JPH1180081A - Liquid crystal (meth)acrylate compound, its composition and optical isomer using the same - Google Patents
Liquid crystal (meth)acrylate compound, its composition and optical isomer using the sameInfo
- Publication number
- JPH1180081A JPH1180081A JP9240996A JP24099697A JPH1180081A JP H1180081 A JPH1180081 A JP H1180081A JP 9240996 A JP9240996 A JP 9240996A JP 24099697 A JP24099697 A JP 24099697A JP H1180081 A JPH1180081 A JP H1180081A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- group
- crystal composition
- compound
- meth
- 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
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 157
- 239000000203 mixture Substances 0.000 title claims description 105
- -1 acrylate compound Chemical class 0.000 title claims description 65
- 230000003287 optical effect Effects 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 230000001747 exhibiting effect Effects 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 230000010287 polarization Effects 0.000 abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 66
- 239000012071 phase Substances 0.000 description 53
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 239000000758 substrate Substances 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 125000000524 functional group Chemical group 0.000 description 18
- 239000012043 crude product Substances 0.000 description 16
- 239000004990 Smectic liquid crystal Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 239000010409 thin film Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 10
- 230000007704 transition Effects 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000003302 alkenyloxy group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000010992 reflux Methods 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
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- XQXPVVBIMDBYFF-UHFFFAOYSA-N 4-hydroxyphenylacetic acid Chemical compound OC(=O)CC1=CC=C(O)C=C1 XQXPVVBIMDBYFF-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JXDXRINTXMVRHU-UHFFFAOYSA-N C1(CCCCC1)N=C=NC1CCCCC1.C(C=C)(=O)O Chemical class C1(CCCCC1)N=C=NC1CCCCC1.C(C=C)(=O)O JXDXRINTXMVRHU-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 239000005643 Pelargonic acid Substances 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
- 229910004298 SiO 2 Inorganic materials 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000000777 acyl halide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 1
- XHRPOTDGOASDJS-UHFFFAOYSA-N cholesterol n-octadecanoate Natural products C12CCC3(C)C(C(C)CCCC(C)C)CCC3C2CC=C2C1(C)CCC(OC(=O)CCCCCCCCCCCCCCCCC)C2 XHRPOTDGOASDJS-UHFFFAOYSA-N 0.000 description 1
- XHRPOTDGOASDJS-XNTGVSEISA-N cholesteryl stearate Chemical compound C([C@@H]12)C[C@]3(C)[C@@H]([C@H](C)CCCC(C)C)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)CCCCCCCCCCCCCCCCC)C1 XHRPOTDGOASDJS-XNTGVSEISA-N 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N noncarboxylic acid Natural products CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000011907 photodimerization Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Liquid Crystal (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光学、表示、記録
材料、また液晶ディスプレイの光学補償板や偏光プリズ
ム材料として利用される新規な液晶性（メタ）アクリレ
ート化合物と液晶組成物及びこれを用いた光学異方体に
関する。[0001] The present invention relates to a novel liquid crystalline (meth) acrylate compound and a liquid crystal composition which are used as optical, display and recording materials, and as optical compensators and polarizing prism materials for liquid crystal displays. Optical anisotropic body.
【０００２】[0002]
【従来の技術】先に我々は、液晶ディスプレイ素子の表
示品位の向上と軽量化に応える光学補償板等の光学異方
体の作製を可能にする技術として、室温において液晶性
を示す重合性液晶組成物とその組成物を配向させた状態
において光重合して得られる内部の配向構造が制御され
た光学異方体を提案した（特開平８−３１１１号）。該
発明の重合性液晶組成物は低分子化合物であり、粘度が
低く所望の配向状態を迅速に達成することができるとい
う長所を有している。しかしながら、該重合性液晶組成
物をガラスやプラスチック等の基板に塗布する場合に
は、均一な厚みをもって塗布するのが困難という問題が
あった。2. Description of the Related Art We have previously developed a polymerizable liquid crystal exhibiting liquid crystallinity at room temperature as a technology that enables the production of an optically anisotropic body such as an optical compensator that can improve the display quality of a liquid crystal display element and reduce its weight. A composition and an optically anisotropic body having a controlled internal orientation structure obtained by photopolymerization in a state where the composition is oriented have been proposed (JP-A-8-3111). The polymerizable liquid crystal composition of the present invention is a low molecular compound and has an advantage that it has a low viscosity and can quickly achieve a desired alignment state. However, when applying the polymerizable liquid crystal composition to a substrate such as glass or plastic, there is a problem that it is difficult to apply the polymerizable liquid crystal composition with a uniform thickness.
【０００３】[0003]
【本発明が解決しようとする課題】本発明が解決しよう
とする課題は、重合性低分子化合物を含有する液晶組成
物において所望の配向状態の迅速な達成を犠牲にするこ
となく、ガラスやプラスチック基板への良好な塗布性を
付与することであり、これを可能にする液晶性化合物と
液晶組成物を提供することにある。An object of the present invention is to provide a liquid crystal composition containing a polymerizable low molecular weight compound without sacrificing the rapid achievement of a desired alignment state without using glass or plastic. An object of the present invention is to provide good coatability to a substrate, and to provide a liquid crystal compound and a liquid crystal composition that enable this.
【０００４】[0004]
【課題を解決するための手段】本発明者等は上記課題を
解決するため、液晶性（メタ）アクリレート化合物の化
学構造とガラスやプラスチック基板へ塗布性との相関に
ついて鋭意検討した結果、かかる課題が、特定の化学構
造を有する液晶性（メタ）アクリレート化合物の利用に
より解決されることを見いだし本発明を提供するに至っ
た。即ち、 １．一般式（Ｉ）Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies on the correlation between the chemical structure of a liquid crystalline (meth) acrylate compound and the applicability to glass or plastic substrates. However, they have found that the problem can be solved by using a liquid crystal (meth) acrylate compound having a specific chemical structure, and have provided the present invention. That is, 1. General formula (I)
【０００５】[0005]
【化６】 Embedded image
【０００６】（式中、Ｘ1及びＸ2はそれぞれ独立的に水
素原子またはメチル基を表し、Ｐ1、Ｐ2、Ｐ3、Ｐ4、Ｐ
5及びＰ6はそれぞれ独立的に炭素原子数１から１８の２
価の炭化水素基を表し、Ｚ1、Ｚ2、Ｚ3、及びＺ4はそれ
ぞれ独立的に、−ＣＯＯ−または−ＯＣＯ−を表し、Ｙ
1及びＹ2はそれぞれ独立的に、単結合、−ＣＨ2ＣＨ
2−、−ＣＨ2Ｏ−、−ＯＣＨ2−、−ＣＯＯ−、−ＯＣ
Ｏ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、
−（ＣＨ2）4−、−ＣＨ2ＣＨ2ＣＨ2Ｏ−、−ＯＣＨ2Ｃ
Ｈ2ＣＨ2−、−ＣＨ＝ＣＨ−ＣＨ2ＣＨ2−、−ＣＨ2Ｃ
Ｈ2ＣＨ2Ｏ−、−ＯＯＣＣＯＯ−を表し、ｊ及びｋはそ
れぞれ独立的に０または１の整数を表し、ｎは０または
１の整数を表し、６員環Ａ、Ｂ及びＣはそれぞれ独立的
に、(Wherein X 1 and X 2 each independently represent a hydrogen atom or a methyl group, and P 1 , P 2 , P 3 , P 4 , P 4
5 and P 6 are each independently 2 to 18 carbon atoms.
Z 1 , Z 2 , Z 3 , and Z 4 each independently represent —COO— or —OCO—;
1 and Y 2 are each independently a single bond, -CH 2 CH
2 -, - CH 2 O - , - OCH 2 -, - COO -, - OC
O-, -C≡C-, -CH = CH-, -CF = CF-,
— (CH 2 ) 4 —, —CH 2 CH 2 CH 2 O—, —OCH 2 C
H 2 CH 2 -, - CH = CH-CH 2 CH 2 -, - CH 2 C
H 2 CH 2 O—, —OOCCOO—, j and k each independently represent an integer of 0 or 1, n represents an integer of 0 or 1, and the 6-membered rings A, B and C each represent an independent ,
【０００７】[0007]
【化７】 Embedded image
【０００８】を表し、Ｗはハロゲン原子またはメチル基
を表し、ｍは１〜４の整数を表す。）で表されることを
特徴とする液晶性（メタ）アクリレート化合物。 ２．一般式（Ｉ）において、Ｐ3及びＰ4がそれぞれ独立
的にメチレン基またはエチレン基であることを特徴とす
る上記１記載の液晶性（メタ）アクリレート化合物。 ３．一般式（Ｉ）において、Ｘ1及びＸ2は水素原子を表
し、Ｐ1、Ｐ2、Ｐ3、Ｐ4、Ｐ5及びＰ6はそれぞれ独立的
にメチレン基またはエチレン基を表し、Ｙ1及びＹ2はそ
れぞれ独立的に、−ＣＯＯ−、−ＯＣＯ−を表し、ｊ及
びｋはそれぞれ独立的に０または１の整数を表し、ｎは
１の整数を表し、６員環Ａ、Ｂ及びＣは、Wherein W represents a halogen atom or a methyl group, and m represents an integer of 1 to 4. A liquid crystalline (meth) acrylate compound represented by the formula: 2. 2. In the general formula (I), P 3 and P 4 are each independently a methylene group or an ethylene group. 3. In the general formula (I), X 1 and X 2 represent a hydrogen atom, P 1 , P 2 , P 3 , P 4 , P 5 and P 6 each independently represent a methylene group or an ethylene group, and Y 1 And Y 2 each independently represent -COO-, -OCO-, j and k each independently represent an integer of 0 or 1, n represents an integer of 1, and a 6-membered ring A, B and C is
【０００９】[0009]
【化８】 Embedded image
【００１０】を表す。）で表されることを特徴とする上
記１記載の液晶性アクリレート化合物。 ４．上記１乃至３記載の液晶性（メタ）アクリレート化
合物を含有し、液晶相を示すことを特徴とする液晶組成
物。 ５．液晶相が少なくとも２０℃〜３０℃の温度範囲で発
現することを特徴とする上記４記載の液晶組成物。 ６．上記１乃至３記載の液晶性（メタ）アクリレート化
合物を２重量％以上、及び少なくとも２つの６員環を有
する液晶骨格を部分構造として有する環状アルコール、
フェノール又は芳香族ヒドロキシ化合物のアクリル酸又
はメタクリル酸エステルである単官能アクリレート又は
単官能メタクリレートを含有し、液晶相を示すことを特
徴とする液晶組成物。 ７．単官能アクリレート又は単官能メタクリレートが一
般式（ＩＩ）、[0010] 2) The liquid crystalline acrylate compound according to the above 1, wherein 4. 4. A liquid crystal composition comprising the liquid crystalline (meth) acrylate compound according to any one of the above 1 to 3, and exhibiting a liquid crystal phase. 5. 5. The liquid crystal composition according to the above item 4, wherein the liquid crystal phase develops in a temperature range of at least 20 ° C to 30 ° C. 6. A cyclic alcohol having at least 2% by weight of the liquid crystal (meth) acrylate compound according to any one of the above 1 to 3 and a liquid crystal skeleton having at least two 6-membered rings as a partial structure;
A liquid crystal composition containing a monofunctional acrylate or a monofunctional methacrylate that is an acrylic acid or methacrylic acid ester of a phenol or an aromatic hydroxy compound, and exhibits a liquid crystal phase. 7. Monofunctional acrylate or methacrylate is represented by the general formula (II),
【００１１】[0011]
【化９】 Embedded image
【００１２】（式中、Ｘ3は水素原子又はメチル基を表
し、ｒは０または１の整数を表し、６員環Ｄ、Ｅ及びＦ
はそれぞれ独立的に、(Wherein X 3 represents a hydrogen atom or a methyl group, r represents an integer of 0 or 1, and a 6-membered ring D, E and F
Are each independently
【００１３】[0013]
【化１０】 Embedded image
【００１４】を表し、ｐは１〜４の整数を表し、Ｙ3及
びＹ4はそれぞれ独立的に、単結合、−ＣＨ2ＣＨ2−、
−ＣＨ2Ｏ−、−ＯＣＨ2−、−ＣＯＯ−、−ＯＣＯ−、
−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−（Ｃ
Ｈ2）4−、−ＣＨ2ＣＨ2ＣＨ2Ｏ−、−ＯＣＨ2ＣＨ2Ｃ
Ｈ2−、−ＣＨ＝ＣＨ−ＣＨ2ＣＨ2−、−ＣＨ2ＣＨ2Ｃ
Ｈ2Ｏ−を表し、Ｙ5は水素原子、ハロゲン原子、シアノ
基、炭素原子数１〜２０のアルキル基、アルコキシ基、
アルケニル基又はアルケニルオキシ基を表す。）で表さ
れることを特徴とする上記６記載の液晶組成物。 ８．液晶相が少なくとも２０℃〜３０℃の温度範囲で発
現することを特徴とする上記７記載の液晶組成物。 ９．上記７乃至８記載の液晶組成物の重合体であること
を特徴とする光学異方体。を前記課題の解決手段として
見出した。Wherein p is an integer of 1 to 4, and Y 3 and Y 4 are each independently a single bond, —CH 2 CH 2 —,
-CH 2 O -, - OCH 2 -, - COO -, - OCO-,
-C≡C-, -CH = CH-, -CF = CF-,-(C
H 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 C
H 2 -, - CH = CH -CH 2 CH 2 -, - CH 2 CH 2 C
H 2 O-a represents, Y 5 is hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group,
Represents an alkenyl group or an alkenyloxy group. 7. The liquid crystal composition according to the above item 6, wherein 8. 8. The liquid crystal composition according to the above 7, wherein the liquid crystal phase develops at least in a temperature range of 20 ° C to 30 ° C. 9. 9. An optically anisotropic body, which is a polymer of the liquid crystal composition described in the above item 7 or 8. Was found as a means for solving the above-mentioned problem.
【００１５】[0015]
【発明の実施の形態】以下に本発明の液晶性（メタ）ア
クリレート化合物と液晶組成物及びこれを用いた液晶組
成物の一例について説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an example of a liquid crystal (meth) acrylate compound of the present invention, a liquid crystal composition and a liquid crystal composition using the same will be described.
【００１６】一般式（Ｉ）の液晶性（メタ）アクリレー
ト化合物は、６員環Ａ、Ｂ、Ｃ及び連結基Ｙ1、Ｙ2から
構成される剛直な液晶骨格の両端に位置するフレキシブ
ルなスペーサー部分において、（メタ）アクリロイルオ
キシ基に含まれるエステル基以外に少なくとも一つのエ
ステル結合を有していることを特徴としている。これに
より、１分子あたり多数のエステル基が存在することに
よる粘度の増大、さらに多数のカルボニル基の分極構造
によりガラス表面等への親和性が増大することにより、
良好な塗布性が得られるものと考えられる。The liquid crystalline (meth) acrylate compound of the general formula (I) is a flexible spacer located at both ends of a rigid liquid crystal skeleton composed of 6-membered rings A, B and C and connecting groups Y 1 and Y 2. It is characterized in that the portion has at least one ester bond other than the ester group contained in the (meth) acryloyloxy group. Thereby, the viscosity increases due to the presence of a large number of ester groups per molecule, and the affinity for the glass surface or the like increases due to the polarization structure of a large number of carbonyl groups.
It is considered that good coatability is obtained.
【００１７】以下、本発明を更に詳細に説明する。本発
明の液晶性（メタ）アクリレート化合物（以下、本発明
の化合物）は、一般式（ＩＩＩ）Hereinafter, the present invention will be described in more detail. The liquid crystalline (meth) acrylate compound of the present invention (hereinafter, compound of the present invention) is represented by the general formula (III):
【００１８】[0018]
【化１１】 Embedded image
【００１９】（式中、Ｐ1、Ｐ2、Ｐ3、Ｐ4、Ｐ5、Ｐ6、
Ｚ1、Ｚ2、Ｚ3、Ｚ4、Ｙ1、Ｙ2、ｊ、ｋ、ｎ、６員環
Ａ、Ｂ及びＣの意味は、一般式（Ｉ）における意味と同
じ。）の化合物の両端の水酸基を、例えば、トリエチル
アミンの如き塩基存在下で（メタ）アクリロイルクロリ
ドのような酸ハロゲン化物との反応によりエステル化さ
せるか、酸触媒存在下で（メタ）アクリル酸との反応に
よりエステル化させることにより製造することができ
る。(Where P 1 , P 2 , P 3 , P 4 , P 5 , P 6 ,
The meanings of Z 1 , Z 2 , Z 3 , Z 4 , Y 1 , Y 2 , j, k, n, and the six-membered rings A, B, and C are the same as those in formula (I). The hydroxyl groups at both ends of the compound are esterified by reaction with an acid halide such as (meth) acryloyl chloride in the presence of a base such as triethylamine, or the reaction with (meth) acrylic acid in the presence of an acid catalyst. It can be produced by esterification by a reaction.
【００２０】また、一般式（ＩＶ）In addition, the general formula (IV)
【００２１】[0021]
【化１２】 Embedded image
【００２２】（式中、Ｐ3、Ｐ4、Ｙ1、Ｙ2、ｎ、６員環
Ａ、Ｂ及びＣの意味は、一般式（Ｉ）における意味と同
じ。）の両端にある水酸基を、（メタ）アクリルロイル
オキシ基及びカルボキシル基を有する一般に市販されて
いる化合物、例えば「Ｍ−５６００」（東亞合成株式会
社製）(Wherein P 3 , P 4 , Y 1 , Y 2 , n, and the six-membered rings A, B, and C have the same meanings as in the general formula (I).) , A generally commercially available compound having a (meth) acryloyloxy group and a carboxyl group, for example, “M-5600” (manufactured by Toagosei Co., Ltd.)
【００２３】[0023]
【化１３】 Embedded image
【００２４】や「ＨＯＡ−ＭＳ」（共栄社化学株式会社
製）And "HOA-MS" (manufactured by Kyoeisha Chemical Co., Ltd.)
【００２５】[0025]
【化１４】 Embedded image
【００２６】とジシクロヘキシルカルボジイミドの如き
縮合剤を用いてエステル化させるか、カルボキシル基を
ハロゲン化アシル基に変換した後に、エステル化させる
ことにより製造することができる。And esterification by using a condensing agent such as dicyclohexylcarbodiimide, or by converting a carboxyl group into an acyl halide group and then esterifying.
【００２７】また、一般式（Ｖ）The general formula (V)
【００２８】[0028]
【化１５】 Embedded image
【００２９】（式中、Ｐ3、Ｐ4、Ｙ1、Ｙ2、ｎ、６員環
Ａ、Ｂ及びＣの意味は、一般式（Ｉ）における意味と同
じ。）の両端にあるカルボキシル基を、２−ヒドロキシ
エチル（メタ）アクリレートや、４−ヒドロキシブチル
（メタ）アクリレート等のヒドロキシアルキル（メタ）
アクリレート化合物の水酸基とジシクロヘキシルカルボ
ジイミドの如き縮合剤を用いてエステル化させることに
より製造することができる。(Wherein P 3 , P 4 , Y 1 , Y 2 , n, and the six-membered rings A, B and C have the same meanings as in the general formula (I)). With hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate
It can be produced by esterifying the hydroxyl group of the acrylate compound with a condensing agent such as dicyclohexylcarbodiimide.
【００３０】また、例えば一般式（ＶＩ）Further, for example, the compound represented by the general formula (VI)
【００３１】[0031]
【化１６】 Embedded image
【００３２】（式中、Ｐ3、６員環Ａの意味は、一般式
（Ｉ）における意味と同じ、Ｘは水酸基、または保護さ
れた水酸基、ハロゲン基、カルボキシル基、保護された
カルボキシル基等を表す。）のＰ3に隣接する水酸基と
「Ｍ−５６００」（東亞合成株式会社製）や「ＨＯＡ−
ＭＳ」（共栄社化学株式会社製）をジシクロヘキシルカ
ルボジイミドの如き縮合剤を用いてエステル化させた
後、これをビルディングブロックとしてＸ基を反応点と
して、液晶骨格を形成していく方法でも製造することが
できる。例えば、Ｘ基がカルボキシル基であった場合に
は、１／２等量のヒドロキノン誘導体とエステル化させ
ることにより、簡便に目的とする化合物を製造すること
ができる。(Wherein, P 3 and the six-membered ring A have the same meanings as in the general formula (I), and X represents a hydroxyl group, a protected hydroxyl group, a halogen group, a carboxyl group, a protected carboxyl group, etc.) Represents a hydroxyl group adjacent to P 3 and “M-5600” (manufactured by Toagosei Co., Ltd.) or “HOA-
MS "(manufactured by Kyoeisha Chemical Co., Ltd.) by esterification using a condensing agent such as dicyclohexylcarbodiimide, and then using this as a building block with the X group as a reaction point to form a liquid crystal skeleton. it can. For example, when the X group is a carboxyl group, the desired compound can be easily produced by esterification with a 1/2 equivalent hydroquinone derivative.
【００３３】また、例えば一般式（ＶＩＩ）Further, for example, the compound represented by the general formula (VII)
【００３４】[0034]
【化１７】 Embedded image
【００３５】（式中、Ｐ3、６員環Ａの意味は、一般式
（Ｉ）における意味と同じ、Ｘは水酸基、または保護さ
れた水酸基、ハロゲン基、カルボキシル基、保護された
カルボキシル基等を表す。）のＰ3に隣接するカルボキ
シル基を、２−ヒドロキシエチル（メタ）アクリレート
や、４−ヒドロキシブチル（メタ）アクリレート等のヒ
ドロキシアルキル（メタ）アクリレート化合物の水酸基
とジシクロヘキシルカルボジイミドの如き縮合剤を用い
てエステル化させることによりエステル化させた後、こ
れをビルディングブロックとして一般式（ＶＩＩ）のＸ
基を反応点として、液晶骨格を形成していく方法でも製
造することができる。例えば、Ｘ基がカルボキシル基で
あった場合には、１／２等量のテレフタル酸誘導体とエ
ステル化させることにより、簡便に目的とする化合物を
製造することができる。(Wherein, P 3 and the six-membered ring A have the same meanings as those in the general formula (I), and X represents a hydroxyl group, a protected hydroxyl group, a halogen group, a carboxyl group, a protected carboxyl group, etc.) the representative. carboxyl group adjacent to P 3) of 2-hydroxyethyl and ethyl (meth) acrylate, 4-hydroxybutyl (meth) hydroxyalkyl (meth) such as condensing agent of hydroxyl group and dicyclohexylcarbodiimide acrylate compounds such as acrylate After esterification by esterification with a compound represented by general formula (VII),
It can also be produced by a method of forming a liquid crystal skeleton using a group as a reaction point. For example, when the X group is a carboxyl group, the desired compound can be easily produced by esterification with a 等 equivalent of a terephthalic acid derivative.
【００３６】一般式（Ｉ）のＸ1及びＸ2には、本発明の
化合物に迅速なる光重合性を要求する場合には、メチル
基よりも水素原子を選択するのが好ましい。また、本発
明の化合物は発明の目的から、単体として液晶相、特に
ネマチック相、スメクチックA相、スメクチックC相を示
すことが好ましい。このことから、Ｐ1、Ｐ2、Ｐ3、
Ｐ4、Ｐ5、Ｐ6はそれぞれ独立的に、炭素原子数１〜１
８の２価の炭化水素基を選択することができるが、炭素
原子数が６以上になると液晶性が発現しにくくなるた
め、炭素原子数１〜６のアルキレン基が好ましく、炭素
原子数１〜２のアルキレン基が更に好ましい。またｎが
０の場合、液晶性が発現しにくくなるため、ｎは１が好
ましい。また、環Ａ、Ｂ及びＣは、化合物の屈折性を大
きくすることができるため、パラフェニレン基を選択す
るのが特に好ましい。また、化合物の転移温度を調節や
誘電率の大きさを調節する目的で、パラフェニレン基の
水素原子を１〜４個までのハロゲン原子やメチル基で置
換するのは特に好ましい。For X 1 and X 2 in the general formula (I), a hydrogen atom is preferably selected over a methyl group when rapid photopolymerization of the compound of the present invention is required. For the purpose of the present invention, the compound of the present invention preferably shows a liquid crystal phase as a simple substance, particularly a nematic phase, a smectic A phase, and a smectic C phase. From this, P 1 , P 2 , P 3 ,
P 4 , P 5 and P 6 each independently represent a group having 1 to 1 carbon atoms.
Although a divalent hydrocarbon group of 8 can be selected, an alkylene group having 1 to 6 carbon atoms is preferable since a liquid crystallinity is hardly developed when the number of carbon atoms is 6 or more, and an alkylene group having 1 to 6 carbon atoms is preferable. Two alkylene groups are more preferred. When n is 0, liquid crystallinity is hardly developed, so n is preferably 1. In addition, it is particularly preferable to select a paraphenylene group for rings A, B, and C since the refractive index of the compound can be increased. Further, for the purpose of controlling the transition temperature of the compound or the magnitude of the dielectric constant, it is particularly preferable to replace the hydrogen atom of the paraphenylene group with 1 to 4 halogen atoms or methyl groups.
【００３７】本発明は更に、本発明の化合物を含有する
液晶組成物をも提供する。本発明の液晶組成物の液晶相
としては、通常この技術分野で液晶相と認識される相で
あれば特に制限なく用いることができるが、その中でも
ネマチック相、スメクチックＡ相、（カイラル）スメク
チックＣ相、コレステリック相を発現するものが特に好
ましい。また、（カイラル）スメクチックＣ相を示す場
合には、該（カイラル）スメクチックＣ相の上の温度領
域でスメクチックＡ相を、スメクチックＡ相を示す場合
には、該スメクチックＡ相の上の温度領域でネマチック
相を発現するようにすると、良好な一軸の配向特性が得
られるため好ましい。実際に紫外線を照射して本発明の
液晶組成物中の（メタ）アクリレート化合物を重合させ
る液晶相の温度領域もしくは実際に使用する液晶相の温
度領域としては、室温付近、即ち少なくとも２０〜３０
℃の温度範囲で液晶相を発現するものが特に好ましい。
例えば（カイラル）スメクチックＣ相で実際に本発明の
液晶組成物を重合させる場合には、（カイラル）スメク
チックＣ相が室温付近で、即ち少なくとも２０〜３０℃
の温度範囲で（カイラル）スメクチックＣ相が発現する
ものが好ましい。The present invention further provides a liquid crystal composition containing the compound of the present invention. As the liquid crystal phase of the liquid crystal composition of the present invention, any phase which is generally recognized as a liquid crystal phase in this technical field can be used without particular limitation. Among them, a nematic phase, a smectic A phase and a (chiral) smectic C And a cholesteric phase are particularly preferred. In addition, in the case of showing a (chiral) smectic C phase, the smectic A phase is in a temperature range above the (chiral) smectic C phase, and in the case of showing a smectic A phase, the temperature range is above the smectic A phase. It is preferable that a nematic phase be developed in such a way that good uniaxial orientation characteristics can be obtained. The temperature range of the liquid crystal phase in which the (meth) acrylate compound in the liquid crystal composition of the present invention is polymerized by actually irradiating ultraviolet rays or the temperature range of the liquid crystal phase actually used is around room temperature, that is, at least 20 to 30.
Those exhibiting a liquid crystal phase in a temperature range of ° C. are particularly preferred.
For example, when the liquid crystal composition of the present invention is actually polymerized in a (chiral) smectic C phase, the (chiral) smectic C phase is kept at around room temperature, that is, at least 20 to 30 ° C.
It is preferable that a (chiral) smectic C phase be developed in the above temperature range.
【００３８】本発明の液晶組成物には、ガラスやプラス
チック基板への良好な塗布性能を確保するため、本発明
の化合物を２重量％以上含有させることが好ましい。本
発明の化合物が２重量％以下である場合には、良好な塗
布性能が確保されない傾向がある。The liquid crystal composition of the present invention preferably contains 2% by weight or more of the compound of the present invention in order to ensure good coating performance on a glass or plastic substrate. When the amount of the compound of the present invention is 2% by weight or less, good coating performance tends not to be secured.
【００３９】また、本発明の液晶組成物には、分子内に
通常この技術分野で液晶骨格と認められる骨格と重合性
官能基を同時に有する重合性の液晶化合物を９８重量％
以下の濃度で特に制限なく添加することができる。液晶
骨格としては、少なくとも２つ又は３つの６員環を有す
るものが特に好ましい。重合性官能基としては、（メ
タ）アクリロイルオキシ基、エポキシ基、ビニルエーテ
ル基、シンナモイル基、ビニル基等を挙げることができ
るが、良好な光重合特性が得られることから、アクリロ
イルオキシ基が特に好ましい。複数以上の重合性官能基
を有する化合物の場合には、重合性官能基の種類が異な
っていても良い。例えば、２つの重合性官能基を有する
液晶化合物の場合、一つがアクリロイルオキシ基、もう
一つがメタアクリロイルオキシ基または、ビニルエーテ
ル基であっても良い。重合性官能基を２つ有する液晶化
合物は多くの種類が知られており、一般的にこれらを重
合させた場合には良好な耐熱性及び強度特性を得られる
ことから、好適に用いることができる。このような重合
性官能基を２つ有する液晶化合物の具体的な例として
は、式（１）〜（１０）に挙げた化合物が好ましいが、
本発明の液晶組成物において使用することができる化合
物はこれらに限定されるものではない。The liquid crystal composition of the present invention contains 98% by weight of a polymerizable liquid crystal compound having simultaneously a skeleton and a polymerizable functional group which are generally recognized as a liquid crystal skeleton in the art.
The following concentrations can be added without particular limitation. As the liquid crystal skeleton, those having at least two or three six-membered rings are particularly preferable. Examples of the polymerizable functional group include a (meth) acryloyloxy group, an epoxy group, a vinyl ether group, a cinnamoyl group, and a vinyl group, and an acryloyloxy group is particularly preferable because good photopolymerization characteristics are obtained. . In the case of a compound having a plurality of polymerizable functional groups, the types of the polymerizable functional groups may be different. For example, in the case of a liquid crystal compound having two polymerizable functional groups, one may be an acryloyloxy group and the other may be a methacryloyloxy group or a vinyl ether group. Many types of liquid crystal compounds having two polymerizable functional groups are known, and generally, when these are polymerized, good heat resistance and strength characteristics can be obtained, and thus, they can be preferably used. . As specific examples of such a liquid crystal compound having two polymerizable functional groups, the compounds listed in formulas (1) to (10) are preferable.
Compounds that can be used in the liquid crystal composition of the present invention are not limited to these.
【００４０】[0040]
【化１８】 Embedded image
【００４１】（式中、シクロヘキサン環はトランスシク
ロヘキサン環を表し、Ｘはハロゲン原子、シアノ基、メ
チル基を表し、ｓは２〜１２の整数を表す。） さらに本発明の液晶組成物には、分子内に一つの重合性
官能基を有する液晶化合物を添加しても良い。このよう
な重合性官能基を一つ有する液晶化合物の具体的な例と
しては、式（１１）〜（５６）に挙げた化合物が好まし
いが、本発明の液晶組成物において使用することができ
る化合物はこれらに限定されるものではない。(In the formula, the cyclohexane ring represents a transcyclohexane ring, X represents a halogen atom, a cyano group, or a methyl group, and s represents an integer of 2 to 12.) Further, in the liquid crystal composition of the present invention, A liquid crystal compound having one polymerizable functional group in the molecule may be added. As specific examples of such a liquid crystal compound having one polymerizable functional group, the compounds listed in formulas (11) to (56) are preferable, but the compounds that can be used in the liquid crystal composition of the present invention Is not limited to these.
【００４２】[0042]
【化１９】 Embedded image
【００４３】[0043]
【化２０】 Embedded image
【００４４】[0044]
【化２１】 Embedded image
【００４５】[0045]
【化２２】 Embedded image
【００４６】（式中、シクロヘキサン環はトランスシク
ロヘキサン環を表し、Ｙは水素原子、ハロゲン原子、シ
アノ基、炭素原子数１〜２０のアルキル基、アルコキシ
基、アルケニル基、アルケニルオキシ基を表し、ｓは２
から１２の整数を表す。） さらに本発明の液晶組成物には、室温付近、即ち少なく
とも２０〜３０℃の温度範囲での液晶相の発現を容易に
し、かつ液晶組成物の光重合物の耐熱性及び強度特性の
確保を図ることを目的として、少なくとも２つの６員環
を有する液晶骨格を部分構造として有する環状アルコー
ル、フェノール又は芳香族ヒドロキシ化合物のアクリル
酸又はメタクリル酸エステルである単官能（メタ）アク
リレートを含有させても良い。なぜなら、このような単
官能（メタ）アクリレートは、（メタ）アクリロイルオ
キシ基と液晶骨格との間に、アルキレン基又はオキシア
ルキレン基等の液晶の技術分野でスペーサーと呼ばれる
柔軟性の連結基が無い。そのため、このような単官能
（メタ）アクリレートを重合させて得られる重合体の主
鎖には、スペーサーを介さず直接剛直な液晶骨格が結合
し、液晶骨格の熱運動は高分子主鎖により制限されるこ
とが予想され、優れた耐熱性及び強度特性が期待できる
ためである。また、分子形状的に液晶性を低下させてし
まう（メタ）アクリロイルオキシ基を分子内に一つ有し
ているだけなので、液晶を発現させる温度範囲の制御も
分子内に複数の（メタ）アクリロイルオキシ基を有する
化合物より容易になる。このよう単官能（メタ）アクリ
レートとしては一般式（ＩＩ）(Wherein the cyclohexane ring represents a transcyclohexane ring, Y represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group; Is 2
From 12 to 12. Further, the liquid crystal composition of the present invention facilitates the development of a liquid crystal phase near room temperature, that is, at least in the temperature range of 20 to 30 ° C., and ensures the heat resistance and strength properties of the photopolymer of the liquid crystal composition. For the purpose of achieving, a monofunctional (meth) acrylate which is an acrylic acid or methacrylic acid ester of a cyclic alcohol, phenol or aromatic hydroxy compound having a liquid crystal skeleton having at least two 6-membered rings as a partial structure may be contained. good. This is because such a monofunctional (meth) acrylate does not have a flexible connecting group called a spacer in the technical field of liquid crystal such as an alkylene group or an oxyalkylene group between the (meth) acryloyloxy group and the liquid crystal skeleton. . Therefore, a rigid liquid crystal skeleton is directly bonded to the main chain of the polymer obtained by polymerizing such a monofunctional (meth) acrylate without using a spacer, and the thermal motion of the liquid crystal skeleton is limited by the polymer main chain. This is because excellent heat resistance and strength properties can be expected. In addition, since there is only one (meth) acryloyloxy group in the molecule that reduces the liquid crystallinity in terms of the molecular shape, the temperature range for developing the liquid crystal can be controlled by multiple (meth) acryloyl groups in the molecule. It is easier than a compound having an oxy group. Such a monofunctional (meth) acrylate is represented by the general formula (II)
【００４７】[0047]
【化２３】 Embedded image
【００４８】（式中、Ｘ3は水素原子又はメチル基を表
し、ｒは０または１の整数を表し、６員環Ｄ、Ｅ及びＦ
はそれぞれ独立的に、(Wherein X 3 represents a hydrogen atom or a methyl group, r represents an integer of 0 or 1, and a 6-membered ring D, E and F
Are each independently
【００４９】[0049]
【化２４】 Embedded image
【００５０】を表し、ｐは１〜４の整数を表し、Ｙ3及
びＹ4はそれぞれ独立的に、単結合、−ＣＨ2ＣＨ2−、
−ＣＨ2Ｏ−、−ＯＣＨ2−、−ＣＯＯ−、−ＯＣＯ−、
−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−（Ｃ
Ｈ2）4−、−ＣＨ2ＣＨ2ＣＨ2Ｏ−、−ＯＣＨ2ＣＨ2Ｃ
Ｈ2−、−ＣＨ＝ＣＨ−ＣＨ2ＣＨ2−、−ＣＨ2ＣＨ2Ｃ
Ｈ2Ｏ−を表し、Ｙ5は水素原子、ハロゲン原子、シアノ
基、炭素原子数１〜２０のアルキル基、アルコキシ基、
アルケニル基、アルケニルオキシ基を表す。）で表され
る化合物が好ましい。このような単官能（メタ）アクリ
レートの具体的な例としては、式（５７）〜（６７）に
挙げた化合物が好ましいが、本発明の液晶組成物におい
て使用することができる単官能（メタ）アクリレートは
これらに限定されるものではない。Wherein p is an integer of 1 to 4, Y 3 and Y 4 are each independently a single bond, —CH 2 CH 2 —,
-CH 2 O -, - OCH 2 -, - COO -, - OCO-,
-C≡C-, -CH = CH-, -CF = CF-,-(C
H 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 C
H 2 -, - CH = CH -CH 2 CH 2 -, - CH 2 CH 2 C
H 2 O-a represents, Y 5 is hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group,
Represents an alkenyl group or an alkenyloxy group. ) Is preferred. As specific examples of such a monofunctional (meth) acrylate, the compounds listed in the formulas (57) to (67) are preferable, but the monofunctional (meth) acrylate that can be used in the liquid crystal composition of the present invention. Acrylates are not limited to these.
【００５１】[0051]
【化２５】 Embedded image
【００５２】[0052]
【化２６】 Embedded image
【００５３】（上記中、シクロヘキサン環はトランスシ
クロヘキサン環を表し、またＣは結晶相、Ｎはネマチッ
ク相、Ｓはスメクチック相、Ｉは等方性液体相を表し、
数字は相転移温度を表す。） また、本発明の液晶組成物には、重合性官能基を有して
いない液晶化合物を用途に応じて添加しても良い。使用
用途として本発明の液晶組成物の重合体を、表示素子と
用いる場合や、温度によって屈折率を変化させたい場合
には、重合性官能基を有していない液晶化合物の総量は
３０〜９８重量％の範囲に設定するのが好ましい。ま
た、温度によって屈折率が変化するのが好ましくない場
合や、耐熱性や機械的特性を重視する場合には、重合性
官能基を有していない液晶化合物の総量は０〜３０重量
％の範囲に設定するのが好ましい。(In the above, the cyclohexane ring represents a transcyclohexane ring, C represents a crystal phase, N represents a nematic phase, S represents a smectic phase, I represents an isotropic liquid phase,
The numbers represent the phase transition temperatures. In addition, a liquid crystal compound having no polymerizable functional group may be added to the liquid crystal composition of the present invention depending on the use. When the polymer of the liquid crystal composition of the present invention is used as a display element, or when it is desired to change the refractive index depending on temperature, the total amount of the liquid crystal compound having no polymerizable functional group is 30 to 98. It is preferable to set the weight% in the range. When it is not preferable that the refractive index changes depending on the temperature, or when importance is placed on heat resistance and mechanical properties, the total amount of the liquid crystal compound having no polymerizable functional group is in the range of 0 to 30% by weight. It is preferable to set
【００５４】また、本発明の液晶組成物には重合性官能
基を有しており、かつ液晶性を示さない化合物も添加す
ることができる。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、アクリレート化合物、メタク
リレート化合物、ビニルエーテル化合物が特に好まし
い。Further, a compound having a polymerizable functional group and having no liquid crystallinity can be added to the liquid crystal composition of the present invention. Such a compound can be used without any particular limitation as long as it is generally recognized as a polymer-forming monomer or a polymer-forming oligomer in this technical field, and acrylate compounds, methacrylate compounds, and vinyl ether compounds can be used. Particularly preferred.
【００５５】以上のような重合性官能基を有する液晶化
合物、重合性官能基を有さない液晶化合物、液晶性を示
さない重合性化合物は適宜組み合わせて添加してもよい
が、少なくとも得られる液晶組成物の液晶性が失われな
いように各成分の添加量を調整することが必要である。The above-mentioned liquid crystal compound having a polymerizable functional group, a liquid crystal compound having no polymerizable functional group, and a polymerizable compound having no liquid crystallinity may be added in appropriate combination. It is necessary to adjust the addition amount of each component so that the liquid crystallinity of the composition is not lost.
【００５６】更に本発明の液晶組成物には、その重合反
応性を向上させることを目的として、熱重合開始剤、光
重合開始剤の重合開始剤を添加しても良い。ここで使用
できる熱重合開始剤としては、過酸化ベンゾイル、ビス
アゾブチロニトリル等から選択することができ、光重合
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等から選択
して使用することができる。その添加量は、液晶組成物
に対して１０重量％以下であることが好ましく、５重量
％以下であることがさらに好ましく、０．５〜１．５重
量％の範囲であることが特に好ましい。Further, to the liquid crystal composition of the present invention, a polymerization initiator such as a thermal polymerization initiator and a photopolymerization initiator may be added for the purpose of improving the polymerization reactivity. The thermal polymerization initiator that can be used here can be selected from benzoyl peroxide, bisazobutyronitrile, and the like, and the photopolymerization initiator is selected from benzoin ethers, benzophenones, acetophenones, benzyl ketals, and the like. Can be used. The addition amount is preferably 10% by weight or less, more preferably 5% by weight or less, particularly preferably in the range of 0.5 to 1.5% by weight, based on the liquid crystal composition.
【００５７】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しても良い。こ
こで使用することができる安定剤としては、例えばヒド
ロキノン、ヒドロキノンモノアルキルエーテル類、第三
ブチルカテコール等から選択して使用することができ
る。その添加量は、液晶組成物に対して１重量％以下が
好ましく、０．５重量％以下がさらに好ましい。Further, a stabilizer may be added to the liquid crystal composition of the present invention in order to improve the storage stability. As the stabilizer that can be used here, for example, hydroquinone, hydroquinone monoalkyl ethers, tert-butyl catechol and the like can be used. The addition amount is preferably 1% by weight or less, more preferably 0.5% by weight or less based on the liquid crystal composition.
【００５８】また、本発明の液晶組成物には、液晶骨格
の螺旋構造を内部に有する重合体を得ることを目的とし
てカイラル（光学活性）化合物を添加しても良い。ここ
で使用することができるカイラル化合物は、それ自体が
液晶性を示す必要は無く、また重合性官能基を有してい
ても、有していなくても良い。またその螺旋の向きは重
合体の使用用途によって適宜選択することができる。そ
のようなカイラル化合物としては光学活性基としてコレ
ステリル基を有するペラルゴン酸コレステロール、ステ
アリン酸コレステロール、光学活性基として２−メチル
ブチル基を有する「ＣＢ−１５」、「Ｃ−１５」（以上
ＢＤＨ社製）、「Ｓ−１０８２」（メルク社製）、「Ｃ
Ｍ−１９」、「ＣＭ−２０」、「ＣＭ」（以上チッソ社
製）、光学活性基として１−メチルヘプチル基を有する
「Ｓ−８１１」（メルク社製）、「ＣＭ−２１」、「Ｃ
Ｍ−２２」（以上チッソ社製）を挙げることができる。
このカイラル化合物の好ましい添加量は液晶組成物の用
途によるが、重合して得られる重合体の厚み（ｄ）を重
合体中での螺旋ピッチ（Ｐ）で除した値（ｄ／Ｐ）が
０．１〜２０の範囲になるよう調整するのが好ましい。Further, a chiral (optically active) compound may be added to the liquid crystal composition of the present invention for the purpose of obtaining a polymer having a helical structure of a liquid crystal skeleton therein. The chiral compound that can be used here need not itself exhibit liquid crystallinity, and may or may not have a polymerizable functional group. The direction of the helix can be appropriately selected according to the intended use of the polymer. As such chiral compounds, cholesteryl pelargonic acid having a cholesteryl group as an optically active group, cholesterol stearate, and “CB-15” and “C-15” having a 2-methylbutyl group as an optically active group (all manufactured by BDH) , "S-1082" (manufactured by Merck), "C
M-19 "," CM-20 "," CM "(manufactured by Chisso)," S-811 "having a 1-methylheptyl group as an optically active group (manufactured by Merck)," CM-21 "," CM-21 " C
M-22 "(all manufactured by Chisso Corporation).
The preferable addition amount of the chiral compound depends on the use of the liquid crystal composition, but the value (d / P) obtained by dividing the thickness (d) of the polymer obtained by polymerization by the helical pitch (P) in the polymer is 0. It is preferable to adjust so as to fall within a range of 0.1 to 20.
【００５９】また、本発明の液晶組成物を偏光フィルム
や配向膜の原料、または印刷インキ及び塗料等として利
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、界面活性剤、ゲル化剤、紫外線吸収
剤、抗酸化剤、イオン交換樹脂、酸化チタンの金属酸化
物等を添加することもできる。When the liquid crystal composition of the present invention is used as a raw material for a polarizing film or alignment film, or as a printing ink or paint, a metal, metal complex, dye, pigment, dye, Activators, gelling agents, ultraviolet absorbers, antioxidants, ion exchange resins, metal oxides of titanium oxide, and the like can also be added.
【００６０】本発明は更に、本発明の液晶組成物の重合
体であることを特徴とする光学異方体をも提供する。本
発明の光学異方体は、本発明の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することがで
きる。例えば、基板表面を布等でラビング、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、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
せる方法を挙げることができる。その他の配向処理方法
としては、液晶組成物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。その中
でも基板表面を布等でラビング処理した基板を用いる方
法は、その簡便性から特に好ましい。The present invention further provides an optically anisotropic material which is a polymer of the liquid crystal composition of the present invention. The optically anisotropic body of the present invention can be produced by polymerizing the liquid crystal composition of the present invention in an oriented state. For example, after the substrate surface is rubbed with a cloth or the like, or the substrate surface on which an organic thin film is formed is rubbed with a cloth or the like, or is carried on a substrate having an alignment film in which SiO 2 is obliquely deposited, or after being sandwiched between substrates. And a method of polymerizing the liquid crystal of the present invention. Examples of other alignment treatment methods include the use of flow alignment of the liquid crystal composition and the use of an electric or magnetic field. These alignment means may be used alone or in combination. Among them, a method using a substrate whose surface is rubbed with a cloth or the like is particularly preferable because of its simplicity.
【００６１】この時使用することができる基板は、有機
材料、無機材料を問わずに用いることができる。具体的
な例を挙げると有機材料としては、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、無機材料としてはシリコン、ガラス、方解
石等を挙げることができる。The substrate that can be used at this time may be an organic material or an inorganic material. Specific examples include organic materials such as polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone, and inorganic materials include silicon, glass, calcite, and the like.
【００６２】これらの基板を布等でラビングすることを
によって適当な配向性を得られないときには、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又はＳＴＮ素子で使用
されているようなプレチルト角を与えるポリイミド薄膜
を利用すると、光学異方体内部の分子配向構造を更に精
密に制御できることから、特に好ましく利用することが
できる。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とができ、この場
合には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。When it is not possible to obtain an appropriate orientation 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 surface of the substrate according to a known method, and this is coated with a cloth or the like. You may rub. Further, when a polyimide thin film giving a pretilt angle as used in a normal TN or STN element is used, the molecular orientation structure inside the optically anisotropic body can be controlled more precisely, so that it can be used particularly preferably. When the orientation state is controlled by an electric field, a substrate having an electrode layer can be used. In this case, it is preferable to form an organic thin film such as the above-mentioned polyimide thin film on the electrode.
【００６３】また、ラビングに代わる配向処理方法とし
て、光配向法も用いることができる。これはポリビニル
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
する有機薄膜や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、このまし
くは偏光した紫外線を照射することによって、配向膜と
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。A photo-alignment method can be used as an alignment treatment method instead of rubbing. This is a polarized light, preferably a polarized light, on an organic thin film having a functional group that undergoes a photodimerization reaction in a molecule such as polyvinyl cinnamate, an organic thin film having a functional group that isomerized by light, or an organic thin film such as a polyimide. The alignment film is formed by irradiating ultraviolet rays. By applying a photomask to this photoalignment method, patterning of the alignment can be easily achieved, so that the molecular orientation inside the optically anisotropic body can be precisely controlled.
【００６４】重合の方法としては、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エネルギーを照射
することによって光重合させる方法が好ましい。この光
重合させる際の光源としては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光重合を行う場合には、
少なくとも照射面側の基板は適当な透明性が与えられて
いなければならない。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
る意味からもできるだけ室温に近い温度で、即ち２０〜
３０℃の温度で重合させることが好ましい。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
をしても良い。熱処理の温度としては５０〜２５０℃の
温度範囲で、また熱処理時間としては３０秒〜１２時間
の範囲にあるのが好ましい。As the polymerization method, since rapid polymerization is desirable, a method of performing photopolymerization by irradiating energy such as ultraviolet rays or an electron beam is preferable. As the light source for the photopolymerization, a polarized light source or a non-polarized light source may be used. In addition, the liquid crystal composition
When performing photopolymerization in a state sandwiched between two substrates,
At least the substrate on the irradiation surface side must be given appropriate transparency. Further, the temperature at the time of irradiation is preferably within a temperature range where the liquid crystal state of the liquid crystal composition of the present invention is maintained. In particular, when an optically anisotropic material is to be produced by photopolymerization, the temperature should be as close to room temperature as possible from the viewpoint of avoiding unintended thermal polymerization, that is, 20 to
It is preferred to polymerize at a temperature of 30 ° C. The optically anisotropic body of the present invention obtained by the polymerization may be subjected to a heat treatment for the purpose of reducing the initial property change and stably exhibiting the property. The temperature of the heat treatment is preferably in a temperature range of 50 to 250 ° C., and the heat treatment time is preferably in a range of 30 seconds to 12 hours.
【００６５】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、基板から剥離して用いても、剥離せず
に用いても良い。The optically anisotropic body of the present invention manufactured by such a method may be used after peeling from the substrate or without peeling.
【００６６】[0066]
【実施例】以下、本発明の実施例を示し、本発明を更に
詳細に説明する。しかしながら、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、相転移温度におけ
るＳｘは詳細な相構造は未決定のスメクチック相を、Ｎ
はネマチック相を、Ｉは等方性液体相を、Ｃは結晶相を
それぞれ表す。 （実施例１） 液晶性アクリレート化合物の合成
（１） ディーンスターク水分離器を装着した３口フラスコに、
４−（ヒドロキシエチル）フェノール１０ｇ、「Ｍ−５
６００」（東亞合成株式会社製）２２．５ｇ、ヒドロキ
ノン０．１ｇ、ｐ−トルエンスルホン酸１水和物３．２
ｇ、ｎ−ヘキサン６０ｍｌ、トルエン６０ｍｌを加えて
撹拌しながら加熱した。３時間加熱環流後、室温まで反
応液を冷却した。これに飽和食塩水５００ｍｌを加えた
後、反応液をトルエン２００ｍｌを加えて抽出を行っ
た。有機層を飽和炭酸水素ナトリウム水溶液及び水で洗
った後、トルエンを減圧留去して化合物（ａ）の粗生成
物１１．８ｇを得た。The present invention will be described below in more detail with reference to Examples of the present invention. However, the invention is not limited to these examples. Further, Sx at the phase transition temperature indicates that the detailed phase structure is undetermined for the smectic phase,
Represents a nematic phase, I represents an isotropic liquid phase, and C represents a crystal phase. Example 1 Synthesis of Liquid Crystalline Acrylate Compound (1) In a three-necked flask equipped with a Dean-Stark water separator,
10 g of 4- (hydroxyethyl) phenol, "M-5
600 "(manufactured by Toagosei Co., Ltd.), 22.5 g, hydroquinone 0.1 g, p-toluenesulfonic acid monohydrate 3.2
g, 60 ml of n-hexane and 60 ml of toluene were added and heated with stirring. After refluxing for 3 hours, the reaction solution was cooled to room temperature. After adding 500 ml of saturated saline to this, the reaction solution was extracted by adding 200 ml of toluene. After the organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate and water, toluene was distilled off under reduced pressure to obtain 11.8 g of a crude product of the compound (a).
【００６７】[0067]
【化２７】 Embedded image
【００６８】次に、化合物（ａ）の粗生成物４．０ｇを
ジクロロメタン２０ｍｌに溶解させ、さらにトリエチル
アミン３．４ｇを加え室温において撹拌した。これに２
０ｍｌのジクロロメタンに溶解させたテレフタル酸クロ
リド１．１ｇを、反応液の内温が３０℃を超えないよう
に滴下した。滴下終了後、反応液を４０℃で１時間反応
させ、その後室温まで冷却した。冷却後、反応液に飽和
食塩水３００ｍｌを加えた。この反応液の水層が弱酸性
になるように希塩酸水溶液を加えた後、酢酸エチル１０
０ｍｌを加えて抽出を行った。有機層を水洗後、酢酸エ
チルを減圧留去して４．０ｇの粗生成物を得た。この粗
生成物を、酢酸エチルとｎ−ヘキサンの混合溶媒（容量
比で酢酸エチル：ｎ−ヘキサン＝１：１）を展開溶媒と
したシリカゲルカラムクロマトグラフィー及びエタノー
ルからの再結晶により精製し、液晶性アクリレート化合
物（ｂ）Next, 4.0 g of the crude product of the compound (a) was dissolved in 20 ml of dichloromethane, and 3.4 g of triethylamine was added, followed by stirring at room temperature. This is 2
1.1 g of terephthalic acid chloride dissolved in 0 ml of dichloromethane was added dropwise so that the internal temperature of the reaction solution did not exceed 30 ° C. After completion of the dropwise addition, the reaction solution was reacted at 40 ° C. for 1 hour, and then cooled to room temperature. After cooling, 300 ml of saturated saline was added to the reaction solution. A diluted hydrochloric acid aqueous solution was added so that the aqueous layer of the reaction solution was weakly acidic, and then ethyl acetate was added.
0 ml was added for extraction. After washing the organic layer with water, ethyl acetate was distilled off under reduced pressure to obtain 4.0 g of a crude product. The crude product was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and n-hexane (volume ratio: ethyl acetate: n-hexane = 1: 1) as a developing solvent and recrystallization from ethanol to give a liquid crystal. Acrylate compound (b)
【００６９】[0069]
【化２８】 Embedded image
【００７０】を０．５０ｇ（Ｒｆ＝０．６０）、液晶性
アクリレート化合物（ｃ）0.50 g (Rf = 0.60) of the liquid crystal acrylate compound (c)
【００７１】[0071]
【化２９】 Embedded image
【００７２】を０．６６ｇ（Ｒｆ＝０．４８）、液晶性
アクリレート化合物（ｄ）0.66 g (Rf = 0.48) of a liquid crystal acrylate compound (d)
【００７３】[0073]
【化３０】 Embedded image
【００７４】を０．７０ｇ（Ｒｆ＝０．３６）を得た。
化合物（ｂ）の相転移温度は、0.70 g (Rf = 0.36) was obtained.
The phase transition temperature of compound (b) is
【００７５】[0075]
【化３１】 Embedded image
【００７６】であり、化合物（ｃ）の相転移温度は、The phase transition temperature of the compound (c) is
【００７７】[0077]
【化３２】 Embedded image
【００７８】であり、化合物（ｄ）の相転移温度はThe phase transition temperature of the compound (d) is
【００７９】[0079]
【化３３】 Embedded image
【００８０】であった。 （実施例２） 液晶性アクリレート化合物の合成
（２） ディーンスターク水分離器を装着した３口フラスコに、
４−（ヒドロキシエチル）フェノール７．０ｇ、「ＨＯ
Ａ−ＭＳ」（共栄社化学株式会社製）３２．６ｇ、ヒド
ロキノン１ｇ、ｐ−トルエンスルホン酸１水和物３．５
ｇ、ｎ−ヘキサン６０ｍｌ、トルエン６０ｍｌを加えて
撹拌しながら加熱した。３時間加熱環流後、室温まで反
応液を冷却した。これに飽和食塩水５００ｍｌを加えた
後、反応液にトルエン２００ｍｌを加えて抽出を行っ
た。有機層を飽和炭酸水素ナトリウム水溶液及び水で洗
った後、トルエンを減圧留去して粗生成物２０．３ｇを
得た。この粗生成物を、酢酸エチルとトルエンの混合溶
媒（容量比で酢酸エチル：トルエン＝１：２、Ｒｆ＝
０．４７）を展開溶媒としたシリカゲルカラムクロマト
グラフィーで精製し、化合物（ｅ）を１２．３ｇ得た。Was as follows. Example 2 Synthesis of Liquid Crystalline Acrylate Compound (2) In a three-necked flask equipped with a Dean-Stark water separator,
7.0 g of 4- (hydroxyethyl) phenol, "HO
A-MS "(manufactured by Kyoeisha Chemical Co., Ltd.) 32.6 g, hydroquinone 1 g, p-toluenesulfonic acid monohydrate 3.5
g, 60 ml of n-hexane and 60 ml of toluene were added and heated with stirring. After refluxing for 3 hours, the reaction solution was cooled to room temperature. After adding 500 ml of a saturated saline solution thereto, 200 ml of toluene was added to the reaction solution for extraction. After the organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate and water, toluene was distilled off under reduced pressure to obtain 20.3 g of a crude product. This crude product was dissolved in a mixed solvent of ethyl acetate and toluene (ethyl acetate: toluene = 1: 2 by volume ratio, Rf =
Purification by silica gel column chromatography using 0.47) as a developing solvent gave 12.3 g of compound (e).
【００８１】[0081]
【化３４】 Embedded image
【００８２】次に、化合物（ｅ）の５．２ｇをテトラヒ
ドロフラン３０ｍｌに溶解させ、さらにトリエチルアミ
ン１．９ｇを加え室温において撹拌した。これに２０ｍ
ｌのテトラヒドロフランに溶解させたテレフタル酸クロ
リド１．３ｇを、反応液の内温が３０℃を超えないよう
に滴下した。滴下終了後、反応液を４０℃で１時間反応
させ、その後室温まで冷却した。冷却後、反応液に飽和
食塩水３００ｍｌを加えた。この反応液の水層が弱酸性
になるように希塩酸水溶液を加えた後、酢酸エチル１０
０ｍｌを加えて抽出を行った。有機層を水洗後、酢酸エ
チルを減圧留去して７．０ｇの粗生成物を得た。この粗
生成物を、酢酸エチルとトルエンの混合溶媒（容量比で
酢酸エチル：トルエン＝１：２、Ｒｆ＝０．４８）を展
開溶媒としたシリカゲルカラムクロマトグラフィー及び
エタノールからの再結晶により精製し、液晶性アクリレ
ート化合物（ｆ）を２．３ｇ得た。Next, 5.2 g of the compound (e) was dissolved in 30 ml of tetrahydrofuran, and 1.9 g of triethylamine was further added, followed by stirring at room temperature. 20m to this
1.3 g of terephthalic acid chloride dissolved in 1 l of tetrahydrofuran was added dropwise so that the internal temperature of the reaction solution did not exceed 30 ° C. After completion of the dropwise addition, the reaction solution was reacted at 40 ° C. for 1 hour, and then cooled to room temperature. After cooling, 300 ml of saturated saline was added to the reaction solution. A diluted hydrochloric acid aqueous solution was added so that the aqueous layer of the reaction solution was weakly acidic, and then ethyl acetate was added.
0 ml was added for extraction. After washing the organic layer with water, ethyl acetate was distilled off under reduced pressure to obtain 7.0 g of a crude product. This crude product was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and toluene (volume ratio: ethyl acetate: toluene = 1: 2, Rf = 0.48) as a developing solvent and recrystallization from ethanol. As a result, 2.3 g of a liquid crystal acrylate compound (f) was obtained.
【００８３】[0083]
【化３５】 Embedded image
【００８４】化合物（ｆ）の相転移温度は、The phase transition temperature of compound (f) is
【００８５】[0085]
【化３６】 Embedded image
【００８６】であった。 （実施例３） 液晶性アクリレート化合物の合成
（３） ディーンスターク水分離器を装着した３口フラスコに、
４−ヒドロキシフェニル酢酸１１．４ｇ、２−ヒドロキ
シエチルアクリレート２６．３ｇ、ヒドロキノン０．３
ｇ、ｐ−トルエンスルホン酸１水和物７．０ｇ、ｎ−ヘ
キサン４０ｍｌ、トルエン６０ｍｌ、テトラヒドロフラ
ン３０ｍｌを加えて撹拌しながら加熱した。３時間加熱
環流後、室温まで反応液を冷却した。これに飽和食塩水
７００ｍｌを加えた後、反応液をトルエン３００ｍｌを
加えて抽出を行った。有機層を飽和炭酸水素ナトリウム
水溶液及び水で洗った後、トルエンを減圧留去して化合
物（ｇ）の粗生成物１９．４ｇを得た。Was as follows. Example 3 Synthesis of Liquid Crystalline Acrylate Compound (3) In a three-necked flask equipped with a Dean-Stark water separator,
4-hydroxyphenylacetic acid 11.4 g, 2-hydroxyethyl acrylate 26.3 g, hydroquinone 0.3
g, 7.0 g of p-toluenesulfonic acid monohydrate, 40 ml of n-hexane, 60 ml of toluene, and 30 ml of tetrahydrofuran, and the mixture was heated with stirring. After refluxing for 3 hours, the reaction solution was cooled to room temperature. After adding 700 ml of saturated saline to this, the reaction solution was extracted by adding 300 ml of toluene. After the organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate and water, toluene was distilled off under reduced pressure to obtain 19.4 g of a crude product of the compound (g).
【００８７】[0087]
【化３７】 Embedded image
【００８８】次に、化合物（ｇ）の粗生成物８．０ｇを
テトラヒドロフラン３０ｍｌに溶解させ、さらにトリエ
チルアミン３．９ｇを加え室温において撹拌した。これ
に２０ｍｌのテトラヒドロフランに溶解させたテレフタ
ル酸クロリド２．０ｇを、反応液の内温が３０℃を超え
ないように滴下した。滴下終了後、反応液を４０℃で１
時間反応させ、その後室温まで冷却した。冷却後、反応
液に飽和食塩水３００ｍｌを加えた。この反応液の水層
が弱酸性になるように希塩酸水溶液を加えた後、酢酸エ
チル１００ｍｌを加えて抽出を行った。有機層を水洗
後、酢酸エチルを減圧留去して８．６ｇの粗生成物を得
た。この粗生成物を、酢酸エチルとトルエンの混合溶媒
（容量比で酢酸エチル：トルエン＝１：２、Ｒｆ＝０．
５８）を展開溶媒としたシリカゲルカラムクロマトグラ
フィー及びエタノールからの再結晶により精製し、液晶
性アクリレート化合物（ｈ）を１．０ｇ得た。Next, 8.0 g of a crude product of the compound (g) was dissolved in 30 ml of tetrahydrofuran, and 3.9 g of triethylamine was further added, followed by stirring at room temperature. To this, 2.0 g of terephthalic acid chloride dissolved in 20 ml of tetrahydrofuran was added dropwise so that the internal temperature of the reaction solution did not exceed 30 ° C. After completion of the dropwise addition, the reaction solution was heated at 40 ° C for 1
The reaction was carried out for an hour, and then cooled to room temperature. After cooling, 300 ml of saturated saline was added to the reaction solution. A diluted hydrochloric acid aqueous solution was added so that the aqueous layer of the reaction solution became weakly acidic, and then 100 ml of ethyl acetate was added to perform extraction. After washing the organic layer with water, ethyl acetate was distilled off under reduced pressure to obtain 8.6 g of a crude product. This crude product was treated with a mixed solvent of ethyl acetate and toluene (ethyl acetate: toluene = 1: 2 by volume ratio, Rf = 0.2).
Purification was performed by silica gel column chromatography using 58) as a developing solvent and recrystallization from ethanol to obtain 1.0 g of a liquid crystal acrylate compound (h).
【００８９】[0089]
【化３８】 Embedded image
【００９０】化合物（ｈ）の相転移温度は、The phase transition temperature of compound (h) is
【００９１】[0091]
【化３９】 Embedded image
【００９２】であった。 （実施例４） 液晶性アクリレート化合物の合成
（４） 実施例１で得た化合物（ａ）をシリカゲルカラムクロマ
トグラフィーで精製して得た化合物（ｉ）１．０ｇWas (Example 4) Synthesis of liquid crystalline acrylate compound (4) 1.0 g of compound (i) obtained by purifying compound (a) obtained in Example 1 by silica gel column chromatography.
【００９３】[0093]
【化４０】 Embedded image
【００９４】をテトラヒドロフラン１５ｍｌに溶解さ
せ、さらにトリエチルアミン０．４ｇを加え室温におい
て撹拌した。これに１０ｍｌのテトラヒドロフランに溶
解させたシュウ酸クロリド０．２ｇを、反応液の内温が
３０℃を超えないように滴下した。滴下終了後、反応液
を４０℃で１時間反応させ、その後室温まで冷却した。
冷却後、反応液に飽和食塩水１００ｍｌを加えた。この
反応液の水層が弱酸性になるように希塩酸水溶液を加え
た後、酢酸エチル１００ｍｌを加えて抽出を行った。有
機層を水洗後、酢酸エチルを減圧留去して１．６ｇの粗
生成物を得た。この粗生成物を、酢酸エチルとｎ−ヘキ
サンの混合溶媒（容量比で酢酸エチル：ｎ−ヘキサン＝
１：１、Ｒｆ＝０．４３）を展開溶媒としたシリカゲル
カラムクロマトグラフィー及びエタノールからの再結晶
により精製し、液晶性アクリレート化合物（ｊ）を０．
８ｇ得た。Was dissolved in 15 ml of tetrahydrofuran, and 0.4 g of triethylamine was further added, followed by stirring at room temperature. To this, 0.2 g of oxalic acid chloride dissolved in 10 ml of tetrahydrofuran was added dropwise so that the internal temperature of the reaction solution did not exceed 30 ° C. After completion of the dropwise addition, the reaction solution was reacted at 40 ° C. for 1 hour, and then cooled to room temperature.
After cooling, 100 ml of a saturated saline solution was added to the reaction solution. A diluted hydrochloric acid aqueous solution was added so that the aqueous layer of the reaction solution became weakly acidic, and then 100 ml of ethyl acetate was added to perform extraction. After washing the organic layer with water, ethyl acetate was distilled off under reduced pressure to obtain 1.6 g of a crude product. This crude product was treated with a mixed solvent of ethyl acetate and n-hexane (ethyl acetate: n-hexane =
(1: 1, Rf = 0.43) as a developing solvent by silica gel column chromatography and recrystallization from ethanol to give the liquid crystalline acrylate compound (j) in 0.1.
8 g were obtained.
【００９５】[0095]
【化４１】 Embedded image
【００９６】化合物（ｊ）の相転移温度は、The phase transition temperature of the compound (j) is
【００９７】[0097]
【化４２】 Embedded image
【００９８】であった。 （実施例５） 液晶性アクリレート化合物の合成
（５） 実施例２で得た化合物（ｅ）５．０ｇ、ブロモテレフタ
ル酸１．２ｇ、ジメチルアミノピリジン０．２ｇをテト
ラヒドロフラン２０ｍｌに溶解させ、室温において撹拌
した。これに２０ｍｌのテトラヒドロフランに溶解させ
たジシクロヘキシルカルボジイミド４．７ｇを反応液の
内温が３０℃を超えないように滴下した。滴下終了後、
反応液を４０℃で１時間反応させ、その後室温まで冷却
した。冷却後、反応液に飽和食塩水１００ｍｌを加え
た。この反応液の水層が弱酸性になるように希塩酸水溶
液を加え、析出したジシクロヘキシル尿素をガラスフィ
ルターによって取り除いた後、酢酸エチル１００ｍｌを
加えて抽出を行った。有機層を水洗後、酢酸エチルを減
圧留去して６．７ｇの粗生成物を得た。この粗生成物
を、酢酸エチルとトルエンの混合溶媒（容量比で酢酸エ
チル：トルエン＝１：２、Ｒｆ＝０．５３）を展開溶媒
としたシリカゲルカラムクロマトグラフィーにより精製
し、液晶性アクリレート化合物（ｋ）を４．９ｇ得た。Was obtained. Example 5 Synthesis of Liquid Crystalline Acrylate Compound (5) 5.0 g of the compound (e) obtained in Example 2, 1.2 g of bromoterephthalic acid, and 0.2 g of dimethylaminopyridine were dissolved in 20 ml of tetrahydrofuran, and the mixture was dissolved at room temperature. Stirred. To this, 4.7 g of dicyclohexylcarbodiimide dissolved in 20 ml of tetrahydrofuran was added dropwise so that the internal temperature of the reaction solution did not exceed 30 ° C. After dropping,
The reaction solution was reacted at 40 ° C. for 1 hour, and then cooled to room temperature. After cooling, 100 ml of a saturated saline solution was added to the reaction solution. A dilute aqueous hydrochloric acid solution was added so that the aqueous layer of the reaction solution became weakly acidic. The precipitated dicyclohexylurea was removed with a glass filter, and then 100 ml of ethyl acetate was added to perform extraction. After washing the organic layer with water, ethyl acetate was distilled off under reduced pressure to obtain 6.7 g of a crude product. The crude product was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and toluene (volume ratio: ethyl acetate: toluene = 1: 2, Rf = 0.53) as a developing solvent to obtain a liquid crystalline acrylate compound ( 4.9 g of k) were obtained.
【００９９】[0099]
【化４３】 Embedded image
【０１００】化合物（Ｋ）は室温にて等方性液体であっ
た。 （実施例６） 液晶組成物の調製（１） 式（５７）の化合物Compound (K) was an isotropic liquid at room temperature. Example 6 Preparation of Liquid Crystal Composition (1) Compound of Formula (57)
【０１０１】[0101]
【化４４】 Embedded image
【０１０２】５０重量部及び式（６０）50 parts by weight and the formula (60)
【０１０３】[0103]
【化４５】 Embedded image
【０１０４】の化合物５０重量部からなる液晶組成物
（ａ）を調製した。この液晶組成物（ａ）は室温で液晶
相を示し、ネマチック−等方性液体相の相転移温度は４
６℃であった。液晶組成物（ａ）５０重量部に実施例１
で合成した液晶性アクリレート化合物（ｂ）５０重量部
からなる液晶組成物（ｂ）を調製した。得られた液晶組
成物（ｂ）は５２℃〜７０℃の温度範囲でネマチック相
を示した。 （実施例７） 液晶組成物の調製（２） 実施例６で調製した液晶組成物（ａ）９０重量部に実施
例１で合成した化合物（ｂ）１０重量部からなる液晶組
成物（ｃ）を調製した。得られた液晶組成物（ｃ）は３
０℃〜４９℃の温度範囲でネマチック相を示した。 （実施例８） 液晶組成物の調製（３） 実施例６で調製した液晶組成物（ａ）９５重量部に実施
例１で合成した化合物（ｂ）５重量部からなる液晶組成
物（ｄ）を調製した。得られた液晶組成物（ｄ）は室温
〜４８℃の温度範囲でネマチック相を示した。 （実施例９） 液晶組成物の調製（４） 実施例６で調製した液晶組成物（ａ）９５重量部に実施
例１で合成した化合物（ｃ）５重量部からなる液晶組成
物（ｅ）を調製した。得られた液晶組成物（ｅ）は室温
〜４７℃の温度範囲でネマチック相を示した。 （実施例１０） 液晶組成物の調製（５） 実施例６で調製した液晶組成物（ａ）９５重量部に実施
例１で合成した化合物（ｄ）５重量部からなる液晶組成
物（ｆ）を調製した。得られた液晶組成物（ｆ）は室温
〜４７℃の温度範囲でネマチック相を示した。 （実施例１１） 液晶組成物の調製（６） 実施例６で調製した液晶組成物（ａ）９５重量部に実施
例２で合成した化合物（ｆ）５重量部からなる液晶組成
物（ｇ）を調製した。得られた液晶組成物（ｇ）は室温
〜５０℃の温度範囲でネマチック相を示した。 （実施例１２） 液晶組成物の調製（７） 実施例６で調製した液晶組成物（ａ）９７重量部に実施
例３で合成した化合物（ｈ）３重量部からなる液晶組成
物（ｈ）を調製した。得られた液晶組成物（ｈ）は室温
〜４８℃の温度範囲でネマチック相を示した。 （実施例１３） 液晶組成物の調製（８） 実施例６で調製した液晶組成物（ａ）９５重量部に実施
例４で合成した化合物（ｊ）５重量部からなる液晶組成
物（ｉ）を調製した。得られた液晶組成物（ｉ）は室温
〜４７℃の温度範囲でネマチック相を示した。 （実施例１４） 液晶組成物の調製（９） 実施例６で調製した液晶組成物（ａ）９７重量部に実施
例５で合成した化合物（ｋ）３重量部からなる液晶組成
物（ｊ）を調製した。得られた液晶組成物（ｊ）は室温
〜３８℃の温度範囲でネマチック相を示した。 （実施例１５） 光学異方体の作製（１） 実施例８で調製した液晶組成物（ｄ）９９重量部に光重
合開始剤「ＩＲＧ−６５１」（チバガイギー社製）１重
量部を溶解させた。次にこれをセルギャップ１０ミクロ
ンの透明ガラス製ＴＮ（ツイステッドネマチック）セル
に注入したところ、良好なＴＮ配向が得られていること
が偏光顕微鏡観察により確認できた。このセルに、２５
℃において高圧水銀ランプを用いて５００ｍＪ／ｃｍ2
の紫外線を照射し、液晶組成物を光重合させた。セルを
偏光顕微鏡で観察したところ、ＴＮ配向が均一に固定化
された光学異方体が得られているのが確認できた。次に
セルのガラスを取り外すことにより、１枚のガラスの上
に担持された厚さ１０ミクロンのＴＮ配向構造を有する
光学異方体を得た。この光学異方体は１５０℃で１００
時間加熱しても、ＴＮ配向構造が保持されることがわか
った。 （実施例１６） 光学異方体の作製（２） 厚さ１ｍｍで２０ｍｍ角の透明ガラス基板に、ポリイミ
ド配向剤「ＡＬ−１２５４」（日本合成ゴム製）を２０
００回転／分でスピンコートした後、１５０℃で１時間
乾燥させることにより、ガラス基板上にポリイミド薄膜
を形成した。このポリイミド薄膜をラビングマシーン
「ＲＭ−５０」（ＥＨＣ社製）でラビングすることによ
り、ポリイミド配向膜とした。このポリイミド配向膜付
きガラス基板に、実施例８で調製した液晶組成物（ｄ）
９９重量部に光重合開始剤「ＩＲＧ−６５１」（チバガ
イギー社製）１重量部を添加し、これを１０００回転／
分でスピンコートした。このスピンコートした基板に、
窒素気流下２５℃において高圧水銀ランプを用いて５０
０ｍＪ／ｃｍ2の紫外線を照射し、液晶組成物を光重合
させた。この基板を偏光顕微鏡で観察したところ、均一
な一軸配向が固定化された光学異方体が得られているの
が確認できた。また、この基板を２枚の偏光板の間に挟
んでところ、基板の全面にわたって均一な干渉色が観察
され、均一な厚みをもった光学異方体が得られたことを
確認できた。また、この基板を１５０℃で加熱しても、
固定化された均一な配向状態はそのまま保持されてい
た。 （比較例１）実施例１６における液晶組成物（ｄ）を、
実施例６で調製した液晶組成物（ａ）に代えた以外は同
様にして光学異方体を作製した。得られた光学異方体を
偏光顕微鏡で観察したところ、均一な一軸配向が固定化
された光学異方体が得られているのが確認できた。しか
しながら、これを２枚の偏光板の間に挟んでところ、基
板の全面にわたる均一な干渉色が観察されず、光学異方
体の膜厚が均一でないことが確認された。 （実施例１７） 光学異方体の作製（３） 厚さ２．０ｍｍで２０ｍｍ角のポリカーボネート基板を
用意し、ポリカーボネート基板の光軸方向と同一方向に
ラビングマシーン「ＲＭ−５０」（ＥＨＣ社製）を用い
てラビングした。このポリカーボネート基板に、実施例
８で調製した液晶組成物（ｄ）９９重量部に光重合開始
剤「ＩＲＧ−６５１」（チバガイギー社製）１重量部を
添加し、これを５００回転／分でスピンコートした。こ
のスピンコートした基板に、窒素気流下２５℃において
高圧水銀ランプを用いて５００ｍＪ／ｃｍ2の紫外線を
照射し、液晶組成物を光重合させた。この基板を偏光顕
微鏡で観察したところ、均一な一軸配向が固定化された
光学異方体が得られているのが確認できた。また、この
基板を２枚の偏光板の間に挟んでところ、基板の全面に
わたって均一な干渉色が観察され、均一な厚みをもった
光学異方体が得られたことを確認できた。また、この基
板を１００℃で加熱しても、固定化された均一な配向状
態はそのまま保持されていた。 （比較例２）実施例１７における液晶組成物（ｄ）を、
実施例６で調製した液晶組成物（ａ）に代えた以外は同
様にして光学異方体を作製した。得られた光学異方体を
偏光顕微鏡で観察したところ、均一な一軸配向が固定化
された光学異方体が得られているのが確認できた。しか
しながら、これを２枚の偏光板の間に挟んでところ、基
板の全面にわたる均一な干渉色が観察されず、光学異方
体の膜厚が均一でないことが確認された。A liquid crystal composition (a) was prepared comprising 50 parts by weight of the compound of the formula (1). This liquid crystal composition (a) shows a liquid crystal phase at room temperature, and the nematic-isotropic liquid phase has a phase transition temperature of 4
6 ° C. Example 1 was added to 50 parts by weight of the liquid crystal composition (a).
A liquid crystal composition (b) comprising 50 parts by weight of the liquid crystal acrylate compound (b) synthesized in the above was prepared. The obtained liquid crystal composition (b) showed a nematic phase in a temperature range of 52 ° C to 70 ° C. (Example 7) Preparation of liquid crystal composition (2) Liquid crystal composition (c) consisting of 90 parts by weight of liquid crystal composition (a) prepared in Example 6 and 10 parts by weight of compound (b) synthesized in Example 1 Was prepared. The obtained liquid crystal composition (c) was 3
A nematic phase was exhibited in a temperature range of 0 ° C to 49 ° C. (Example 8) Preparation of liquid crystal composition (3) Liquid crystal composition (d) consisting of 95 parts by weight of liquid crystal composition (a) prepared in Example 6 and 5 parts by weight of compound (b) synthesized in Example 1 Was prepared. The obtained liquid crystal composition (d) showed a nematic phase in a temperature range from room temperature to 48 ° C. (Example 9) Preparation of liquid crystal composition (4) Liquid crystal composition (e) comprising 95 parts by weight of liquid crystal composition (a) prepared in Example 6 and 5 parts by weight of compound (c) synthesized in Example 1 Was prepared. The obtained liquid crystal composition (e) showed a nematic phase in a temperature range from room temperature to 47 ° C. (Example 10) Preparation of liquid crystal composition (5) A liquid crystal composition (f) comprising 95 parts by weight of the liquid crystal composition (a) prepared in Example 6 and 5 parts by weight of the compound (d) synthesized in Example 1 Was prepared. The obtained liquid crystal composition (f) showed a nematic phase in a temperature range from room temperature to 47 ° C. Example 11 Preparation of Liquid Crystal Composition (6) A liquid crystal composition (g) consisting of 95 parts by weight of the liquid crystal composition (a) prepared in Example 6 and 5 parts by weight of the compound (f) synthesized in Example 2 Was prepared. The obtained liquid crystal composition (g) showed a nematic phase in a temperature range from room temperature to 50 ° C. (Example 12) Preparation of liquid crystal composition (7) A liquid crystal composition (h) comprising 97 parts by weight of the liquid crystal composition (a) prepared in Example 6 and 3 parts by weight of the compound (h) synthesized in Example 3 Was prepared. The obtained liquid crystal composition (h) showed a nematic phase in a temperature range from room temperature to 48 ° C. (Example 13) Preparation of liquid crystal composition (8) Liquid crystal composition (i) consisting of 95 parts by weight of liquid crystal composition (a) prepared in Example 6 and 5 parts by weight of compound (j) synthesized in Example 4 Was prepared. The obtained liquid crystal composition (i) showed a nematic phase in a temperature range from room temperature to 47 ° C. (Example 14) Preparation of liquid crystal composition (9) A liquid crystal composition (j) consisting of 97 parts by weight of the liquid crystal composition (a) prepared in Example 6 and 3 parts by weight of the compound (k) synthesized in Example 5 Was prepared. The obtained liquid crystal composition (j) showed a nematic phase in a temperature range from room temperature to 38 ° C. Example 15 Production of Optical Anisotropic Body (1) 1 part by weight of a photopolymerization initiator “IRG-651” (manufactured by Ciba Geigy) was dissolved in 99 parts by weight of the liquid crystal composition (d) prepared in Example 8. Was. Next, when this was injected into a transparent glass TN (twisted nematic) cell having a cell gap of 10 μm, it was confirmed by polarization microscope observation that a good TN orientation was obtained. In this cell, 25
500 mJ / cm 2 using a high pressure mercury lamp at
Was irradiated, and the liquid crystal composition was photopolymerized. When the cell was observed with a polarizing microscope, it was confirmed that an optically anisotropic body in which the TN orientation was uniformly fixed was obtained. Next, the glass of the cell was removed to obtain an optically anisotropic body having a TN alignment structure with a thickness of 10 μm supported on one glass. This optically anisotropic material is 100
It was found that the TN alignment structure was maintained even after heating for a time. Example 16 Production of Optical Anisotropic Body (2) A polyimide alignment agent “AL-1254” (manufactured by Nippon Synthetic Rubber Co., Ltd.) was applied to a 20 mm square transparent glass substrate having a thickness of 1 mm.
After spin-coating at 00 revolutions / minute, it was dried at 150 ° C. for 1 hour to form a polyimide thin film on a glass substrate. This polyimide thin film was rubbed with a rubbing machine "RM-50" (manufactured by EHC) to obtain a polyimide alignment film. The liquid crystal composition (d) prepared in Example 8 was placed on this glass substrate with a polyimide alignment film.
To 99 parts by weight, 1 part by weight of a photopolymerization initiator "IRG-651" (manufactured by Ciba Geigy) was added, and the mixture was added at 1000 rpm.
Spin coated in minutes. On this spin-coated substrate,
Using a high-pressure mercury lamp at 25 ° C under a nitrogen stream
The liquid crystal composition was irradiated with an ultraviolet ray of 0 mJ / cm 2 to cause photopolymerization. When this substrate was observed with a polarizing microscope, it was confirmed that an optically anisotropic body in which uniform uniaxial orientation was fixed was obtained. When the substrate was sandwiched between two polarizing plates, a uniform interference color was observed over the entire surface of the substrate, and it was confirmed that an optically anisotropic body having a uniform thickness was obtained. Also, even if this substrate is heated at 150 ° C.,
The fixed and uniform orientation state was maintained as it was. Comparative Example 1 The liquid crystal composition (d) in Example 16 was
An optically anisotropic body was prepared in the same manner except that the liquid crystal composition (a) prepared in Example 6 was used. Observation of the obtained optically anisotropic body with a polarizing microscope confirmed that an optically anisotropic body in which uniform uniaxial orientation was fixed was obtained. However, when this was sandwiched between two polarizing plates, no uniform interference color was observed over the entire surface of the substrate, and it was confirmed that the film thickness of the optically anisotropic body was not uniform. Example 17 Production of Optical Anisotropic Body (3) A 20 mm square polycarbonate substrate having a thickness of 2.0 mm was prepared, and a rubbing machine “RM-50” (manufactured by EHC) was formed in the same direction as the optical axis direction of the polycarbonate substrate. Rubbed using To this polycarbonate substrate, 1 part by weight of a photopolymerization initiator "IRG-651" (manufactured by Ciba-Geigy) was added to 99 parts by weight of the liquid crystal composition (d) prepared in Example 8, and the mixture was spun at 500 rpm. Coated. The spin-coated substrate was irradiated with ultraviolet rays of 500 mJ / cm 2 using a high-pressure mercury lamp at 25 ° C. under a nitrogen stream to photopolymerize the liquid crystal composition. When this substrate was observed with a polarizing microscope, it was confirmed that an optically anisotropic body in which uniform uniaxial orientation was fixed was obtained. When the substrate was sandwiched between two polarizing plates, a uniform interference color was observed over the entire surface of the substrate, and it was confirmed that an optically anisotropic body having a uniform thickness was obtained. Even when the substrate was heated at 100 ° C., the fixed and uniform orientation state was maintained as it was. (Comparative Example 2) The liquid crystal composition (d) in Example 17 was replaced with
An optically anisotropic body was prepared in the same manner except that the liquid crystal composition (a) prepared in Example 6 was used. Observation of the obtained optically anisotropic body with a polarizing microscope confirmed that an optically anisotropic body in which uniform uniaxial orientation was fixed was obtained. However, when this was sandwiched between two polarizing plates, no uniform interference color was observed over the entire surface of the substrate, and it was confirmed that the film thickness of the optically anisotropic body was not uniform.
【０１０５】[0105]
【発明の効果】本発明の液晶性（メタ）アクリレート化
合物と液晶組成物は、プラスチックやガラス基板への塗
布性に優れている。従って、塗布等の手段によって位相
差フィルム等の光学異方体を作製するのに有用な材料で
ある。また本発明の液晶性（メタ）アクリレート化合物
と液晶組成物を用いて作製した光学異方体は、配向の均
一性及び膜厚の均一性に優れており、位相差フィルム等
への応用に適している。The liquid crystal (meth) acrylate compound and the liquid crystal composition of the present invention have excellent coatability on plastics and glass substrates. Therefore, it is a material useful for producing an optically anisotropic body such as a retardation film by means such as coating. Further, the optically anisotropic material prepared by using the liquid crystal (meth) acrylate compound of the present invention and the liquid crystal composition has excellent uniformity of alignment and film thickness, and is suitable for application to a retardation film or the like. ing.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｄ 213/28 Ｃ０７Ｄ 213/28 239/26 239/26 239/34 239/34 Ｃ０８Ｆ 20/10 Ｃ０８Ｆ 20/10 Ｃ０９Ｋ 19/12 Ｃ０９Ｋ 19/12 19/14 19/14 19/18 19/18 19/20 19/20 19/30 19/30 19/34 19/34 19/38 19/38 19/46 19/46 Ｇ０２Ｆ 1/1335 ５１０ Ｇ０２Ｆ 1/1335 ５１０ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C07D 213/28 C07D 213/28 239/26 239/26 239/34 239/34 C08F 20/10 C08F 20/10 C09K 19/12 C09K 19/12 19/14 19/14 19/18 19/18 19/20 19/20 19/30 19/30 19/34 19/34 19/38 19/38 19/46 19/46 G02F 1/1335 510 G02F 1/1335 510
Claims (9)
メチル基を表し、Ｐ1、Ｐ2、Ｐ3、Ｐ4、Ｐ5及びＰ6はそ
れぞれ独立的に炭素原子数１から１８の２価の炭化水素
基を表し、Ｚ1、Ｚ2、Ｚ3、及びＺ4はそれぞれ独立的
に、−ＣＯＯ−または−ＯＣＯ−を表し、Ｙ1及びＹ2は
それぞれ独立的に、単結合、−ＣＨ2ＣＨ2−、−ＣＨ2
Ｏ−、−ＯＣＨ2−、−ＣＯＯ−、−ＯＣＯ−、−Ｃ≡
Ｃ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−（ＣＨ2）4
−、−ＣＨ2ＣＨ2ＣＨ2Ｏ−、−ＯＣＨ2ＣＨ2ＣＨ2−、
−ＣＨ＝ＣＨ−ＣＨ2ＣＨ2−、−ＣＨ2ＣＨ2ＣＨ2Ｏ
−、−ＯＯＣＣＯＯ−を表し、ｊ及びｋはそれぞれ独立
的に０または１の整数を表し、ｎは０または１の整数を
表し、６員環Ａ、Ｂ及びＣはそれぞれ独立的に、 【化２】 を表し、Ｗはハロゲン原子またはメチル基を表し、ｍは
１〜４の整数を表す。）で表されることを特徴とする液
晶性（メタ）アクリレート化合物。1. A compound of the general formula (I) (Wherein, X 1 and X 2 each independently represent a hydrogen atom or a methyl group, and P 1 , P 2 , P 3 , P 4 , P 5 and P 6 each independently represent a carbon atom number of 1 to 18). Wherein Z 1 , Z 2 , Z 3 , and Z 4 each independently represent —COO— or —OCO—; Y 1 and Y 2 each independently represent a monovalent hydrocarbon group; bond, -CH 2 CH 2 -, - CH 2
O -, - OCH 2 -, - COO -, - OCO -, - C≡
C -, - CH = CH - , - CF = CF -, - (CH 2) 4
-, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -,
-CH = CH-CH 2 CH 2 -, - CH 2 CH 2 CH 2 O
-, -OOCCOO-, wherein j and k each independently represent an integer of 0 or 1, n represents an integer of 0 or 1, and the 6-membered rings A, B and C each independently represent: 2] W represents a halogen atom or a methyl group, and m represents an integer of 1 to 4. A liquid crystalline (meth) acrylate compound represented by the formula:
れぞれ独立的にメチレン基またはエチレン基であること
を特徴とする請求項１記載の液晶性（メタ）アクリレー
ト化合物。2. The liquid crystalline (meth) acrylate compound according to claim 1, wherein in formula (I), P 3 and P 4 are each independently a methylene group or an ethylene group.
素原子を表し、Ｐ1、Ｐ2、Ｐ3、Ｐ4、Ｐ5及びＰ6はそれ
ぞれ独立的にメチレン基またはエチレン基を表し、Ｙ1
及びＹ2はそれぞれ独立的に、−ＣＯＯ−、−ＯＣＯ−
を表し、ｊ及びｋはそれぞれ独立的に０または１の整数
を表し、ｎは１の整数を表し、６員環Ａ、Ｂ及びＣは、 【化３】 を表す。）で表されることを特徴とする請求項１記載の
液晶性アクリレート化合物。3. In the general formula (I), X 1 and X 2 represent a hydrogen atom, and P 1 , P 2 , P 3 , P 4 , P 5 and P 6 each independently represent a methylene group or an ethylene group. And Y 1
And Y 2 are each independently -COO-, -OCO-
Wherein j and k each independently represent an integer of 0 or 1, n represents an integer of 1, and the 6-membered rings A, B and C are represented by the following formula: Represents The liquid crystalline acrylate compound according to claim 1, which is represented by:
クリレート化合物を含有し、液晶相を示すことを特徴と
する液晶組成物。4. A liquid crystal composition comprising the liquid crystalline (meth) acrylate compound according to claim 1 and exhibiting a liquid crystal phase.
度範囲で発現することを特徴とする請求項４記載の液晶
組成物。5. The liquid crystal composition according to claim 4, wherein the liquid crystal phase develops in a temperature range of at least 20 ° C. to 30 ° C.
クリレート化合物を２重量％以上、及び少なくとも２つ
の６員環を有する液晶骨格を部分構造として有する環状
アルコール、フェノール又は芳香族ヒドロキシ化合物の
アクリル酸又はメタクリル酸エステルである単官能アク
リレート又は単官能メタクリレートを含有し、液晶相を
示すことを特徴とする液晶組成物。6. A cyclic alcohol, phenol or aromatic hydroxy compound having at least 2% by weight of the liquid crystalline (meth) acrylate compound according to claim 1 and a liquid crystal skeleton having at least two 6-membered rings as a partial structure. A liquid crystal composition comprising a monofunctional acrylate or a monofunctional methacrylate which is an acrylic acid or methacrylic acid ester, and exhibiting a liquid crystal phase.
レートが一般式（ＩＩ）、 【化４】 （式中、Ｘ3は水素原子又はメチル基を表し、ｒは０ま
たは１の整数を表し、６員環Ｄ、Ｅ及びＦはそれぞれ独
立的に、 【化５】 を表し、ｐは１〜４の整数を表し、Ｙ3及びＹ4はそれぞ
れ独立的に、単結合、−ＣＨ2ＣＨ2−、−ＣＨ2Ｏ−、
−ＯＣＨ2−、−ＣＯＯ−、−ＯＣＯ−、−Ｃ≡Ｃ−、
−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−（ＣＨ2）4−、−
ＣＨ2ＣＨ2ＣＨ2Ｏ−、−ＯＣＨ2ＣＨ2ＣＨ2−、−ＣＨ
＝ＣＨ−ＣＨ2ＣＨ2−、−ＣＨ2ＣＨ2ＣＨ2Ｏ−を表
し、Ｙ5は水素原子、ハロゲン原子、シアノ基、炭素原
子数１〜２０のアルキル基、アルコキシ基、アルケニル
基又はアルケニルオキシ基を表す。）で表されることを
特徴とする請求項６記載の液晶組成物。7. The monofunctional acrylate or methacrylate is represented by the general formula (II): (Wherein X 3 represents a hydrogen atom or a methyl group, r represents an integer of 0 or 1, and the 6-membered rings D, E and F each independently represent: And p represents an integer of 1 to 4, and Y 3 and Y 4 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—,
—OCH 2 —, —COO—, —OCO—, —C≡C—,
-CH = CH -, - CF = CF -, - (CH 2) 4 -, -
CH 2 CH 2 CH 2 O - , - OCH 2 CH 2 CH 2 -, - CH
＝ CH—CH 2 CH 2 —, —CH 2 CH 2 CH 2 O—, wherein Y 5 is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group or an alkenyl Represents an oxy group. The liquid crystal composition according to claim 6, which is represented by:
度範囲で発現することを特徴とする請求項７記載の液晶
組成物。8. The liquid crystal composition according to claim 7, wherein the liquid crystal phase develops at least in a temperature range of 20 ° C. to 30 ° C.
体であることを特徴とする光学異方体。9. An optically anisotropic body, which is a polymer of the liquid crystal composition according to claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24099697A JP3963035B2 (en) | 1997-09-05 | 1997-09-05 | Liquid crystalline (meth) acrylate compound and composition, and optical anisotropic body using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24099697A JP3963035B2 (en) | 1997-09-05 | 1997-09-05 | Liquid crystalline (meth) acrylate compound and composition, and optical anisotropic body using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1180081A true JPH1180081A (en) | 1999-03-23 |
| JP3963035B2 JP3963035B2 (en) | 2007-08-22 |
Family
ID=17067783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24099697A Expired - Fee Related JP3963035B2 (en) | 1997-09-05 | 1997-09-05 | Liquid crystalline (meth) acrylate compound and composition, and optical anisotropic body using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3963035B2 (en) |
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