JP5545516B2 - Polymerizable compound - Google Patents
Polymerizable compound Download PDFInfo
- Publication number
- JP5545516B2 JP5545516B2 JP2009220581A JP2009220581A JP5545516B2 JP 5545516 B2 JP5545516 B2 JP 5545516B2 JP 2009220581 A JP2009220581 A JP 2009220581A JP 2009220581 A JP2009220581 A JP 2009220581A JP 5545516 B2 JP5545516 B2 JP 5545516B2
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- JP
- Japan
- Prior art keywords
- group
- coo
- liquid crystal
- oco
- diyl
- 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.)
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- 150000001875 compounds Chemical class 0.000 title claims description 101
- 239000004973 liquid crystal related substance Substances 0.000 claims description 87
- 239000000203 mixture Substances 0.000 claims description 71
- -1 pyridine-2,5-diyl group Chemical group 0.000 claims description 70
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 230000003287 optical effect Effects 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 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 11
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 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
- 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 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- YGGXZTQSGNFKPJ-UHFFFAOYSA-N methyl 2-naphthalen-1-ylacetate Chemical compound C1=CC=C2C(CC(=O)OC)=CC=CC2=C1 YGGXZTQSGNFKPJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 38
- 239000000758 substrate Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 19
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000010409 thin film Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000005886 esterification reaction Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 12
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 11
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000004988 Nematic liquid crystal Substances 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 9
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical class OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- ILYSAKHOYBPSPC-UHFFFAOYSA-N 2-phenylbenzoic acid Chemical class OC(=O)C1=CC=CC=C1C1=CC=CC=C1 ILYSAKHOYBPSPC-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000002585 base Substances 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 150000002921 oxetanes Chemical class 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HTRNHWBOBYFTQF-UHFFFAOYSA-N 4-bromo-2-fluoro-1-phenylbenzene Chemical group FC1=CC(Br)=CC=C1C1=CC=CC=C1 HTRNHWBOBYFTQF-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- AAMNDVXGSYGJHG-UHFFFAOYSA-M C=1(C(=CC=CC1)C(=O)O)C1=CC=CC=C1.[OH-].[Na+] Chemical class C=1(C(=CC=CC1)C(=O)O)C1=CC=CC=C1.[OH-].[Na+] AAMNDVXGSYGJHG-UHFFFAOYSA-M 0.000 description 3
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- APFZZAZXXBWRCP-UHFFFAOYSA-N 6-(4-oxohex-5-enoxy)naphthalene-2-carboxylic acid Chemical compound C(C=C)(=O)CCCOC=1C=C2C=CC(=CC2=CC1)C(=O)O APFZZAZXXBWRCP-UHFFFAOYSA-N 0.000 description 2
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 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
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 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
- 239000000178 monomer Substances 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 238000007699 photoisomerization reaction Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- QSVXXQNLMJMOPL-UHFFFAOYSA-N 1-bromo-2-fluoro-4-phenylbenzene Chemical group C1=C(Br)C(F)=CC(C=2C=CC=CC=2)=C1 QSVXXQNLMJMOPL-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
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical group NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- LDQRPWJIHDBXFV-UHFFFAOYSA-N 3-(4-hydroxyphenoxy)propyl prop-2-enoate Chemical compound OC1=CC=C(OCCCOC(=O)C=C)C=C1 LDQRPWJIHDBXFV-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
- UBHQPRAAGGFDID-UHFFFAOYSA-N 4-(2-prop-2-enoyloxyethoxy)benzoic acid Chemical compound OC(=O)C1=CC=C(OCCOC(=O)C=C)C=C1 UBHQPRAAGGFDID-UHFFFAOYSA-N 0.000 description 1
- AHBWYWGJQFTBRO-UHFFFAOYSA-N 4-(3-prop-2-enoyloxypropoxy)benzoic acid Chemical compound OC(=O)C1=CC=C(OCCCOC(=O)C=C)C=C1 AHBWYWGJQFTBRO-UHFFFAOYSA-N 0.000 description 1
- ARUBXNBYMCVENE-UHFFFAOYSA-N 4-(4-bromophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(Br)C=C1 ARUBXNBYMCVENE-UHFFFAOYSA-N 0.000 description 1
- FLPSQLAEXYKMGQ-UHFFFAOYSA-N 4-(6-prop-2-enoyloxyhexoxy)benzoic acid Chemical compound OC(=O)C1=CC=C(OCCCCCCOC(=O)C=C)C=C1 FLPSQLAEXYKMGQ-UHFFFAOYSA-N 0.000 description 1
- GFBCWCDNXDKFRH-UHFFFAOYSA-N 4-(oxan-2-yloxy)phenol Chemical compound C1=CC(O)=CC=C1OC1OCCCC1 GFBCWCDNXDKFRH-UHFFFAOYSA-N 0.000 description 1
- VWDSGKYABCFREO-UHFFFAOYSA-N 6-(4-hydroxyphenoxy)hexyl prop-2-enoate Chemical compound OC1=CC=C(OCCCCCCOC(=O)C=C)C=C1 VWDSGKYABCFREO-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical compound ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical group C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
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Description
本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液晶デバイスに関する。 The present invention relates to a polymerizable compound, a liquid crystal composition containing the compound, and an optical anisotropic body or liquid crystal device which is a cured product of the liquid crystal composition.
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ィ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ィルムには重合性の液晶組成物の重合物を使用する例が報告されている。光学補償フィ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。 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. Reported an example using a polymer of a polymerizable liquid crystal composition. Optical anisotropic materials used for optical compensation films, etc. are not only optical properties but also important factors such as compound polymerization rate, solubility, melting point, glass transition point, polymer transparency, mechanical strength, surface hardness and heat resistance. It becomes.
重合性の液晶組成物を構成する化合物として従来は、１，４−フェニレン基をエステル結合によって連結した構造を有する化合物（特許文献１参照）や、フルオレン基を有する化合物（特許文献２参照）が提案されている。しかしながら、当該引用文献記載の重合性化合物は溶解性が低い等の問題があった。一方、溶解性を向上させるために桂皮酸構造をとした重合性化合物が開示されているが（特許文献３参照）、光異性化を行わせて配向を乱れさせる目的の化合物であり、熱及び光により容易にシス−トランス異性化を起こすため本目的の位相差の耐熱性及び、表面硬度等の機械的強度が改善されない。光異性化を利用できる重合性化合物であり、熱及び光により耐熱性や機械強度が改善されていない。 Conventionally, as a compound constituting a polymerizable liquid crystal composition, a compound having a structure in which 1,4-phenylene groups are linked by an ester bond (see Patent Document 1) and a compound having a fluorene group (see Patent Document 2) are used. Proposed. However, the polymerizable compound described in the cited document has problems such as low solubility. On the other hand, a polymerizable compound having a cinnamic acid structure in order to improve solubility is disclosed (see Patent Document 3), but is a compound intended to disturb orientation by performing photoisomerization, Since cis-trans isomerization is easily caused by light, the heat resistance of the target phase difference and the mechanical strength such as surface hardness are not improved. It is a polymerizable compound that can utilize photoisomerization, and heat resistance and mechanical strength are not improved by heat and light.
本発明が解決しようとする課題は、重合性の液晶組成物を構成した場合に他の重合性化合物及び液晶化合物との優れた溶解性を有し、前記重合性の液晶組成物を硬化させた場合に優れた耐熱性及び表面硬度を示す重合性化合物を提供することである。更に高分子安定化液晶表示素子に有用な材料を提供することである。 The problem to be solved by the present invention is that when a polymerizable liquid crystal composition is constituted, it has excellent solubility with other polymerizable compounds and liquid crystal compounds, and the polymerizable liquid crystal composition is cured. It is intended to provide a polymerizable compound exhibiting excellent heat resistance and surface hardness in some cases. Furthermore, it is providing the material useful for a polymer stabilization liquid crystal display element.
本願発明者らは重合性化合物における種々の置換基の検討を行った結果、特定の構造を有する重合性化合物が前述の課題を解決できることを見出し本願発明を完成するに至った。 As a result of studying various substituents in the polymerizable compound, the present inventors have found that a polymerizable compound having a specific structure can solve the above-described 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、Ｒ１は以下の式（Ｒ−１）から式（Ｒ−１５）の何れか (Wherein R 1 is any one of the following formulas (R-1) to (R-15):
を表し、Ｘ１、Ｘ２、Ｘ３、Ｘ４、Ｘ５、Ｘ６、Ｘ７及びＸ８は、お互い独立して水素原子、炭素数１〜１２のアルキル基、炭素数１〜１２のハロゲン化アルキル基、炭素数１〜１２のアルコキシ基、炭素数１〜１２のハロゲン化アルコキシ基、ハロゲン、シアノ基、又はニトロ基を表し、Ｓ１は、酸素原子同士が直接結合しないものとしてメチレン基が酸素原子、−ＣＯＯ−、−ＯＣＯ−、又は−ＯＣＯＯ−、−Ｃ≡Ｃ−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、Ｌ１及びＬ２はお互い独立して、単結合、−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−Ｃ２Ｈ４−、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯＣＨ２−、−ＣＨ２ＯＣＯＯ−、−ＣＯ−ＮＲ１１−、−ＮＲ１１−ＣＯ−、−ＳＣＨ２−、−ＣＨ２Ｓ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、―ＣＯＯＣ２Ｈ４−、−ＯＣＯＣ２Ｈ４−、−Ｃ２Ｈ４ＯＣＯ−、−Ｃ２Ｈ４ＣＯＯ−、−ＯＣＯＣＨ２−、−ＣＨ２ＣＯＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−ＣＦ２−、−ＣＦ２Ｏ−、−ＯＣＦ２−、−ＣＦ２ＣＨ２−、−ＣＨ２ＣＦ２−、−ＣＦ２ＣＦ２−又は−Ｃ≡Ｃ−を表し（式中、Ｒ１１は炭素原子１〜４のアルキル基を表す。）、Ｍ１及びＭ２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−ジイル基を表し、Ｍ３は１，４−フェニレン基、１，３，４−ベンゼントリイル基、１，３，５−ベンゼントリイル基、１，３，４，５−ベンゼンテトライル基、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、１，３−ジオキサン−２，５−ジイル基、１，４−シクロヘキシレン基、１，３，５−シクロヘキサントリイル基又は１，３，４−シクロヘキサントリイル基を表し、Ｍ１、Ｍ２及びＭ３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、ハロゲン基、シアノ基、又はニトロ基で置換されていても良く、ｍは１、２又は３を表し、ｎは０、１又は２を表し、ｍ及びｎが２又は３を表す場合、２個あるいは３個存在するＬ１、Ｌ２、Ｍ１及びＭ２は同一であっても異なっていても良く、Ｚは、Ｈ、Ｆ、Ｃｌ、ＣＮ、ＳＣＮ、ＯＣＦ３、又は１〜１２個の炭素原子を有するアルキル基を表し、該アルキル基は酸素原子同士が直接結合しないものとしてメチレン基が酸素原子、硫黄原子、−ＣＯ−、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ、−ＣＨ＝ＣＨ−、又は−Ｃ≡Ｃ−で置換されても良く、又はＺは−Ｌ３−Ｓ２−Ｒ２（式中Ｒ２、Ｓ２及びＬ３はＲ１、Ｓ１及びＬ１と同じ意味を表す。）を表し、ｋは１、２又は３を表すが、ｋが２又は３を表す場合にＺは同一であっても異なっていても良い。）で表される重合性化合物を提供し、当該化合物を構成部材とする液晶組成物、更に、当該液晶組成物を用いた光学異方体、又は液晶液晶表示素子を提供する。 X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. halogenated alkyl group represents an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, halogen, a cyano group, or a nitro group, S 1 is methylene as between oxygen atoms are not linked directly The group represents an oxygen atom, —COO—, —OCO—, —OCOO—, —C≡C—, an alkylene group having 1 to 12 carbon atoms, or a single bond, and L 1 and L 2 are Independently of each other, a single bond, —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —C 2 H 4 —, —COO—, —OCO—, —OCOOCH 2 — , —CH 2 OCOO—, —CO—NR 11 —, —NR 11 —CO—, —SCH 2 —, —CH 2 S—, —CH═CH—COO—, —COO—CH═CH—, —CH═CH—OCO—, —OCO—CH═CH—, —COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - OCOCH 2 -, - CH 2 COO -, - CH = CH -, - CF = CH- , —CH═CF—, —CF 2 —, —CF 2 O—, —OCF 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 — or —C≡C— (Wherein R 11 represents an alkyl group having 1 to 4 carbon atoms), M 1 and M 2 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2. , 5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group Represents tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, M 3 is 1,4-phenylene, 1,3,4-benzenetriyl group, 1,3, 5-benzenetriyl group, 1,3,4,5-benzenetetrayl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, tetrahydronaphthalene- 2,6-diyl group, 1,3-dioxane-2,5-diyl group, 1,4-cyclohexylene group, 1,3,5-cyclohexanetriyl group or 1,3,4-cyclohexanetriyl group And M 1 , M 2 and M 3 are each independently unsubstituted or substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group, or a nitro group, m is Represents 2 or 3, n is 0, 1 or 2, when m and n is 2 or 3, L 1, L 2, M 1 and M 2 that there are two or three in a same Z may represent H, F, Cl, CN, SCN, OCF 3 , or an alkyl group having 1 to 12 carbon atoms, and the alkyl group does not directly bond oxygen atoms to each other. The methylene group may be substituted with an oxygen atom, a sulfur atom, -CO-, -COO-, -OCO-, -OCOO, -CH = CH-, or -C≡C-, or Z is -L 3- S 2 -R 2 (wherein R 2 , S 2 and L 3 represent the same meaning as R 1 , S 1 and L 1 ). ), K represents 1, 2 or 3, but when k represents 2 or 3, Z may be the same or different. ), A liquid crystal composition comprising the compound as a constituent member, and an optical anisotropic body using the liquid crystal composition, or a liquid crystal liquid crystal display element.
本願発明の重合性化合物は、他の重合性化合物及び液晶化合物との優れた溶解性を有することから重合性組成物の構成部材として有用である。又、本願発明の重合性化合物を含有する重合性成物は、硬化速度が速く、且つ液晶相温度範囲が広い。当該重合性組成物を用いた光学異方体は、耐熱性が高く、偏向板、位相差板等の用途に有用であり、また高分子安定化液晶表示素子にも有用である。 The polymerizable compound of the present invention is useful as a component of the polymerizable composition because it has excellent solubility with other polymerizable compounds and liquid crystal compounds. In addition, the polymerizable composition containing the polymerizable compound of the present invention has a high curing rate and a wide liquid crystal phase temperature range. An optical anisotropic body using the polymerizable composition has high heat resistance and is useful for applications such as a deflecting plate and a retardation plate, and also useful for a polymer-stabilized liquid crystal display element.
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.
Ｓ１及びＳ２はお互い独立してスペーサー基又は単結合を表すが、スペーサー基としては、炭素数２〜６のアルキレン基又は単結合が好ましく、該アルキレン基は酸素原子同士が直接結合しないものとして炭素原子が酸素原子、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−に置き換えられても良い。 S 1 and S 2 each independently represent a spacer group or a single bond, and the spacer group is preferably an alkylene group or a single bond having 2 to 6 carbon atoms, and the alkylene group does not directly bond oxygen atoms to each other. The carbon atom may be replaced by an oxygen atom, -COO-, -OCO-, -OCOO-.
Ｌ１、Ｌ２及びＬ３はお互い独立して、単結合、−ＯＣＨ２−、−Ｃ２Ｈ４−、−ＣＨ２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯＣＨ２−、−ＣＨ２ＯＣＯＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＯＣ−ＣＨ＝ＣＨ−、−ＣＯＯＣ２Ｈ４−、−ＯＣＯＣ２Ｈ４−、−Ｃ２Ｈ４ＯＣＯ−、−Ｃ２Ｈ４ＣＯＯ−、−ＣＦ２Ｏ−が好ましく、製造の容易性及び液晶配向性の観点から、単結合、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＨ２−、又は−ＣＨ２Ｏ−がより好ましい。 L 1 , L 2 and L 3 are each independently a single bond, —OCH 2 —, —C 2 H 4 —, —CH 2 O—, —COO—, —OCO—, —OCOOCH 2 —, —CH. 2 OCOO -, - CH = CH -COO -, - OOC-CH = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO-, —CF 2 O— is preferable, and a single bond, —COO—, —OCO—, —OCH 2 —, or —CH 2 O— is more preferable from the viewpoint of ease of production and liquid crystal orientation.
Ｍ１及びＭ２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−ジイル基が好ましく、Ｍ３は、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、１，３−ジオキサン−２，５−ジイル基、１，３，５−ベンゼントリイル基、１，３，４−ベンゼントリイル基、１，３，４，５−ベンゼンテトライル基、１，３，５−シクロヘキサントリイル基又は１，３，４−シクロヘキサントリイル基が好ましく、１，４−フェニレン基、１，４−シクロヘキシレン基、１，３，５−ベンゼントリイル基、１，３，４−ベンゼントリイル基又はナフタレン−２，６−ジイル基が更に好ましい。Ｚは、フッ素原子、塩素原子、シアノ基、１〜１２個の炭素原子を有するアルキル基、又は−Ｌ３−Ｓ２−Ｒ２（式中Ｒ２、Ｓ２及びＬ３はＲ１、Ｓ１及びＬ１と同じ意味を表す）がより好ましい。ｍは１、２又は３を表し、ｎは０、１又は２を表すが、特にｍ＝１、ｑ＝０又は１が好ましい。ｋは１又は２が好ましい。 M 1 and M 2 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 is preferred, and M 3 is a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, or a naphthalene-2,6-diyl group. Tetrahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5-diyl group, 1,3,5-benzenetriyl group, 1,3,4-benzenetriyl group, 1,3, 4,5-benzenetetrayl group, 1,3,5-cyclohexanetriyl group or 1,3,4-cyclohexanetriyl group is preferable, 1,4-phenylene group, 1,4-cyclohexylene group, 1, 3,5-benzene Riiru group, 1,3,4-benzenetriyl group or a naphthalene-2,6-diyl group are more preferable. Z is a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or -L 3 -S 2 -R 2 (wherein R 2 , S 2 and L 3 are R 1 , S 1 and L 1 have the same meaning). m represents 1, 2 or 3, and n represents 0, 1 or 2. Particularly, m = 1, q = 0 or 1 is preferable. k 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−２４）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-24).
（製法１） 一般式（Ｉ−５）で表される化合物の製造
４−ブロモ−４’−ヒドロキシビフェニルとアクリル酸ターシャリーブチルとのパラジウム触媒による溝呂木−ヘック反応により、ビフェニル誘導体(Ｓ−１)を得て、更に４−（６−アクリロイルオキシヘキシルオキシ）安息香酸と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、アクリロイル基を有するビフェニル誘導体（Ｓ−２）を得る。
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カルボキシル基に変換したビフェニル誘導体（Ｓ−３）を得る。
(Production Method 1) Production of Compound Represented by General Formula (I-5) A biphenyl derivative (S-1) is obtained by a Mizorogi-Heck reaction of 4-bromo-4′-hydroxybiphenyl and tertiary butyl acrylate with a palladium catalyst. And a biphenyl derivative (S-2) having an acryloyl group is obtained by an esterification reaction using 4- (6-acryloyloxyhexyloxy) benzoic acid and a dehydration condensing agent such as dicyclohexylcarbodiimide.
Furthermore, the tertiary butyl group is eliminated with trifluoroacetic acid to obtain a biphenyl derivative (S-3) converted into a carboxyl group.
次いで４−（２−アクリロイルオキシ）エチルフェノールと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−５）を得ることができる。 Subsequently, the target compound (I-5) can be obtained by esterification using 4- (2-acryloyloxy) ethylphenol and a dehydrating condensing agent such as dicyclohexylcarbodiimide.
（製法２） 一般式（Ｉ−８）で表される化合物の製造
２−フルオロ−４−ブロモビフェニルと塩化アセチルとを塩化アルミニム（ＩＩＩ）を用いたフリーデルクラフト反応を行い、更にギ酸と過酸化水素水から調製した過ギ酸によりフッ素原子が置換したヒドロキシビフェニル化合物（Ｓ−４）を得る。更にアクリル酸ターシャリーブチルとのパラジウム触媒による溝呂木−ヘック反応により、ビフェニル誘導体（Ｓ−５）を得て、次いで６−（３−アクリロイルプロピルオキシ）−２−ナフトエ酸と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、アクリロイル基を有するビフェニル誘導体（Ｓ−６）を得る。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カルボキシル基に変換したビフェニル誘導体（Ｓ−７）を得る。
(Production Method 2) Production of Compound Represented by General Formula (I-8) 2-Fluoro-4-bromobiphenyl and acetyl chloride are subjected to Friedel-Craft reaction using aluminum chloride (III), and further formic acid and peroxygen are reacted. A hydroxybiphenyl compound (S-4) having a fluorine atom substituted with performic acid prepared from hydrogen oxide water is obtained. Furthermore, a biphenyl derivative (S-5) is obtained by Mizorogi-Heck reaction with tertiary butyl acrylate by a palladium catalyst, and then dehydration condensation of 6- (3-acryloylpropyloxy) -2-naphthoic acid and dicyclohexylcarbodiimide or the like. A biphenyl derivative (S-6) having an acryloyl group is obtained by an esterification reaction using an agent. Furthermore, the tertiary butyl group is eliminated with trifluoroacetic acid to obtain a biphenyl derivative (S-7) converted to a carboxyl group.
次いで４−(６−アクリロイルオキシヘキシルオキシ）フェノールと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-8）を得ることができる。 Subsequently, the target compound (I-8) can be obtained by esterification using 4- (6-acryloyloxyhexyloxy) phenol and a dehydration condensing agent such as dicyclohexylcarbodiimide.
（製法３） 一般式（Ｉ−１０）で表される化合物の製造
ｐ−ヒドロキシビフェニルカルボン酸エチルエステルと６−クロロヘキサノールとの炭酸カリウム等の塩基を用いたエーテル化反応、及び水酸化ナトリウムによる加水分解により、ビフェニルカルボン酸誘導体（Ｓ−８）を得る。次いでｐ−トルエンスルホン酸を用いたアクリル酸とビフェニルカルボン酸誘導体（Ｓ−８）とのエステル化反応によりアクリル基を有するビフェニルカルボン酸誘導体（Ｓ−９）を得る。
(Production Method 3) Production of Compound Represented by General Formula (I-10) Etherification reaction of p-hydroxybiphenylcarboxylic acid ethyl ester and 6-chlorohexanol using a base such as potassium carbonate, and sodium hydroxide Biphenyl carboxylic acid derivative (S-8) is obtained by hydrolysis. Next, a biphenylcarboxylic acid derivative (S-9) having an acrylic group is obtained by an esterification reaction between acrylic acid and a biphenylcarboxylic acid derivative (S-8) using p-toluenesulfonic acid.
次いで、製法１で合成したビフェニル誘導体（Ｓ−１）とアクリル基を有するビフェニルカルボン酸誘導体（Ｓ−９）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、アクリロイル基を有するビフェニル誘導体を得て、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カルボキシル基に変換したビフェニル誘導体（Ｓ−１０）を得る。次いで４−（３−アクリロイルオキシプロポキシ）フェノールとジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応により目的物化合物（Ｉ−１０）を得ることができる。 Subsequently, the biphenyl having an acryloyl group is obtained by an esterification reaction between the biphenyl derivative (S-1) synthesized by the production method 1 and the biphenylcarboxylic acid derivative (S-9) having an acrylic group using a dehydration condensing agent such as dicyclohexylcarbodiimide. A derivative is obtained, and a biphenyl derivative (S-10) obtained by further removing a tertiary butyl group and converting it to a carboxyl group with trifluoroacetic acid is obtained. Subsequently, the target compound (I-10) can be obtained by an esterification reaction using 4- (3-acryloyloxypropoxy) phenol and a dehydration condensing agent such as dicyclohexylcarbodiimide.
（製法４） 一般式（Ｉ−１４）で表される化合物の製造
製法２において６−（３−アクリロイルプロピルオキシ）−２−ナフトエ酸に換えて６−（３−アクリロイルプロピルオキシ）−２−シクロヘキサンカルボン酸を用いる以外は同様にして目的物化合物（Ｉ−１４）を得ることができる。
（製法５） 一般式（Ｉ−１８）で表される化合物の製造
製法１で合成したビフェニル誘導体（Ｓ−１）と４−（２−アクリロイルオキシエトキシ）安息香酸とのジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応により、アクリロイル基を有するビフェニル誘導体を得て、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カルボン酸基に変換したビフェニル誘導体（Ｓ−１１）を得る。
(Production Method 4) Production of Compound Represented by General Formula (I-14) In Production Method 2, instead of 6- (3-acryloylpropyloxy) -2-naphthoic acid, 6- (3-acryloylpropyloxy) -2- The target compound (I-14) can be obtained in the same manner except that cyclohexanecarboxylic acid is used.
(Manufacturing method 5) Manufacture of the compound represented by general formula (I-18) Dehydration condensation of the biphenyl derivative (S-1) synthesize | combined by manufacturing method 1 and 4- (2-acryloyloxy ethoxy) benzoic acid, such as dicyclohexyl carbodiimide. A biphenyl derivative having an acryloyl group is obtained by an esterification reaction using an agent, and a tertiary butyl group is eliminated with trifluoroacetic acid to obtain a biphenyl derivative (S-11) converted to a carboxylic acid group.
次いで、ｐ−トルエンスルホン酸を用いたｐ−ヒドロキシフェニルプロピオン酸とヒドロシキエチルメタクリレートとのエステル化反応によりメタクリル基を有するフェノール化合物（Ｓ−１２）を得る。次いでビフェニル誘導体（Ｓ−１１）とのジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応により目的物化合物（Ｉ−１８）を得ることができる。 Subsequently, a phenol compound (S-12) having a methacryl group is obtained by esterification reaction of p-hydroxyphenylpropionic acid and hydroxyethyl methacrylate using p-toluenesulfonic acid. Subsequently, the target compound (I-18) can be obtained by an esterification reaction with a biphenyl derivative (S-11) using a dehydration condensing agent such as dicyclohexylcarbodiimide.
（製法６） 一般式（Ｉ−２２）で表される化合物の製造
３−エチル−３−ヒドロキシメチルオキセタン（商品名ＥＯＸＡ、東亜合成社製）と１−ブロモ−３−クロロプロパンとを水酸化ナトリウム等の塩基の存在下でエーテル化反応させ、オキセタン誘導体（Ｓ−１３）を得る。次いでｐ−ヒドロキシ安息香酸メチルとの炭酸カリウム等の塩基存在下でエーテル化反応、更に水酸化ナトリウムによる加水分解により、オキセタン基を有する安息香酸（Ｓ−１４）を得る。次いで製法１で合成したビフェニル誘導体（Ｓ−１）とのジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応、更にトリフルオロ酢酸によるターシャリーブチル基を脱離によりオキセタニル基を有するカルボン酸誘導体（Ｓ−１５）を得る。
(Production Method 6) Production of Compound Represented by General Formula (I-22) 3-Ethyl-3-hydroxymethyloxetane (trade name EOXA, manufactured by Toagosei Co., Ltd.) and 1-bromo-3-chloropropane are mixed with sodium hydroxide. The oxetane derivative (S-13) is obtained by the etherification reaction in the presence of a base such as Subsequently, benzoic acid (S-14) having an oxetane group is obtained by etherification reaction with methyl p-hydroxybenzoate in the presence of a base such as potassium carbonate and further hydrolysis with sodium hydroxide. Next, an esterification reaction with a biphenyl derivative (S-1) synthesized in Production Method 1 using a dehydration condensing agent such as dicyclohexylcarbodiimide, and a carboxylic acid derivative having an oxetanyl group by elimination of a tertiary butyl group with trifluoroacetic acid ( S-15) is obtained.
次いで、ハイドロキノンと３，４−ジヒドロ−２Ｈ−ピランとの反応物であるハイドロキノンモノテトラヒドロピラニルエーテルとオキセタン誘導体（Ｓ−１３）を炭酸カリウム等の塩基存在下でエーテル化反応させ、更に塩酸にてフェノールの保護基を脱離させて、フェノール誘導体（Ｓ−１６）を得る。更にオキセタニル基を有するカルボン酸誘導体（Ｓ−１５）とのジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応により目的物化合物（Ｉ−２２）を得ることができる。 Subsequently, hydroquinone monotetrahydropyranyl ether which is a reaction product of hydroquinone and 3,4-dihydro-2H-pyran and an oxetane derivative (S-13) are etherified in the presence of a base such as potassium carbonate, and further with hydrochloric acid. Phenol derivative (S-16) is obtained by removing the protecting group of phenol. Furthermore, the target compound (I-22) can be obtained by an esterification reaction with a carboxylic acid derivative (S-15) having an oxetanyl group using a dehydration condensing agent such as dicyclohexylcarbodiimide.
（製法７）一般式（Ｉ−１９）で表される化合物の製造
４−ベンジルオキシフェノールとプロトカテク酸とをｐ−トルエンスルホン酸を用いてエステル化反応させることにより、プロトカテク酸誘導体（Ｓ−１７） を得る。ついで、６−クロロヘキサノールとプロトカテク酸誘導体（Ｓ−１７）を炭酸カリウム等の塩基存在下でエーテル化反応させ、更にパラジウムカーボンを用いた水添反応によりベンジル基を脱離させて、水酸基とフェノール基を有するプロトカテク酸誘導体（Ｓ−１８）を得る。次いでｐ−トルエンスルホン酸を用いてアクリル酸とエステル化反応させることによりアクリル基を２つ有する化合物（Ｓ−１９）を得る。
(Production Method 7) Production of Compound Represented by General Formula (I-19)
Protocatechuic acid derivative (S-17) is obtained by esterifying 4-benzyloxyphenol and protocatechuic acid with p-toluenesulfonic acid. Subsequently, 6-chlorohexanol and protocatechuic acid derivative (S-17) are etherified in the presence of a base such as potassium carbonate, and the benzyl group is eliminated by hydrogenation reaction using palladium carbon, whereby hydroxyl group and phenol are obtained. A protocatechuic acid derivative (S-18) having a group is obtained. Subsequently, the compound (S-19) which has two acrylic groups is obtained by making it esterify with acrylic acid using p-toluenesulfonic acid.
更にビフェニル誘導体（Ｓ−３）とアクリル基を２つ有する化合物（Ｓ−１９）とのジシクロヘキシルカルボジイミド等の脱水縮合剤を用いたエステル化反応により目的物化合物（Ｉ−２２）を得ることができる。 Furthermore, the target compound (I-22) can be obtained by esterification reaction of the biphenyl derivative (S-3) and the compound (S-19) having two acrylic groups using a dehydration condensing agent such as dicyclohexylcarbodiimide. .
本願発明の化合物は、ネマチック液晶、スメクチック液晶、キラルネマチック、キラルスメクチック、及びコレステリック液晶組成物に使用できる。本願発明の液晶組成物は、本願発明の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。本願発明の重合性液晶組成物中に含まれる重合性液晶化合物としては、重合性官能基としてアクリロイルオキシ基、メタアクリロイルオキシ基を有するものが特に好ましい。更に重合性液晶化合物としては、重合性官能基を分子内に２つ以上持つものが好ましい。また、本願発明の液晶組成物がコレステリック液晶の場合は、キラル化合物の添加が好ましい。更に重合性基を有しない液晶組成物を添加しても構わなく、それにより得られる液晶組成物は特に高分子安定化液晶表示素子に有用な材料である。 The compounds of the present invention can be used in nematic liquid crystals, smectic liquid crystals, chiral nematics, chiral smectics, and cholesteric liquid crystal compositions. The liquid crystal composition of the present invention may contain other polymerizable compounds in an arbitrary range other than using one or more compounds of the present invention. As the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention, those having an acryloyloxy group or a methacryloyloxy group as a polymerizable functional group are particularly preferable. Further, as the polymerizable liquid crystal compound, those having two or more polymerizable functional groups in the molecule are preferable. When the liquid crystal composition of the present invention is a cholesteric liquid crystal, addition of a chiral compound is preferable. Further, a liquid crystal composition having no polymerizable group may be added, and the liquid crystal composition obtained thereby is a particularly useful material for a polymer-stabilized liquid crystal display element.
本願発明以外の重合性化合物の具体例としては、一般式（Ｉ）で表される化合物を含有する以外に制限はないが、組み合わせて使用する重合性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。 Specific examples of the polymerizable compound other than the invention of the present application are not limited except that the compound represented by the general formula (I) is contained, but as a polymerizable liquid crystal compound used in combination, an acryloyloxy group is contained in the compound. Those having (R-1) or a methacryloyloxy group (R-2) 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Ａは、Ｈ、Ｆ、Ｃｌ、ＣＮ、ＳＣＮ、ＯＣＦ３、１〜１２個の炭素原子を有するアルキル基であり、酸素原子同士が直接結合しないものとして炭素原子が酸素原子、硫黄原子、−ＣＯ−、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−で置換されて良く、又はＡは−Ｌ６−Ｓ４−Ｒ４であり、Ｒ３及びＲ４は、重合性基であり、Ｓ３及びＳ４は、お互い独立して単結合、又は１〜１２個の炭素原子を有するアルキレン基を表し、ここで一つ以上の−ＣＨ２−は、酸素原子同士が直接結合しないものとして炭素原子が酸素原子、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−に置き換えられても良く、Ｌ４、Ｌ５、及びＬ６はお互い独立して、単結合、−Ｏ−、−Ｓ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯＣＨ２−、−ＣＨ２ＯＣＯＯ−、−ＣＯ−ＮＲ１１−、−ＮＲ１１−ＣＯ−、−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−を表すが（式中、Ｒ１１は炭素原子１〜４のアルキル基を表す。）、Ｍ４、及びＭ５はお互い独立して、１，４−フェニレン基、１，４−シクロヘキシレン基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ナフタレン−２，６−ジイル基、テトラヒドロナフタレン−２，６−ジイル基又は１，３−ジオキサン−２，５−ジイル基を表すが、Ｍ４、及びＭ５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、ハロゲノ基、シアノ基、又はニトロ基に置換されていても良く、ｌは０、１、２又は３を表すが、ｌが２又は３を表す場合、２個あるいは３個存在するＬ５及びＭ５は同一であっても異なっていても良い。）で表される化合物が挙げられる。 (In the formula, A is H, F, Cl, CN, SCN, OCF 3 , an alkyl group having 1 to 12 carbon atoms, and the carbon atoms are oxygen atoms and sulfur atoms as those in which oxygen atoms are not directly bonded to each other. , -CO-, -COO-, -OCO-, -OCOO, -CH = CH-, -C≡C-, or A is -L 6 -S 4 -R 4 , R 3 And R 4 are polymerizable groups, and S 3 and S 4 each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms, wherein one or more —CH 2 — In which carbon atoms may be replaced by oxygen atoms, —COO—, —OCO—, —OCOO—, in which oxygen atoms are not directly bonded to each other, and L 4 , L 5 , and L 6 are independent of each other, Single bond, —O—, —S—, —OCH 2 —, —CH 2 O—, —C O—, —COO—, —OCO—, —OCOOCH 2 —, —CH 2 OCOO—, —CO—NR 11 —, —NR 11 —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 -, - OCOCH 2 -, - CH 2 COO -, - CH = CH -, - C 2 H 4 -, - CF = CH -, - CH = CF -, - CF 2 -, - CF 2 O -, - OCF 2 - , —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 — or —C≡C— (wherein R 11 represents an alkyl group having 1 to 4 carbon atoms); M 4 and M 5 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group And M 4 and M 5 are each independently unsubstituted or substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogeno group, a cyano group, or a nitro group. And l represents 0, 1, 2, or 3, but when l represents 2 or 3, two or three L 5 and M 5 may be the same or different.) The compound represented by these is mentioned.
特に、Ｌ４、Ｌ５、及びＬ６がお互い独立して、単結合、−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を表し、Ｍ３、及びＭ４がお互い独立して、１，４−フェニレン基、１，４−シクロヘキシレン基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ナフタレン−２，６−ジイル基で表される化合物が好ましい。 In particular, L 4 , L 5 , and L 6 each independently represent a single bond, —O—, —COO—, or —OCO—, and M 3 and M 4 each independently represent 1,4- A compound represented by a phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, or naphthalene-2,6-diyl group is preferable.
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−２２）で表される化合物が好ましい。 Specifically, the compound represented by the general formula (II) is preferably a compound represented by the general formula (II-1) to the general formula (II-22).
（式中、ａ及びｂは、０〜１２の整数を表すが、ａ又は／及びｂが０であって酸素原子同士が直結した構造となる場合には、酸素原子をひとつ除去する。）また本願発明の液晶組成物に使用する重合性液晶化合物としては、液晶温度範囲や複屈折率の調節、粘度低減を目的として一般式（ＩＩ−２３）〜一般式（ＩＩ−３３）を配合することが好ましい。 (In the formula, a and b represent integers of 0 to 12, but when a or / and b are 0 and the oxygen atoms are directly connected to each other, one oxygen atom is removed.) As the polymerizable liquid crystal compound used in the liquid crystal composition of the present invention, general formula (II-23) to general formula (II-33) are blended for the purpose of adjusting the liquid crystal temperature range, birefringence, and reducing viscosity. Is preferred.
（式中、ａ及びｂは、０〜１２の整数を表すが、ａ又は／及びｂが０であって酸素原子同士が直結した構造となる場合には、酸素原子をひとつ除去する。）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（ＩＩＩ−１）〜一般式（ＩＩＩ−８）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。 (In the formula, a and b represent integers of 0 to 12, but when a or / and b are 0 and the oxygen atoms are directly connected to each other, one oxygen atom is removed.) When the liquid crystal composition of the invention is a cholesteric liquid crystal, a chiral compound is usually added, and specific compounds are represented by general formulas (III-1) to (III-8). 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、ｐ及びｑは、０〜１２の整数を表すが、ｐ又は／及びｑが０であって酸素原子同士が直結した構造となる場合には、酸素原子をひとつ除去する。）
更に本発明の液晶組成物に、重合性基を有しない液晶組成物に添加してもよく、通常の液晶デバイス、例えばＳＴＮ（スーパー・ツイステッド・ネマチック）液晶や、ＴＮ（ツイステッド・ネマチック）液晶、ＴＦＴ（薄膜トランジスター）液晶等に使用されるネマチック液晶組成物、強誘電液晶組成物等が挙げられる。
(In the formula, p and q represent integers of 0 to 12, but when p or / and q are 0 and the oxygen atoms are directly connected to each other, one oxygen atom is removed.)
Furthermore, the liquid crystal composition of the present invention may be added to a liquid crystal composition having no polymerizable group, such as a normal liquid crystal device such as STN (super twisted nematic) liquid crystal, TN (twisted nematic) liquid crystal, Examples thereof include nematic liquid crystal compositions and ferroelectric liquid crystal compositions used for TFT (thin film transistor) liquid crystals.
また、重合性官能基を有する化合物であって、液晶性を示さない化合物を添加することもできる。このような化合物としては、通常、この技術分野で高分子形成性モノマーあるいは高分子形成性オリゴマーとして認識されるものであれば特に制限なく使用することができるが、その添加量は組成物として液晶性を呈するように調整する必要がある。 Moreover, it is a compound which has a polymerizable functional group, Comprising: The compound which does not show liquid crystallinity can also be added. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field. It is necessary to adjust to exhibit sex.
本発明の液晶組成物は、π電子が広く共役したビフェニル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、光重合開始剤の添加が好ましい。添加する光重合開始剤の濃度は、０．１〜１０質量%が好ましく、０．２〜１０質量%が更に好ましく、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。 Since the liquid crystal composition of the present invention has a biphenyl skeleton in which π electrons are widely conjugated, polymerization by heat and light is possible without adding a polymerization initiator, but the addition of a photopolymerization initiator is preferred. The concentration of the photopolymerization initiator to be added is preferably 0.1 to 10% by mass, more preferably 0.2 to 10% by mass, and particularly preferably 0.4 to 5% by mass. Examples of the photoinitiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides.
また、本発明の液晶組成物には、その保存安定性を向上させるために、安定剤を添加することもできる。使用できる安定剤としては、例えば、ヒドロキノン類、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、β−ナフチルアミン類、β−ナフトール類、ニトロソ化合物等が挙げられる。安定剤を使用する場合の添加量は、液晶組成物に対して０．００５〜１質量％の範囲が好ましく、０．０２〜０．５質量％が更に好ましく、０．０３〜０．１質量％が特に好ましい。 In addition, a stabilizer can be added to the liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. When the stabilizer is used, the amount added is preferably 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% by mass with respect to the liquid crystal composition. % Is particularly preferred.
また、本発明の液晶組成物を位相差フィルム、偏光フィルムや配向膜の原料、又は印刷インキ及び塗料、保護膜等の用途に利用する場合には、その目的に応じて金属、金属錯体、染料、顔料、色素、蛍光材料、燐光材料、界面活性剤、レベリング剤、チキソ剤、ゲル化剤、多糖類、紫外線吸収剤、赤外線吸収剤、抗酸化剤、イオン交換樹脂、酸化チタン等の金属酸化物等を添加することもできる。 In addition, when the liquid crystal composition of the present invention is used for a retardation film, a material for a polarizing film or an alignment film, a printing ink, a paint, a protective film or the like, a metal, a metal complex, or a dye is used depending on the purpose. , Pigments, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, titanium oxide, etc. A thing etc. can also be added.
次に本発明の光学異方体について説明する。本発明の液晶組成物を重合させることによって製造される光学異方体は種々の用途に利用できる。例えば、本発明の重合性液晶組成物を、配向させない状態で重合させた場合、光散乱板、偏光解消板、モアレ縞防止板として利用可能である。また、本発明の重合性液晶組成物を配向させた状態において、重合させることにより製造された光学異方体は、物理的性質に光学異方性を有しており、有用である。このような光学異方体は、例えば、本発明の重合性液晶組成物表面を、布等でラビング処理した基板、もしくは有機薄膜を形成した基板表面を布等でラビング処理した基板、あるいはＳｉＯ２を斜方蒸着した配向膜を有する基板上に担持させるか、基板間に挟持させた後、本発明の液晶を重合させることによって製造することができる。 Next, the optical anisotropic body of the present invention will be described. The optical anisotropic body produced by polymerizing the liquid crystal composition of the present invention can be used for various applications. For example, when the polymerizable liquid crystal composition of the present invention is polymerized without being oriented, it can be used as a light scattering plate, a depolarizing plate, or a moire fringe prevention plate. Moreover, the optically anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention in an aligned state has optical anisotropy in physical properties and is useful. Such an optical anisotropic body is, for example, a substrate obtained by rubbing the surface of the polymerizable liquid crystal composition of the present invention with a cloth or the like, a substrate obtained by rubbing a substrate surface on which an organic thin film is formed with a cloth, or SiO 2. Can be produced by polymerizing the liquid crystal of the present invention after it is supported on a substrate having an orientation film deposited obliquely or sandwiched between the substrates.
重合性液晶組成物を基板上に担持させる際の方法としては、スピンコーティング、ダイコーティング、エクストルージョンコーティング、ロールコーティング、ワイヤーバーコーティング、グラビアコーティング、スプレーコーティング、ディッピング、プリント法等を挙げることができる。またコーティングの際、重合性液晶組成物をそのまま使用しても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、塩化メチレン、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更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, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolve, cyclohexanone, γ-butyllactone, acetoxy-2-ethoxyethane, propylene glycol Examples thereof include monomethyl 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. .
液晶組成物を基板間に挟持させる方法としては、毛細管現象を利用した注入法が挙げられる。基板間に形成された空間を減圧し、その後液晶材料を注入する手段も有効である。 Examples of a method for sandwiching the liquid crystal composition between the substrates include an injection method using a capillary phenomenon. It is also effective to depressurize the space formed between the substrates and then inject a liquid crystal material.
ラビング処理、あるいはＳｉＯ２の斜方蒸着以外の配向処理としては、液晶材料の流動配向の利用や、電場又は磁場の利用を挙げることができる。これらの配向手段は単独で用いても、また組み合わせて用いても良い。更に、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 also 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、更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 during 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.
また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。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。 Further, 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 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. 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.
更に、本願記載の重合性化合物を非重合性の液晶組成物に添加してもよい。液晶表示素子に関しては液晶媒体に重合性化合物を添加して表示特性を向上させる例が報告されており、液晶セル内の液晶分子の配向を制御するために本願化合物を使用することもできる。具体的な液晶組成物としては通常の液晶表示素子、例えばＳＴＮ（スーパー・ツイステッド・ネマチック）液晶や、ＴＮ（ツイステッド・ネマチック）液晶、ＴＦＴ（薄膜トランジスター）液晶等に使用されるネマチック液晶組成物、強誘電液晶組成物等が挙げられる。 Furthermore, the polymerizable compound described in the present application may be added to the non-polymerizable liquid crystal composition. With respect to the liquid crystal display element, an example in which a display compound is improved by adding a polymerizable compound to a liquid crystal medium has been reported, and the compound of the present application can also be used to control the alignment of liquid crystal molecules in a liquid crystal cell. Specific liquid crystal compositions include nematic liquid crystal compositions used for ordinary liquid crystal display elements such as STN (super twisted nematic) liquid crystal, TN (twisted nematic) liquid crystal, TFT (thin film transistor) liquid crystal, Examples thereof include a ferroelectric liquid crystal composition.
また、重合性官能基を有する化合物であって、液晶性を示さない化合物を添加することもできる。このような化合物としては、通常、この技術分野で高分子形成性モノマーあるいは高分子形成性オリゴマーとして認識されるものであれば特に制限なく使用することができるが、その添加量は組成物として液晶性を呈するように調整する必要があり、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。一般式（Ｉ）で表される化合物の含有率は、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２．０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。 Moreover, it is a compound which has a polymerizable functional group, Comprising: The compound which does not show liquid crystallinity can also be added. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field. It is necessary to adjust so as to exhibit properties, and contains at least one polymerizable compound represented by the general formula (I), preferably 1 to 5 types, preferably 1 to 3 types. It is particularly preferred. If the content of the 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 rises and the polymerization remains without being polymerized. The lower limit value is preferably 0.01% by mass, more preferably 0.03% by mass, and the upper limit value is preferably 2.0% by mass, since the amount of the active compound increases. More preferably, it is 1.0 mass%.
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。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塩化アルミニウム（ＩＩＩ）を１２．８ｇ（９６ミリモル）、ジクロロメタン１００ｍｌを加え攪拌した。次いで塩化アセチル ８．４ｇ（１１０ミリモル）を９０分かけてゆっくり滴下し、更に４−ブロモ−２−フルオロビフェニル ２０ｇ（８０ミリモル）のジクロロメタン溶液８０ｍｌを２時間かけてゆっくり滴下した。滴下終了後、更に２時間攪拌し、反応を終了させた。反応液を５００ｍｌの氷水にゆっくり注ぎ、ジクロロメタンで抽出し、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、乾燥を行いアセチル基を導入した化合物を２３ｇ得た。次いで、撹拌装置、冷却器、及び温度計を備えた反応容器にアセチル基を導入した化合物２３ｇ、ギ酸３００ｍｌを仕込み、３４．５％の過酸化水素水２０ｍｌを加え、加熱還流を６時間行った。反応終了後、１０％の亜硫酸水素ナトリウム水溶液４５０ｍｌ行い、過酸化物を分解した。析出した固体をろ過し酢酸エチルで溶解させ水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（１）に示す化合物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
To a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 12.8 g (96 mmol) of aluminum (III) chloride and 100 ml of dichloromethane were added and stirred. Next, 8.4 g (110 mmol) of acetyl chloride was slowly added dropwise over 90 minutes, and further 80 ml of a dichloromethane solution of 20 g (80 mmol) of 4-bromo-2-fluorobiphenyl was slowly added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by further stirring for 2 hours. The reaction solution was slowly poured into 500 ml of ice water, extracted with dichloromethane, and the organic layer was washed with pure water and saturated brine. After the solvent was distilled off, drying was performed to obtain 23 g of a compound having an acetyl group introduced. Next, 23 g of a compound having an acetyl group introduced therein and 300 ml of formic acid were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and 20 ml of 34.5% hydrogen peroxide solution was added, followed by heating and refluxing for 6 hours. . After completion of the reaction, 450 ml of 10% aqueous sodium bisulfite solution was used to decompose the peroxide. The precipitated solid was filtered, dissolved with ethyl acetate, and the organic layer was washed with water and saturated brine. After distilling off the solvent, purification was carried out with a double amount (weight ratio) silica gel column to obtain 18 g of a compound represented by the formula (1).
撹拌装置、冷却器、及び温度計を備えた反応容器に４−ブロモ−３−フルオロビフェニル １０ｇ（３７．４ミリモル）、ターシャリーブチルアクリレート ５．７ｇ（４４．８ミリモル）、トリエチルアミン ５．６ｇ（５６ミリモル）、酢酸パラジウム ４１０ｍｇ、ジメチルホルムアミド ３００ｍｌを仕込み、窒素ガス雰囲気下で反応器を１００℃に加熱し反応させた。反応終了後、酢酸エチル、ＴＨＦを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（２）に示す化合物１０．５ｇを得た。 In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 10 g (37.4 mmol) of 4-bromo-3-fluorobiphenyl, 5.7 g (44.8 mmol) of tertiary butyl acrylate, 5.6 g of triethylamine ( 56 mmol), 410 mg of palladium acetate and 300 ml of dimethylformamide were charged, and the reactor was heated to 100 ° C. for reaction under a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 10.5 g of a compound represented by the formula (2).
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（２）に示す化合物１０ｇ（３１ミリモル）、４−（３−アクリロイルオキシプロピルオキシ）安息香酸 ７．７ｇ（３１ミリモル）、ジメチルアミノピリジン ４００ｍｇ、塩化メチレン １００ｍｌ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 ４．６ｇ（３７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、ろ液に塩化メチレン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い、塩化メチレン／メタノールによる再結晶により式（３）に示す目的の化合物１１ｇを得た。 Next, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 10 g (31 mmol) of the compound represented by the above formula (2), 7.7 g (31 mmol) of 4- (3-acryloyloxypropyloxy) benzoic acid. Then, 400 mg of dimethylaminopyridine and 100 ml of methylene chloride are charged, and the reaction vessel is kept at 5 ° C. or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 4.6 g (37 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a double amount (weight ratio) silica gel column, and 11 g of the desired compound represented by the formula (3) was obtained by recrystallization with methylene chloride / methanol.
更に撹拌装置、冷却器及び温度計を備えた反応容器に、式（３）に示す化合物 １１ｇを塩化メチレン１５ｍｌに溶解させた後、トリフルオロ酢酸１５ｍｌを滴下し、室温で３０分攪拌した。その後、純水を加えて固体を析出させた。その固体を酢酸エチル１５０ｍｌ、テトラヒドロフラン１５０ｍｌに溶解させ、飽和食塩水で有機層を洗浄した。溶媒を留去し式（４）に示す化合物 ８ｇを得た。 Further, 11 g of the compound represented by the formula (3) was dissolved in 15 ml of methylene chloride in a reaction vessel equipped with a stirrer, a cooler and a thermometer, and then 15 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 30 minutes. Thereafter, pure water was added to precipitate a solid. The solid was dissolved in 150 ml of ethyl acetate and 150 ml of tetrahydrofuran, and the organic layer was washed with saturated brine. The solvent was distilled off to obtain 8 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、上記式（４）に示す化合物８ｇ（１５．５ミリモル）、アクリル酸＝２−（４−ヒドロキシフェニル）エチル ３ｇ（１５．５ミリモル）、ジメチルアミノピリジン ２００ｍｇ、塩化メチレン １００ｍｌ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（１８．６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、ろ液に塩化メチレン２００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い、塩化メチレン／メタノールによる再結晶により式（５）に示す目的の化合物３ｇを得た。この化合物は、１１４℃から１８０℃以上まで幅広い温度でネマチック液晶相を示した。 Next, in a reaction vessel equipped with a stirrer, a condenser and a thermometer, 8 g (15.5 mmol) of the compound represented by the above formula (4), 3 g (15.5 mmol) of acrylic acid = 2- (4-hydroxyphenyl) ethyl. Mmol), 200 mg of dimethylaminopyridine, and 100 ml of methylene chloride, and keep the reaction vessel at 5 ° C. or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 2.3 g (18.6 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a double amount (weight ratio) silica gel column, and recrystallization with methylene chloride / methanol gave 3 g of the desired compound represented by formula (5). This compound exhibited a nematic liquid crystal phase at a wide temperature range from 114 ° C. to 180 ° C. or higher.
（物性値）
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：２．２２（ｔ，２Ｈ）， ３．００（ｔ，２Ｈ），４．１６（ｔ，２Ｈ），４．３７−４．４０（ｍ，４Ｈ），５．８２−５．８６（ｍ，２Ｈ），６．０８−６．１７（ｍ，２Ｈ），６．３７−６．４５（ｍ，２Ｈ），６．６３（ｄ，１Ｈ），６．９８（ｄｄ，２Ｈ），７．１３（ｄｄ，２Ｈ），７．２５−７．３７（ｍ，４Ｈ），７．３７−７．４５（ｍ，２Ｈ），７．４９−７．５２（ｍ，１Ｈ），７．６２（ｄｄ，２Ｈ），７．８２（ｄ，１Ｈ），８．１６−８．１８（ｍ，２Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：２８．４，３４．４，６１．１，６４．６，６４．８，１１４．３，１１５．２，１１５．５，１１８．５，１２１．５，１２１．７，１２２．０，１２４．５，１２８．３，１２９．９，１３０．０，１３０．３，１３０．９，１３１．１，１３２．３，１３５．４，１４４．７，１４９．３，１５１．０，１５８．６，１６１．０，１６３．１，１６４．７，１６５．０，１６６．０
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９ ｃｍ−１
融点：１１４℃
（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４−ブロモ−２−フルオロビフェニル ３０ｇ（１２０ミリモル）、ジクロロメタン １２０ｍｌを加え攪拌した。反応容器を０℃に冷却し、塩化アルミニウム（ＩＩＩ）１８ｇを加え、更にシュウ酸クロリドを１７ｇを３０分かけてゆっくり滴下した。
(Physical property value)
1 H-NMR (solvent: deuterated chloroform): δ: 2.22 (t, 2H), 3.00 (t, 2H), 4.16 (t, 2H), 4.37-4.40 (m, 4H), 5.82-5.86 (m, 2H), 6.08-6.17 (m, 2H), 6.37-6.45 (m, 2H), 6.63 (d, 1H) 6.98 (dd, 2H), 7.13 (dd, 2H), 7.25-7.37 (m, 4H), 7.37-7.45 (m, 2H), 7.49-7. .52 (m, 1H), 7.62 (dd, 2H), 7.82 (d, 1H), 8.16-8.18 (m, 2H)
13 C-NMR (solvent: deuterated chloroform): δ: 28.4, 34.4, 61.1, 64.6, 64.8, 114.3, 115.2, 115.5, 118.5, 121 5, 121.7, 122.0, 124.5, 128.3, 129.9, 130.0, 130.3, 130.9, 131.1, 132.3, 135.4, 144.7 , 149.3, 151.0, 158.6, 161.0, 163.1, 164.7, 165.0, 166.0
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm −1
Melting point: 114 ° C
(Example 2)
To a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 30 g (120 mmol) of 4-bromo-2-fluorobiphenyl and 120 ml of dichloromethane were added and stirred. The reaction vessel was cooled to 0 ° C., 18 g of aluminum (III) chloride was added, and 17 g of oxalic chloride was slowly added dropwise over 30 minutes.
滴下終了後、反応容器を室温に戻し２時間攪拌し、反応を終了させた。反応液を５００ｍｌの氷水にゆっくり注ぎ、ジクロロメタンで抽出し、硫酸ナトリウムで有機層を乾燥させた。溶媒を留去した後、反応物をトルエン２００ｍｌに溶解させ、エタノール７ｍｌ加え反応容器を０℃に冷却する。その後、トリエチルアミン１５ｇ（１５０ミリモル）をゆっくり滴下する。滴下終了後、反応容器を室温に戻し２時間攪拌し反応を終了させた。反応終了後、トリエチルアミンの塩酸塩を炉別し、有機層を、１０％塩酸、純水、飽和食塩水で洗浄した。溶媒を留去し式（６）に示す化合物 ３５ｇを得た。 After completion of the dropping, the reaction vessel was returned to room temperature and stirred for 2 hours to complete the reaction. The reaction solution was slowly poured into 500 ml of ice water, extracted with dichloromethane, and the organic layer was dried over sodium sulfate. After distilling off the solvent, the reaction product is dissolved in 200 ml of toluene, 7 ml of ethanol is added, and the reaction vessel is cooled to 0 ° C. Thereafter, 15 g (150 mmol) of triethylamine is slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and stirred for 2 hours to complete the reaction. After completion of the reaction, triethylamine hydrochloride was filtered off and the organic layer was washed with 10% hydrochloric acid, pure water and saturated saline. The solvent was distilled off to obtain 35 g of a compound represented by the formula (6).
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（６）に示す化合物３５ｇ（１０８ミリモル）、エチルアクリレート １３ｇ（１３０ミリモル）、トリエチルアミン １３ｇ（１３０ミリモル）、酢酸パラジウム ８００ｍｇ、ジメチルホルムアミド ５００ｍｌを仕込み、窒素ガス雰囲気下で反応器を１００℃に加熱し反応させた。反応終了後、酢酸エチル、ＴＨＦを加え、１０％塩酸水溶液、純水、飽和食塩水で有機層を洗浄した。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い式（７）に示す化合物３３ｇを得た。 Next, in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 35 g (108 mmol) of the compound represented by the above formula (6), 13 g (130 mmol) of ethyl acrylate, 13 g (130 mmol) of triethylamine, 800 mg of palladium acetate, 500 ml of dimethylformamide was charged, and the reaction was performed by heating the reactor to 100 ° C. in a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 33 g of a compound represented by the formula (7).
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（７）に示す化合物３３ｇ（９６ミリモル）、エタノール ２００ｍｌを加え、６０℃に加熱し溶解させる。次いで、水酸化ナトリウム１０ｇを溶解させた水溶液５０ｍｌをゆっくり滴下した。滴下終了後、そのままの温度で２時間反応させた。反応終了後、１０％塩酸水溶液 １００ｍｌ加え、固体を析出させる。固体をろ別し、アセトンで固体を洗浄後、乾燥して式（８）に示す化合物を２６ｇ得た。 Furthermore, 33 g (96 mmol) of the compound represented by the above formula (7) and 200 ml of ethanol are added to a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and heated to 60 ° C. for dissolution. Next, 50 ml of an aqueous solution in which 10 g of sodium hydroxide was dissolved was slowly added dropwise. After completion of dropping, the reaction was allowed to proceed for 2 hours at the same temperature. After completion of the reaction, 100 ml of 10% aqueous hydrochloric acid solution is added to precipitate a solid. The solid was filtered off, washed with acetone and dried to obtain 26 g of the compound represented by formula (8).
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（８）に示す化合物２６ｇ（９１ミリモル）、アクリル酸＝２−（４−ヒドロキシフェニル）エチル ３５ｇ（１８１ミリモル）、ジメチルアミノピリジン ２．２ｇ、塩化メチレン ３００ｍｌ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 ２７．３ｇ（２１０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、ろ液に塩化メチレン４００ｍｌを加え、１０％塩酸水溶液で洗浄し、更に飽和食塩水で洗浄し、有機層を無水硫酸ナトリウムで乾燥させた。溶媒を留去した後、２倍量（重量比）のシリカゲルカラムにより精製を行い、塩化メチレン／メタノールによる再結晶により式（９）に示す目的の化合物４５ｇを得た。この化合物は、１０６℃から１８０℃以上まで幅広い温度でネマチック液晶相を示した。 Next, in a reaction vessel equipped with a stirrer, a condenser and a thermometer, 26 g (91 mmol) of the compound represented by the above formula (8), 35 g (181 mmol) of acrylic acid = 2- (4-hydroxyphenyl) ethyl, dimethyl Charge 2.2 g of aminopyridine and 300 ml of methylene chloride, and keep the reaction vessel at 5 ° C or lower with an ice-cooled bath. Under an atmosphere of nitrogen gas, 27.3 g (210 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 400 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was carried out with a double amount (weight ratio) silica gel column, and 45 g of the desired compound represented by the formula (9) was obtained by recrystallization with methylene chloride / methanol. This compound exhibited a nematic liquid crystal phase at a wide temperature from 106 ° C. to 180 ° C. or higher.
（物性値）
１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ： ３．００（ｔ，４Ｈ），４．４０（ｔ，４Ｈ），５．８２−５．８５（ｍ，２Ｈ），６．０９−６．１６（ｍ，２Ｈ），６．３８−６．４３（ｍ，２Ｈ），６．６６（ｄ，１Ｈ），７．１１−７．１９（ｍ，４Ｈ），７．２６−７．３２（ｍ，４Ｈ），７．４０−７．４９（ｍ，２Ｈ），７．５４−７．６１（ｍ，１Ｈ），７．７１（ｄｄ，２Ｈ），７．８３（ｄ，１Ｈ），８．２８−８．３０（ｍ，２Ｈ）
１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：３４．４，６４．８，１１５．４，１１５．６，１１９．１，１２１．５，１２１．６，１２４．６，１２８．３，１２９．１，１２９．９，１３０．４，１３０．８，１３１．１，１３５．５，１４４．４，１４９．３，１４９．５，１６４．８，１６４．９，１６６．０
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６０，１６５２−１６２２，８０９ ｃｍ−１
融点：１０６℃
（実施例３）
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: 3.00 (t, 4H), 4.40 (t, 4H), 5.82-5.85 (m, 2H), 6.09-6. 16 (m, 2H), 6.38-6.43 (m, 2H), 6.66 (d, 1H), 7.11-7.19 (m, 4H), 7.26-7.32 ( m, 4H), 7.40-7.49 (m, 2H), 7.54-7.61 (m, 1H), 7.71 (dd, 2H), 7.83 (d, 1H), 8 .28-8.30 (m, 2H)
13 C-NMR (solvent: deuterated chloroform): δ: 34.4, 64.8, 115.4, 115.6, 119.1, 121.5, 121.6, 124.6, 128.3, 129 1, 129.9, 130.4, 130.8, 131.1, 135.5, 144.4, 149.3, 149.5, 164.8, 164.9, 166.0
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm −1
Melting point: 106 ° C
(Example 3)
A polymerizable liquid crystal composition (Composition 1) having the following composition was prepared.
重合性液晶組成物は、良好な相溶安定性を有し、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、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 compatibility 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 2). When the cyclohexanone solution of composition 2 was spin-coated on polyimide-coated glass and irradiated with 4 mW / cm 2 of ultraviolet light for 120 seconds using a high-pressure mercury lamp, composition 2 remained in a uniform alignment state. Polymerization yielded an optically anisotropic body. 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、溶解性が悪く室温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 solubility 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、良好な相溶安定性を有し、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、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３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 compatibility 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). The cyclohexanone solution of composition 5 was spin-coated on a polyimide-coated glass, and irradiated with 4 mW / cm 2 of ultraviolet light for 120 seconds using a high-pressure mercury lamp. As a result, composition 3 remained in a uniform alignment state. Polymerization yielded an optically anisotropic body. 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。 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.
Claims (9)
Ｌ ２ は、単結合、−Ｏ−、−Ｓ−、−ＯＣＨ ２ −、−ＣＨ ２ Ｏ−、−ＣＯ−、−Ｃ ２ Ｈ ４ −、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯＣＨ ２ −、−ＣＨ ２ ＯＣＯＯ−、−ＣＯ−ＮＲ １１ −、−ＮＲ １１ −ＣＯ−、−ＳＣＨ ２ −、−ＣＨ ２ Ｓ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、―ＣＯＯＣ ２ Ｈ ４ −、−ＯＣＯＣ ２ Ｈ ４ −、−Ｃ ２ Ｈ ４ ＯＣＯ−、−Ｃ ２ Ｈ ４ ＣＯＯ−、−ＯＣＯＣＨ ２ −、−ＣＨ ２ ＣＯＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−ＣＦ ２ −、−ＣＦ ２ Ｏ−、−ＯＣＦ ２ −、−ＣＦ ２ ＣＨ ２ −、−ＣＨ ２ ＣＦ ２ −、−ＣＦ ２ ＣＦ ２ −又は−Ｃ≡Ｃ−を表し（式中、Ｒ １１ は炭素原子１〜４のアルキル基を表す。）、Ｍ１及びＭ２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−ジイル基を表し、Ｍ３は１，４−フェニレン基、１，３，４−ベンゼントリイル基、１，３，５−ベンゼントリイル基、１，３，４，５−ベンゼンテトライル基、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、１，３−ジオキサン−２，５−ジイル基、１，４−シクロヘキシレン基、１，３，５−シクロヘキサントリイル基又は１，３，４−シクロヘキサントリイル基を表し、Ｍ１、Ｍ２及びＭ３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、ハロゲン基、シアノ基、又はニトロ基で置換されていても良く、ｍは１、２又は３を表し、ｎは０、１又は２を表し、ｍ及びｎが２又は３を表す場合、２個あるいは３個存在するＬ１、Ｌ２、Ｍ１及びＭ２は同一であっても異なっていても良く、Ｚは、Ｈ、Ｆ、Ｃｌ、ＣＮ、ＳＣＮ、ＯＣＦ３、又は１〜１２個の炭素原子を有するアルキル基を表し、該アルキル基は酸素原子同士が直接結合しないものとしてメチレン基が酸素原子、硫黄原子、−ＣＯ−、―ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ、−ＣＨ＝ＣＨ−、又は−Ｃ≡Ｃ−で置換されても良く、又はＺは−Ｌ３−Ｓ２−Ｒ２（式中Ｒ２、Ｓ２及びＬ３はＲ１、Ｓ１及びＬ ２ と同じ意味を表す。）を表し、ｋは１、２又は３を表すが、ｋが２又は３を表す場合にＺは同一であっても異なっていても良い。）で表される重合性化合物。 Formula (I)
L 2 represents a single bond, —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —C 2 H 4 —, —COO—, —OCO—, —OCOOCH 2 —, -CH 2 OCOO -, - CO- NR 11 -, - NR 11 -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - COO-CH = CH -, - CH = CH-OCO -, - OCOCH = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - OCOCH 2 -, - CH 2 COO—, —CH═CH—, —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 (wherein -C≡C-, R 11 is of 1 to 4 carbon atoms alkylene Represents a group.), M 1 and M 2 are independently from each other, 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, Represents a naphthalene-2,6-diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, M 3 represents a 1,4-phenylene group, 1,3,4- Benzenetriyl group, 1,3,5-benzenetriyl group, 1,3,4,5-benzenetetrayl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2 , 6-diyl group, tetrahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5-diyl group, 1,4-cyclohexylene group, 1,3,5-cyclohexanetriyl group or 1, 3,4-cyclohexane Represents Riiru group, M 1, M 2 and M 3 are, independently of one another, are a non or substituted by an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen group, substituted with a cyano group, or a nitro group M is 1, 2 or 3, n is 0, 1 or 2, and when m and n are 2 or 3, 2 or 3 L 1 , L 2 , M 1 and M 2 may be the same or different and Z represents H, F, Cl, CN, SCN, OCF 3 , or an alkyl group having 1 to 12 carbon atoms, the alkyl group being oxygen The methylene group may be substituted with an oxygen atom, a sulfur atom, —CO—, —COO—, —OCO—, —OCOO, —CH═CH—, or —C≡C— as those in which atoms are not directly bonded to each other. or Z is -L 3 -S 2 -R 2 (wherein R 2, S 2 and L 3 have the same meanings as R 1, S 1及beauty L 2. ), K represents 1, 2 or 3, but when k represents 2 or 3, Z may be the same or different. ) A polymerizable compound represented by:
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| JP5545518B2 (en) * | 2009-09-30 | 2014-07-09 | Ｄｉｃ株式会社 | Polymerizable biphenyl compound |
| CN103619803B (en) * | 2011-05-31 | 2016-01-20 | Dic株式会社 | Cinnamic acid derivative and polymkeric substance thereof and the liquid crystal aligning layer be made up of its cured article |
| CN102936504A (en) * | 2012-10-29 | 2013-02-20 | 深圳市华星光电技术有限公司 | Liquid crystal composition and liquid crystal panel |
| KR20150096449A (en) * | 2012-12-12 | 2015-08-24 | 메르크 파텐트 게엠베하 | Liquid-crystalline medium |
| JP6209864B2 (en) * | 2013-05-29 | 2017-10-11 | Dic株式会社 | Polymerizable liquid crystal composition, retardation film, retardation patterning film, and homogeneous alignment liquid crystal film |
| KR101628288B1 (en) * | 2013-09-30 | 2016-06-08 | 주식회사 엘지화학 | Composition for manufacturing optical elements with negative optical dispersion and optically anisotropic body manufactured therefrom |
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| JP2575885B2 (en) * | 1989-08-23 | 1997-01-29 | シャープ株式会社 | Liquid crystal composition and liquid crystal device containing the same |
| CN1173891A (en) | 1995-02-06 | 1998-02-18 | 默克专利股份有限公司 | Direactive mesogenic compounds and intermediates |
| JP4517416B2 (en) * | 1999-03-30 | 2010-08-04 | Ｄｉｃ株式会社 | Polymerizable compound, synthetic intermediate of the compound, polymerizable liquid crystal composition containing the polymerizable compound, optical anisotropic body comprising the composition, and method for producing the optical anisotropic body |
| JP4561218B2 (en) | 2003-07-30 | 2010-10-13 | チッソ株式会社 | Photocurable fluorene derivatives and compositions containing them |
| DE602004001650T2 (en) | 2003-10-17 | 2007-07-19 | Merck Patent Gmbh | Polymerizable cinnamic acid derivatives with a lateral substitution |
| JP2005222777A (en) * | 2004-02-04 | 2005-08-18 | Seiko Epson Corp | ORGANIC ELECTROLUMINESCENCE ELEMENT, ITS MANUFACTURING METHOD, AND ELECTRONIC DEVICE |
| JP5168976B2 (en) * | 2007-03-28 | 2013-03-27 | Ｄｉｃ株式会社 | Biphenyl and terphenyl compounds and polymerizable liquid crystal compositions containing the compounds |
| JP2008262074A (en) * | 2007-04-13 | 2008-10-30 | Fujifilm Corp | Liquid crystal aligning agent, alignment layer, liquid crystal cell and liquid crystal display |
| JP4450261B2 (en) * | 2007-10-19 | 2010-04-14 | Ｊｓｒ株式会社 | Liquid crystal aligning agent, method for forming liquid crystal aligning film, and liquid crystal display element |
| JP5505686B2 (en) * | 2009-01-23 | 2014-05-28 | Ｄｉｃ株式会社 | Polymerizable biphenyl compound |
| WO2010119779A1 (en) * | 2009-04-14 | 2010-10-21 | Dic株式会社 | Liquid crystal composition containing polymerizable compound and liquid crystal display element using same |
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| CN102030653A (en) | 2011-04-27 |
| KR20110033773A (en) | 2011-03-31 |
| CN102030653B (en) | 2015-07-01 |
| JP2011068590A (en) | 2011-04-07 |
| TW201124509A (en) | 2011-07-16 |
| TWI482845B (en) | 2015-05-01 |
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