product was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and the solvent was distilled off. Thereafter, dispersion washing with toluene and purification with an alumina column were performed to obtain 27 g of a compound represented by the formula (11).
次いで撹拌装置、冷却器及び温度計を備えた反応容器に、上記式（１１）で表される化合物１５ｇ（５５ミリモル）、メタクリル酸 ７ｇ（８３ミリモル）、ジメチルアミノピリジン ４００ｍｇ、ジクロロメタン １５０ｍｌを仕込み、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 ８．３ｇ（６６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１５０ｍｌを加え、５％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、２倍量（重量比）のアルミナカラムにより精製を行い、ジクロロメタンとメタノールの混合溶液による分散洗浄により式（１２）で表される化合物１８ｇを得た。 Next, a reaction vessel equipped with a stirrer, a cooler and a thermometer was charged with 15 g (55 mmol) of the compound represented by the above formula (11), 7 g (83 mmol) of methacrylic acid, 400 mg of dimethylaminopyridine, and 150 ml of dichloromethane, The reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath, and 8.3 g (66 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 150 ml of dichloromethane was added to the filtrate, washed with a 5% 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 with a double amount (weight ratio) alumina column, and 18 g of the compound represented by the formula (12) was obtained by dispersion washing with a mixed solution of dichloromethane and methanol.
更に撹拌装置、温度計を備えた反応容器に、上記式（１２）で表される化合物１８ｇ、ＴＨＦ １００ｍｌを仕込み、メタノール溶液１０ｍｌと塩酸１ｍｌの混合溶液をゆっくり滴下した。滴下終了後、更に２時間させた。反応終了後、反応液に酢酸エチル２００ｍｌを加え有機層を純水、飽和炭酸水素ナトリウム５％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、式（１３）で表される化合物１１ｇを得た。 Furthermore, 18 g of the compound represented by the above formula (12) and 100 ml of THF were charged into a reaction vessel equipped with a stirrer and a thermometer, and a mixed solution of 10 ml of methanol solution and 1 ml of hydrochloric acid was slowly added dropwise. After completion of dropping, the reaction was further continued for 2 hours. After completion of the reaction, 200 ml of ethyl acetate was added to the reaction solution, and the organic layer was washed with pure water and saturated aqueous sodium hydrogen carbonate 5% hydrochloric acid, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 11 g of a compound represented by the formula (13).
撹拌装置、冷却器、及び温度計を備えた反応容器に式（１３）で表される化合物３ｇ、３−（４−（３−アクリロイルオキシプロピルオキシ）フェニル）プロピオン酸 ３ｇ（１１ミリモル）、ジメチルアミノピリジン １００ｍｇ、ジクロロメタン ５０ｍｌを仕込み、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 １．７ｇ（１３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１５０ｍｌを加え、５％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、２倍量（重量比）のシリカゲルを用いたカラムクロマトグラフィーにより精製を行い式（１４）で表される化合物を２ｇ得た。 In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 3 g of the compound represented by the formula (13), 3 g (11 mmol) of 3- (4- (3-acryloyloxypropyloxy) phenyl) propionic acid, dimethyl Aminopyridine 100 mg and dichloromethane 50 ml were charged, and the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath, and 1.7 g (13 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 150 ml of dichloromethane was added to the filtrate, washed with a 5% 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, the residue was purified by column chromatography using a double amount (weight ratio) of silica gel to obtain 2 g of the compound represented by the formula (14).
（物性値）
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ： ２．０４（ｓ，３Ｈ），２．０８−２．１７（ｍ，２Ｈ），２．８５（ｔ，２Ｈ），３．０３（ｔ，２Ｈ），４．０２−４．０５（ｍ，２Ｈ），４．３５−４．３８（ｍ，２Ｈ），５．７７−５．８４（ｍ，２Ｈ），６．０９−６．１７（ｍ，１Ｈ），６．３３−６．４４（ｍ，２Ｈ），６．８２−６．９１（ｄ，２Ｈ），７．０５−７．１７（ｄ，２Ｈ），７．１９−７．２８（ｍ，４Ｈ），７．５２−７．６１（ｍ，４Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１８．４，２８．６，３０．０，３６．２，６１．３，６４．２，１１４．５，１２１．８，１２１．９，１２７．４，１２８．０，１２８．３，１２９．４，１３０．８，１３２．２，１３５．７，１３７．９，１３８．０，１５０．０，１５０．３，１５７．３，１６５．８，１６６．１，１７１．５
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：１７６０，１６５２−１６２２，８０９ｃｍ−１
融点：１１７℃
（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式（１３）で表される化合物２．４ｇ、３−（４−（２−アクリロイルオキシエチル）フェニル）プロピオン酸 ２．３ｇ（９ミリモル）、ジメチルアミノピリジン ７０ｍｇ、ジクロロメタン ５０ｍｌを仕込み、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 １．４ｇ（１１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１５０ｍｌを加え、５％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、２倍量（重量比）のシリカゲルを用いたカラムクロマトグラフィーにより精製を行い式（１５）で表される化合物を１．８ｇ得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 2.04 (s, 3H), 2.08-2.17 (m, 2H), 2.85 (t, 2H), 3.03 (t, 2H), 4.02-4.05 (m, 2H), 4.35-4.38 (m, 2H), 5.77-5.84 (m, 2H), 6.09-6.17 ( m, 1H), 6.33-6.44 (m, 2H), 6.82-6.91 (d, 2H), 7.05-7.17 (d, 2H), 7.19-7. 28 (m, 4H), 7.52-7.61 (m, 4H)
13 C-NMR (solvent: deuterated chloroform): δ: 18.4, 28.6, 30.0, 36.2, 61.3, 64.2, 114.5, 121.8, 121.9, 127 4, 128.0, 128.3, 129.4, 130.8, 132.2, 135.7, 137.9, 138.0, 150.0, 150.3, 157.3, 165.8 , 166.1, 171.5
Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622, 809 cm −1
Melting point: 117 ° C
Example 4
In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 2.4 g of the compound represented by the formula (13), 2.3 g of 3- (4- (2-acryloyloxyethyl) phenyl) propionic acid (9 mmol) ), 70 mg of dimethylaminopyridine and 50 ml of dichloromethane were charged, the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath, and 1.4 g (11 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 150 ml of dichloromethane was added to the filtrate, washed with a 5% 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, the residue was purified by column chromatography using a double amount (weight ratio) of silica gel to obtain 1.8 g of the compound represented by the formula (15).
（物性値）
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ： ２．０４（ｓ，３Ｈ），２．８４−３．０７（ｍ，６Ｈ），４．３１（ｔ，２Ｈ），５．７６−５．８１（ｍ，２Ｈ），６．０７−６．１６（ｍ，１Ｈ），６．３１−６．４２（ｍ，２Ｈ），７．０３−７．１０（ｍ，２Ｈ），７．１２−７．２６（ｍ，６Ｈ），７．５２−７．６２（ｍ，４Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１８．３，３０．４，３４．５，３５．８，６４．９，１２１．７，１２１．８，１２７．３，１２８．０，１２８．３，１２８．４，１２９．０，１３０．７，１３５．７，１３５．８，１３７．８，１３８．０，１３８．３，１４９．９，１５０．３，１６５．７，１６６．０，１７１．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：１７６０，１６５２−１６２２，８０９ｃｍ−１
融点：１０１℃
（実施例５）
撹拌装置、冷却器、及び温度計を備えた反応容器に式（１３）で表される化合物３．８ｇ、３−（４−アクリロイルオキシメチルフェニル）プロピオン酸 ３．５ｇ（１５ミリモル）、ジメチルアミノピリジン １００ｍｇ、ジクロロメタン ５０ｍｌを仕込み、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 ２．３ｇ（１８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１５０ｍｌを加え、５％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、２倍量（重量比）のシリカゲルカラムにより精製を行い式（１６）で表される化合物を４ｇ得た。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 2.04 (s, 3H), 2.84-3.07 (m, 6H), 4.31 (t, 2H), 5.76-5. 81 (m, 2H), 6.07-6.16 (m, 1H), 6.31-6.42 (m, 2H), 7.03-7.10 (m, 2H), 7.12- 7.26 (m, 6H), 7.52-7.62 (m, 4H)
13 C-NMR (solvent: deuterated chloroform): δ: 18.3, 30.4, 34.5, 35.8, 64.9, 121.7, 121.8, 127.3, 128.0, 128 .3,128.4,129.0,130.7,135.7,135.8,137.8,138.0,138.3,149.9,150.3,165.7,166.0 , 171.3
Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622, 809 cm −1
Melting point: 101 ° C
(Example 5)
In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 3.8 g of the compound represented by the formula (13), 3.5 g (15 mmol) of 3- (4-acryloyloxymethylphenyl) propionic acid, dimethylamino 100 mg of pyridine and 50 ml of dichloromethane were charged, and the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath, and 2.3 g (18 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 150 ml of dichloromethane was added to the filtrate, washed with a 5% 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 with a double amount (weight ratio) silica gel column to obtain 4 g of a compound represented by the formula (16).
（物性値）
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ： ２．０６（ｓ，３Ｈ），２．９３（ｔ，２Ｈ），４．３４−４．４７（ｍ，４Ｈ），５．７８−５．８５（ｍ，２Ｈ），６．０８−６．１５（ｍ，１Ｈ），６．３７−６．４２（ｍ，２Ｈ），６．９２−６．９５（ｍ，２Ｈ），７．１５−７．３２（ｍ，６Ｈ），７．６８−７．７９（ｍ，４Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１８．４，３４．２，６５．２，６６．４，６６．５，１０６．６，１１４．７，１１９．４，１２１．９，１２５．５，１２５．９，１２７．３，１２８．１，１２８．４，１２９．２，１３０．３，１３０．７，１３３．６，１５６．７，１５７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：１７６０，１６５２−１６２２，８０９ｃｍ−１
融点：１１２℃
（実施例６）
以下に示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: 2.06 (s, 3H), 2.93 (t, 2H), 4.34-4.47 (m, 4H), 5.78-5. 85 (m, 2H), 6.08-6.15 (m, 1H), 6.37-6.42 (m, 2H), 6.92-6.95 (m, 2H), 7.15- 7.32 (m, 6H), 7.68-7.79 (m, 4H)
13 C-NMR (solvent: deuterated chloroform): δ: 18.4, 34.2, 65.2, 66.4, 66.5, 106.6, 114.7, 119.4, 121.9, 125 5, 125.9, 127.3, 128.1, 128.4, 129.2, 130.3, 130.7, 133.6, 156.7, 157.3
Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622, 809 cm −1
Melting point: 112 ° C
(Example 6)
A polymerizable liquid crystal composition (Composition 1) having the following composition was prepared.
重合性液晶組成物は、良好な保存安定性を有し、広い温度範囲でネマチック液晶相を示した。この重合性液晶組成物に光重合開始剤 イルガキュアー９０７（チバスペシャリティーケミカル社製）を３％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のシクロヘキサノン溶液を、ポリイミド付きガラスにスピンコートし、１００℃で５分乾燥させた後に室温で放冷し、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。この光学異方体の表面硬度（ＪＩＳ−Ｓ−Ｋ−５４００による）はＨであった。得られた光学異方体の加熱前の位相差を１００％としたとき、２４０℃、１時間加熱後の位相差は９０％であり、位相差減少率は１０％だった。
（比較例１）
以下に示す組成の重合性液晶組成物（組成物３）を調製した。
The polymerizable liquid crystal composition had good storage stability and exhibited a nematic liquid crystal phase over a wide temperature range. A photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to this polymerizable liquid crystal composition at 3% to prepare a polymerizable liquid crystal composition (Composition 2). The cyclohexanone solution of composition 2 was spin-coated on a glass with polyimide, dried at 100 ° C. for 5 minutes, allowed to cool at room temperature, and irradiated with 4 mW / cm 2 ultraviolet rays for 120 seconds using a high-pressure mercury lamp. As a result, the composition 2 was polymerized while maintaining a uniform alignment state, and an optically anisotropic body was obtained. The surface hardness (according to JIS-SK-5400) of this optical anisotropic body was H. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 1 hour was 90%, and the retardation reduction rate was 10%.
(Comparative Example 1)
A polymerizable liquid crystal composition (Composition 3) having the following composition was prepared.
重合性液晶組成物は、ネマチック液晶相を示したが、保存安定性が悪く室温１時間で結晶が析出した。
（比較例２）
以下に示す組成の重合性液晶組成物（組成物４）を調製した。
The polymerizable liquid crystal composition showed a nematic liquid crystal phase, but the storage stability was poor and crystals were precipitated at room temperature for 1 hour.
(Comparative Example 2)
A polymerizable liquid crystal composition (Composition 4) having the following composition was prepared.
重合性液晶組成物は、良好な保存安定性を有し、ネマチック液晶相を示した。この組成物に光重合開始剤 イルガキュアー９０７（チバスペシャリティーケミカル社製）を３％添加して重合性液晶組成物（組成物５）を調製した。この組成物５を用い実施例６と同様な方法により光学異方体を得た。得られた光学異方体は、組成物５が均一な配向状態を保ったまま重合していることが確認できた。この光学異方体の表面硬度（ＪＩＳ−Ｓ−Ｋ−５４００による）は２Ｂであった。得られた光学異方体の加熱前の位相差を１００％としたとき、２４０℃、１時間加熱後の位相差は７５％であり、位相差減少率は２５％だった。 The polymerizable liquid crystal composition had good storage stability and exhibited a nematic liquid crystal phase. A photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to this composition at 3% to prepare a polymerizable liquid crystal composition (Composition 5). Using this composition 5, an optical anisotropic body was obtained in the same manner as in Example 6. It was confirmed that the obtained optical anisotropic body was polymerized while the composition 5 maintained a uniform alignment state. The surface hardness (according to JIS-S-K-5400) of this optical anisotropic body was 2B. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 1 hour was 75%, and the phase difference reduction rate was 25%.
このように、比較例２の組成物５は、本願発明の組成物２と比較して、作製できる光学異方体の位相差減少率が大きく、耐熱性に劣ることが明らかである。又、表面硬度も２Ｂと不十分なものであった。
（実施例７）
下記に示す化合物を含有した液晶組成物ＬＣ−１を調製した。構成する化合物及び含有する比率は以下の通りである。
Thus, it is clear that the composition 5 of Comparative Example 2 has a larger retardation reduction rate of the optically anisotropic body that can be produced and is inferior in heat resistance than the composition 2 of the present invention. Also, the surface hardness was 2B, which was insufficient.
(Example 7)
A liquid crystal composition LC-1 containing the compound shown below was prepared. The constituent compounds and the ratios contained are as follows.
９９．７％の上記液晶組成物ＬＣ−１及び実施例５で合成した式（１６）で表される化合物０．３％からなる重合性液晶組成物を調製した。この重合性液晶組成物は−１０℃で１週間保管しても析出は見られず、保存安定性に優れていた。この組成物を３．５μｍのポリイミド付きガラスセル注入し、紫外線を照射後垂直配向性液晶表示素子を得た。得られた垂直配向性液晶表示素子は、液晶分子が垂直方向から傾いた上体でプレチルト角を固定化されていることが確認できた。この垂直配向性液晶表示素子から液晶組成物を抽出し、高速液体クロマトグラフィーでモノマー残留量の測定を行ったが、検出限界以下であった。
（垂直配向性液晶表示素子の作成方法）
ＣＬＣ−Ａをセルギャップ３．５μｍでホメオトロピック配向を誘起するポリイミド配向膜を塗布したＩＴＯ付きセルに真空注入法で注入した。このセルのプレチルト角を測定した後、周波数１ｋＨｚで１．８Ｖの矩形波を印加しながら、３００ｎｍ以下の紫外線をカットするフィルターを介して、高圧水銀灯により液晶セルに紫外線を照射した。セル表面の照射強度が１０ｍＷ／ｃｍ２となるように調整して６００秒間照射して、重合性液晶組成物中の重合性化合物を重合させた垂直配向性液晶表示素子を得た。
（ＵＶ硬化後のモノマー残存量の測定方法）
液晶セルに液晶組成物を注入後、ＵＶを照射し重合性化合物を重合させる。その後、液晶セルを分解し、液晶材料、重合物、未重合の重合性化合物を含む溶出成分のアセトニトリル溶液を得る。これを高速液体クロマトグラフィー（検出器：ＵＶ、カラム：逆相非極性カラム、展開溶媒：アセトニトリル）により、各成分のピーク面積を測定する。指標とする液晶材料のピーク面積と未重合の重合性化合物のピーク面積比から、残存する重合性化合物の量を決定した。この値と当初添加した重合性化合物の量からモノマー残存量を決定した。なお、重合性化合物の残存量の検出限界は１００ｐｐｍであった。（比較例３）
実施例７において式（１６）で表される化合物に換えて一般式（Ａ）
A polymerizable liquid crystal composition comprising 99.7% of the above liquid crystal composition LC-1 and 0.3% of the compound represented by the formula (16) synthesized in Example 5 was prepared. This polymerizable liquid crystal composition was excellent in storage stability with no precipitation even when stored at −10 ° C. for 1 week. This composition was injected into a 3.5 μm polyimide-coated glass cell and irradiated with ultraviolet rays to obtain a vertically aligned liquid crystal display element. It was confirmed that the obtained vertical alignment liquid crystal display element had a fixed pretilt angle with the upper body in which liquid crystal molecules were tilted from the vertical direction. A liquid crystal composition was extracted from the vertically aligned liquid crystal display element, and the residual monomer amount was measured by high performance liquid chromatography, which was below the detection limit.
(Method for producing vertical alignment liquid crystal display element)
CLC-A was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of the cell, the liquid crystal cell was irradiated with ultraviolet rays by a high pressure mercury lamp through a filter that cuts ultraviolet rays of 300 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 kHz. The cell surface was adjusted to have an irradiation intensity of 10 mW / cm 2 and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable liquid crystal composition was polymerized.
(Measurement method of residual amount of monomer after UV curing)
After injecting the liquid crystal composition into the liquid crystal cell, UV is irradiated to polymerize the polymerizable compound. Thereafter, the liquid crystal cell is disassembled to obtain an acetonitrile solution of an elution component containing a liquid crystal material, a polymer, and an unpolymerized polymerizable compound. The peak area of each component is measured by high performance liquid chromatography (detector: UV, column: reverse phase nonpolar column, developing solvent: acetonitrile). The amount of the remaining polymerizable compound was determined from the peak area ratio of the liquid crystal material as an index and the peak area ratio of the unpolymerized polymerizable compound. The residual monomer amount was determined from this value and the amount of the polymerizable compound initially added. The detection limit of the remaining amount of the polymerizable compound was 100 ppm. (Comparative Example 3)
Instead of the compound represented by the formula (16) in Example 7, the formula (A)
で示される化合物を使用する以外は同様にして重合性液晶組成物を調製し、更に垂直配向性液晶表示素子を作成した後にモノマー残存量の測定を行った。この重合性液晶組成物は−１０℃で１週間保管することにより結晶の析出が起こった。垂直配向性液晶表示素子のプレチルト角は、傾きは小さいが液晶分子が垂直方向から傾いた状態でプレチルト角を固定化されていた。また、モノマー残存量、検出限界以下にはなっていないことが分かり、一般式（Ａ）で表される重合性化合物は重合速度が遅いことがわかった。 A polymerizable liquid crystal composition was prepared in the same manner except that the compound represented by the formula (1) was used, and a monomer alignment amount was measured after a vertical alignment liquid crystal display device was prepared. The polymerizable liquid crystal composition was crystallized by storing at -10 ° C for 1 week. The pretilt angle of the vertically aligned liquid crystal display element is small, but the pretilt angle is fixed in a state where the liquid crystal molecules are tilted from the vertical direction. Further, it was found that the residual monomer amount was not below the detection limit, and it was found that the polymerizable compound represented by the general formula (A) has a low polymerization rate.
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|---|---|---|---|---|
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002220421A (en) * | 2000-01-21 | 2002-08-09 | Dainippon Ink & Chem Inc | Polymerizable composition exhibiting liquid crystalline phase and optically anisotropic body using the same |
| JP2004175728A (en) * | 2002-11-27 | 2004-06-24 | Chisso Corp | LIQUID-CRYSTALLINE alpha-TRIFLUOROMETHYLACRYLATE DERIVATIVE AND ITS POLYMER |
| JP2004231638A (en) * | 2003-01-06 | 2004-08-19 | Chisso Corp | Polymerizable compound and its polymer |
| JP2005023019A (en) * | 2003-07-02 | 2005-01-27 | Chisso Corp | Liquid crystalline compound having optically active group and polymer thereof |
| JP2005035985A (en) * | 2003-06-23 | 2005-02-10 | Chisso Corp | Liquid crystalline compound, liquid crystal composition and polymer of them |
| JP2005179557A (en) * | 2003-12-22 | 2005-07-07 | Chisso Corp | Low refractive index anisotropic compound, its composition, polymer or polymer composition of them |
| US20100124623A1 (en) * | 2008-11-14 | 2010-05-20 | Chi Mei Optoelectronics Corp. | Liquid crystal composition for use in liquid crystal display |
| JP2010241814A (en) * | 2003-01-06 | 2010-10-28 | Chisso Corp | Polymerizable compound and polymer thereof |
| JP2011084477A (en) * | 2009-10-13 | 2011-04-28 | Dic Corp | Polymerizable naphthalene compound |
| WO2011062017A1 (en) * | 2009-11-18 | 2011-05-26 | 株式会社Adeka | Liquid crystal composition comprising polymerizable compound, and liquid crystal display element using said liquid crystal composition |
| JP2011162571A (en) * | 2010-02-04 | 2011-08-25 | Dic Corp | Liquid crystal composition containing polymerizable compound and liquid crystal display element using the same |
-
2012
- 2012-03-01 JP JP2012045324A patent/JP6031781B2/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002220421A (en) * | 2000-01-21 | 2002-08-09 | Dainippon Ink & Chem Inc | Polymerizable composition exhibiting liquid crystalline phase and optically anisotropic body using the same |
| JP2004175728A (en) * | 2002-11-27 | 2004-06-24 | Chisso Corp | LIQUID-CRYSTALLINE alpha-TRIFLUOROMETHYLACRYLATE DERIVATIVE AND ITS POLYMER |
| JP2004231638A (en) * | 2003-01-06 | 2004-08-19 | Chisso Corp | Polymerizable compound and its polymer |
| JP2010241814A (en) * | 2003-01-06 | 2010-10-28 | Chisso Corp | Polymerizable compound and polymer thereof |
| JP2005035985A (en) * | 2003-06-23 | 2005-02-10 | Chisso Corp | Liquid crystalline compound, liquid crystal composition and polymer of them |
| JP2005023019A (en) * | 2003-07-02 | 2005-01-27 | Chisso Corp | Liquid crystalline compound having optically active group and polymer thereof |
| JP2005179557A (en) * | 2003-12-22 | 2005-07-07 | Chisso Corp | Low refractive index anisotropic compound, its composition, polymer or polymer composition of them |
| US20100124623A1 (en) * | 2008-11-14 | 2010-05-20 | Chi Mei Optoelectronics Corp. | Liquid crystal composition for use in liquid crystal display |
| JP2011084477A (en) * | 2009-10-13 | 2011-04-28 | Dic Corp | Polymerizable naphthalene compound |
| WO2011062017A1 (en) * | 2009-11-18 | 2011-05-26 | 株式会社Adeka | Liquid crystal composition comprising polymerizable compound, and liquid crystal display element using said liquid crystal composition |
| JP2011162571A (en) * | 2010-02-04 | 2011-08-25 | Dic Corp | Liquid crystal composition containing polymerizable compound and liquid crystal display element using the same |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014148472A1 (en) * | 2013-03-21 | 2014-09-25 | Dic株式会社 | Polymerizable compound-containing liquid crystal composition and liquid crystal display element using same |
| US9725651B2 (en) | 2013-03-21 | 2017-08-08 | Dic Corporation | Polymerizable compound-containing liquid crystal composition and liquid crystal display element using same |
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| JP2016017034A (en) * | 2014-07-04 | 2016-02-01 | Dic株式会社 | Polymerizable compound and optical anisotropic body |
| US10113115B2 (en) | 2014-09-05 | 2018-10-30 | DIC Corporation (Tokyo) | Nematic liquid crystal composition and liquid crystal display device using the same |
| US10323186B2 (en) | 2014-12-25 | 2019-06-18 | Dic Corporation | Nematic liquid crystal composition and liquid crystal display element using the same |
| US20190025656A1 (en) * | 2016-02-02 | 2019-01-24 | Dic Corporation | Liquid crystal display element and method for producing same |
| WO2017134841A1 (en) * | 2016-02-02 | 2017-08-10 | Dic株式会社 | Liquid crystal display element and method for producing same |
| KR102313718B1 (en) * | 2016-04-27 | 2021-10-18 | 디아이씨 가부시끼가이샤 | Polymerizable compound and liquid crystal composition using same |
| KR20190003459A (en) * | 2016-04-27 | 2019-01-09 | 디아이씨 가부시끼가이샤 | Polymerizable compound and liquid crystal composition using same |
| US11555152B2 (en) | 2016-04-27 | 2023-01-17 | Dic Corporation | Liquid crystal composition and liquid crystal display element |
| CN108884392A (en) * | 2016-06-17 | 2018-11-23 | Dic株式会社 | Liquid-crystal composition and liquid crystal display element |
| WO2019124345A1 (en) * | 2017-12-22 | 2019-06-27 | Dic株式会社 | Polymerizable liquid crystal composition, liquid crystal display element, and polymerizable compound |
| CN111417700A (en) * | 2017-12-22 | 2020-07-14 | Dic株式会社 | Polymerizable liquid crystal composition, liquid crystal display element, and polymerizable compound |
| CN111417700B (en) * | 2017-12-22 | 2024-01-30 | Dic株式会社 | Polymerizable liquid crystal composition, liquid crystal display element, and polymerizable compound |
| JP2020002065A (en) * | 2018-06-28 | 2020-01-09 | Dic株式会社 | Polymerizable compound and liquid crystal composition and liquid crystal element using the same |
| JPWO2020116555A1 (en) * | 2018-12-06 | 2021-02-15 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
| WO2020116555A1 (en) * | 2018-12-06 | 2020-06-11 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
| WO2023199630A1 (en) * | 2022-04-11 | 2023-10-19 | 住友化学株式会社 | Polymerizable compound and mixed composition |
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