JP5708966B2 - Liquid crystal composition for polymer dispersed liquid crystal element and liquid crystal element using the same - Google Patents
Liquid crystal composition for polymer dispersed liquid crystal element and liquid crystal element using the same Download PDFInfo
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- JP5708966B2 JP5708966B2 JP2009264924A JP2009264924A JP5708966B2 JP 5708966 B2 JP5708966 B2 JP 5708966B2 JP 2009264924 A JP2009264924 A JP 2009264924A JP 2009264924 A JP2009264924 A JP 2009264924A JP 5708966 B2 JP5708966 B2 JP 5708966B2
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 285
- 239000000203 mixture Substances 0.000 title claims description 258
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 title claims description 124
- 150000001875 compounds Chemical class 0.000 claims description 105
- 125000000217 alkyl group Chemical group 0.000 claims description 61
- -1 tetrahydropyran-2 , 5-diyl group Chemical group 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 42
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 239000003999 initiator Substances 0.000 claims description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 34
- 239000004815 dispersion polymer Substances 0.000 claims description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 26
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 19
- 125000001153 fluoro group Chemical group F* 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 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 10
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000004434 sulfur atom Chemical group 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 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 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 101100132433 Arabidopsis thaliana VIII-1 gene Proteins 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004988 Nematic liquid crystal Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 150000001923 cyclic compounds Chemical group 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims 1
- 230000007704 transition Effects 0.000 description 69
- 238000000034 method Methods 0.000 description 41
- 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 28
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 27
- 150000002148 esters Chemical class 0.000 description 26
- 229920000728 polyester Polymers 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 3
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000002433 hydrophilic molecules Chemical class 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 2
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- KJKZLEIRAQXDGH-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone;phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1.CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 KJKZLEIRAQXDGH-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- SDXHBDVTZNMBEW-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol Chemical compound CCOC(O)COCCO SDXHBDVTZNMBEW-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- JMVZGKVGQDHWOI-UHFFFAOYSA-N 2-(2-methylpropoxy)-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC(C)C)C(=O)C1=CC=CC=C1 JMVZGKVGQDHWOI-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- OADIZUFHUPTFAG-UHFFFAOYSA-N 2-[2-(2-ethylhexoxy)ethoxy]ethanol Chemical compound CCCCC(CC)COCCOCCO OADIZUFHUPTFAG-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-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
- 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 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- UVRCNEIYXSRHNT-UHFFFAOYSA-N 3-ethylpent-2-enamide Chemical compound CCC(CC)=CC(N)=O UVRCNEIYXSRHNT-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 101100459319 Arabidopsis thaliana VIII-2 gene Proteins 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 1
- SEEVRZDUPHZSOX-UHFFFAOYSA-N [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(C)=NOC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-UHFFFAOYSA-N 0.000 description 1
- URLYGBGJPQYXBN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methyl prop-2-enoate Chemical compound OCC1CCC(COC(=O)C=C)CC1 URLYGBGJPQYXBN-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical group CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QKQSRIKBWKJGHW-UHFFFAOYSA-N morpholine;prop-2-enoic acid Chemical compound OC(=O)C=C.C1COCCN1 QKQSRIKBWKJGHW-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJAAOMWUWOTVHA-UHFFFAOYSA-N oxetan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCO1 FJAAOMWUWOTVHA-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QFXCGXNPCMKTJQ-UHFFFAOYSA-N prop-2-enoic acid;1,1,3-trimethylcyclohexane Chemical compound OC(=O)C=C.CC1CCCC(C)(C)C1 QFXCGXNPCMKTJQ-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Liquid Crystal Substances (AREA)
Description
本発明は高分子分散型液晶素子に有用な液晶組成物、及びこれを用いた高分子分散型液晶素子に関する。 The present invention relates to a liquid crystal composition useful for a polymer-dispersed liquid crystal element and a polymer-dispersed liquid crystal element using the same.
高分子分散型液晶素子は、偏光板を必要としないため、従来の偏光板を用いた、TN、STN、IPS又はVAモードの液晶表示素子に比べ、明るい表示が実現できるメリットがあり、素子の構成も単純であることから、調光ガラス等の光シャッター用途、時計等セグメント表示用途に応用されている。 The polymer-dispersed liquid crystal element does not require a polarizing plate, so it has the advantage of achieving brighter display compared to TN, STN, IPS or VA mode liquid crystal display elements using conventional polarizing plates. Since the structure is simple, it is applied to optical shutter applications such as light control glass and segment display applications such as watches.
この高分子分散型液晶素子には、いくつかの種類があり、例えば、ＮＣＡＰと呼ばれるタイプ（特許文献１）、ＰＤＬＣ（Ｐｏｌｙｍｅｒ Ｄｉｓｐｅｒｓｅｄ ＬＣ）と呼ばれるタイプ（特許文献２、特許文献３）、ＰＮＬＣ（Ｐｏｌｙｍｅｒ Ｎｅｔｗｏｒｋ ＬＣ）と呼ばれるタイプ（特許文献４）等が提案されている。 There are several types of polymer dispersed liquid crystal elements, for example, a type called NCAP (Patent Document 1), a type called PDLC (Polymer Dispersed LC) (Patent Document 2, Patent Document 3), PNLC ( A type called “Polymer Network LC” (Patent Document 4) has been proposed.
ここで、高分子分散型液晶の中でも、ＰＤＬＣやＰＮＬＣと呼ばれるタイプについて簡単に説明する。これらの高分子分散型液晶素子用液晶組成物は、通常非重合性のネマチック液晶組成物と１種又は２種以上の重合性化合物、及び光重合開始剤から構成され、これらの混合物（高分子分散型液晶素子用液晶組成物）を均一な状態にして、ガラスセルやプラスチックフィルムで挟み、紫外線を照射することによって、重合性化合物又はその組成物を重合させると同時に、重合したポリマーと液晶組成物とを相分離させ、ポリマーの３次元ネットワーク構造中に液晶組成物が連続層をなす構造、液晶組成物のドロップレットがポリマー中に分散している構造、又は両者が混在する構造を形成させる。この高分子分散型液晶素子用液晶組成物は、Ｔｎｍ（高分子分散型液晶素子用液晶組成物のネマチック−アイソトロピック転移点）以下では液晶リッチ相とモノマーリッチ相に分かれており、均一な状態にするにはＴｎｍ以上の温度にしなければならない。実験的には加熱して均一な状態にすればよいが、実用的にはＴｎｍを室温以下にして、加熱することなしに取り扱えることが求められることになる。この高分子分散型液晶素子用液晶組成物のＴｎｍは、液晶組成物自身のＴｎｉ（液晶組成物のネマチック−アイソトロピック転移点）から、重合性化合物又はその組成物を添加するに従い比例的に低下する傾向を示すので、高分子分散型液晶素子用液晶組成物のＴｎｍを室温以下にするためには、液晶組成物自身のＴｎｉ、及び重合性化合物又はその組成物の添加量を適切にコントロールする必要がる。 Here, among polymer dispersed liquid crystals, types called PDLC and PNLC will be briefly described. These liquid crystal compositions for polymer-dispersed liquid crystal elements are usually composed of a non-polymerizable nematic liquid crystal composition, one or more polymerizable compounds, and a photopolymerization initiator, and a mixture thereof (polymer The liquid crystal composition for the dispersion type liquid crystal element) is made uniform, sandwiched between glass cells or plastic films, and irradiated with ultraviolet rays to polymerize the polymerizable compound or the composition, and at the same time, the polymerized polymer and the liquid crystal composition To form a structure in which a liquid crystal composition forms a continuous layer in a three-dimensional network structure of a polymer, a structure in which droplets of a liquid crystal composition are dispersed in a polymer, or a structure in which both are mixed . This liquid crystal composition for a polymer dispersed liquid crystal device is divided into a liquid crystal rich phase and a monomer rich phase below Tnm (nematic-isotropic transition point of the liquid crystal composition for polymer dispersed liquid crystal device) and is in a uniform state. In order to achieve this, the temperature must be equal to or higher than Tnm. Although it may be experimentally heated to obtain a uniform state, practically, it is required that Tnm be set to room temperature or lower and that the film can be handled without heating. The Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements is proportionally decreased from the Tni of the liquid crystal composition itself (nematic-isotropic transition point of the liquid crystal composition) as the polymerizable compound or the composition is added. Therefore, in order to bring the Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements to room temperature or lower, the Tni of the liquid crystal composition itself and the amount of the polymerizable compound or the composition added are appropriately controlled. I need it.
この高分子分散型液晶素子用液晶組成物をガラス、又はフィルムに挟み、紫外線を照射すること等によって得られる、高分子分散型液晶素子は、電圧無印加状態では、液晶組成物はランダムな配向状態をとり、硬化したポリマーと液晶組成物との屈折率差や、液晶組成物自身のランダム配向より光を散乱する状態、すなわち白濁した状態となる。この白濁性は、用途によって違いはあるが、一般的には白濁性の高い方が好まれる傾向にある。高い白濁性を得るには、液晶組成物のΔｎ（屈折率異方性）は大きい方が良く、ポリマーのネットワーク構造、又は液晶ドロップレットの粒径サイズには最適な大きさが存在する。一方十分に高い電圧をかけた場合、液晶組成物は電界方向に配向し、液晶組成物自身の散乱性はなくなる。ここでポリマーの屈折率と液晶組成物のｎｏ（常光屈折率）との差が十分小さければ、光散乱は起きず、透明状態となる。そのため、高い透明性を得るにはポリマーの屈折率と液晶組成物のｎｏとを合わせる必要がある。 This polymer-dispersed liquid crystal element is obtained by sandwiching a liquid crystal composition for a polymer-dispersed liquid crystal element between glass or a film and irradiating with ultraviolet rays. The polymer-dispersed liquid crystal element is randomly oriented when no voltage is applied. It takes a state and becomes a state in which light is scattered from the difference in refractive index between the cured polymer and the liquid crystal composition, or the random orientation of the liquid crystal composition itself, that is, a cloudy state. Although this cloudiness varies depending on the application, generally, the cloudiness tends to be preferred. In order to obtain high turbidity, the Δn (refractive index anisotropy) of the liquid crystal composition should be large, and there is an optimum size for the polymer network structure or the particle size of the liquid crystal droplets. On the other hand, when a sufficiently high voltage is applied, the liquid crystal composition is aligned in the direction of the electric field, and the scattering property of the liquid crystal composition itself is lost. Here, if the difference between the refractive index of the polymer and the no (ordinary refractive index) of the liquid crystal composition is sufficiently small, light scattering does not occur and a transparent state is obtained. Therefore, in order to obtain high transparency, it is necessary to match the refractive index of the polymer with the no of the liquid crystal composition.
駆動電圧については、液晶のΔε（誘電率異方性）、液晶組成物とポリマー界面とのアンカリング力、ポリマーのネットワーク構造の大きさ、又は液晶ドロップレットの粒径サイズが支配的な因子となる。当然液晶のΔεは大きい方が駆動電圧は低くなり、液晶組成物とポリマー界面とのアンカリング力は小さい方が低駆動電圧となる。また、ポリマーのネットワーク構造の大きさ、又は液晶ドロップレットの粒径サイズは大きく均一である方が低駆動電圧となる。 Regarding the driving voltage, the Δε (dielectric anisotropy) of the liquid crystal, the anchoring force between the liquid crystal composition and the polymer interface, the size of the polymer network structure, or the particle size of the liquid crystal droplets are the dominant factors. Become. Naturally, the larger the Δε of the liquid crystal, the lower the driving voltage, and the smaller the anchoring force between the liquid crystal composition and the polymer interface, the lower the driving voltage. In addition, a smaller driving voltage is obtained when the size of the polymer network structure or the particle size of the liquid crystal droplets is larger and uniform.
この高分子分散型液晶素子用液晶組成物を調光ガラスのような大面積を必要とする用途に用いる場合は、一般的に初めからガラス基板で挟むのではなく、一端プラスチックフィルム間に挟んだ調光フィルムを作製し、その調光フィルムを合わせガラスで挟む方法を用いる場合が多い。また、このような大面積の調光フィルムを作製する場合は、これまでは塗布、乾燥、張り合わせ工程のみで作製でき、ＵＶ照射工程を必要としないＮＣＡＰタイプのもので作製されていた。しかし、ＮＣＡＰタイプでは、均一な粒径を有する液晶ドロップレットを、均一な状態に塗布することが難しく、歩留まりが悪い状態が続いていた。 When this polymer-dispersed liquid crystal composition liquid crystal composition is used for applications requiring a large area such as light control glass, it is generally not sandwiched between glass substrates from the beginning, but is sandwiched between plastic films. In many cases, a method of preparing a light control film and sandwiching the light control film between laminated glasses is used. In the case of producing such a large-area light control film, it has so far been produced by an NCAP type which can be produced only by a coating, drying and laminating process and does not require a UV irradiation process. However, in the NCAP type, it is difficult to apply liquid crystal droplets having a uniform particle size in a uniform state, and the yield is still poor.
一方、ＰＤＬＣ、及びＰＮＬＣタイプのものは、これまでは表示素子や光学シャッター等の光学部材への応用が中心であったが、近年、非特許文献１に見られるように、大面積の調光フィルムの作製が実現されている。ＮＣＡＰ方式と異なり、均一な状態に作製することが容易であり、低コストでの作製が可能である。 On the other hand, PDLC and PNLC types have so far been mainly applied to optical members such as display elements and optical shutters, but in recent years, as shown in Non-Patent Document 1, large-area dimming is possible. Production of the film has been realized. Unlike the NCAP method, it can be easily manufactured in a uniform state and can be manufactured at low cost.
しかしながら、従来の高分子分散型液晶用組成物を用いると、フィルム基板との密着性が悪く、すぐ剥がれてしまう問題があった。この問題は古くからの課題であり、リン系の添加剤添加、カルボキシル基を有するアクリレートモノマー、又はオリゴマーを使用するという改善策（特許文献５及び特許文献６）が開発されたが、これだけでは十分ではなかった。 However, when a conventional polymer-dispersed liquid crystal composition is used, there is a problem that the adhesiveness to the film substrate is poor and the film is easily peeled off. This problem has been a problem for a long time, and improvement measures (Patent Document 5 and Patent Document 6) using phosphorus-based additive addition, an acrylate monomer having a carboxyl group, or an oligomer have been developed. It wasn't.
また、フィルム基板で作製できるということは、ガラス基板とは異なり湾曲した状態にすることが可能になるが、従来の材料で作製した調光フィルムは湾曲させると、その応力によって液晶材料が配向してしまい散乱性が弱くなってしまう問題もあった。この問題に対しては片側基板から調光層形成材料を剥離させるという手法が特許文献７に記載されているが、基板との密着性はほとんどなくなってしまうため、課題の根本的解決には至っていない。 In addition, the fact that it can be produced with a film substrate allows it to be in a curved state unlike a glass substrate, but when a light control film produced with a conventional material is curved, the liquid crystal material is oriented by the stress. There is also a problem that the scattering property is weakened. For this problem, Patent Document 7 describes a method of peeling the light-control layer forming material from the one-side substrate, but since the adhesion with the substrate is almost lost, the problem has been fundamentally solved. Not in.
また、ウレタン系ジアクリレートソフトオリゴマー等を用いた方法（特許文献７）も試みられているが、まだ十分ではないと共に、湾曲させたときの白濁維持性についてはなんら述べられていない。 Also, a method using a urethane diacrylate soft oligomer or the like (Patent Document 7) has been tried, but it is not yet sufficient, and there is no mention of white turbidity maintenance property when bent.
特許文献９には、本願請求項１記載の第２成分、第３成分、を含有する例が比較例として記載されているが、駆動電圧が１３０ｖ以上と高く、また、密着性、及び湾曲させたときの白濁維持性についてはなんら述べられていない。 In Patent Document 9, an example containing the second component and the third component described in claim 1 of the present application is described as a comparative example. However, the driving voltage is as high as 130 V or more, and adhesion and curving are also performed. There is no mention of the maintenance of white turbidity.
更に、上記密着性と湾曲させたときでも白濁性を維持する特性を両立し、且つ低電圧で駆動できる高分子分散型液晶用組成物、及びそれを用いた素子は今までなかった。 Furthermore, there has not been a polymer-dispersed liquid crystal composition that achieves both the above adhesiveness and the characteristics of maintaining white turbidity even when curved and can be driven at a low voltage, and a device using the same.
本発明の目的は、フィルム基板との密着性に優れ、且つ曲げた場合でも白濁性を維持し、低電圧で駆動可能な高分子分散型液晶素子、及びそれに用いる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 polymer-dispersed liquid crystal element that has excellent adhesion to a film substrate, maintains white turbidity even when bent, and can be driven at a low voltage, and a liquid crystal composition used therefor. is there.
本発明は、上記課題を解決するために、種々のモノマー、オリゴマー化合物と液晶組成物との組み合わせを検討した結果、課題を解決するに至った。
すなわち、第１成分として、一般式（Ｉ−１）
In order to solve the above-mentioned problems, the present invention has studied the combinations of various monomers, oligomer compounds and liquid crystal compositions, and as a result, has come to solve the problems.
That is, as the first component, the general formula (I-1)
（式中、Ｒ１は、炭素原子数１〜１０のアルキル基を表し、該アルキル基中の非隣接の１つ又は２つ以上の非隣接の−ＣＨ２−は酸素原子、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−で置き換えられていてもよく、
Ｒ２は、フッ素原子、塩素原子、シアノ基、ＣＦ３基、ＯＣＦ３基、ＯＣＨＦ２基、ＮＣＳ基、又は炭素原子数１〜１０のアルキル基を表し、該アルキル基中の非隣接の１つ又は２つ以上の−ＣＨ２−は酸素原子、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−で置き換えられていてもよく、
環Ａ１、環Ａ２、環Ａ３、及び環Ａ４は、それぞれ独立して、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又は2,6-ナフチレン基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又は2,6-ナフチレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、塩素原子、ＣＦ３基、ＯＣＦ３基又はＣＨ３基を有することができ、
Ｚ１、Ｚ２、及びＺ３は、それぞれ独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ２−ＣＨ２−、−ＣＦ２−ＣＦ２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ２Ｏ−、−ＯＣＨ２−、−ＣＦ２Ｏ−、−ＯＣＦ２−、又は−Ｃ≡Ｃ−を表す。）で表される液晶化合物を少なくとも１種含有し、
第２成分として、一般式（ＩＩ−１）
(In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent —CH 2 — in the alkyl group represents an oxygen atom, —CH═CH -, -COO-, -OCO- may be substituted,
R 2 represents a fluorine atom, a chlorine atom, a cyano group, a CF 3 group, an OCF 3 group, an OCHF 2 group, an NCS group, or an alkyl group having 1 to 10 carbon atoms, and the non-adjacent 1 in the alkyl group One or more —CH 2 — may be replaced by an oxygen atom, —CH═CH—, —COO—, —OCO—,
Ring A 1 , Ring A 2 , Ring A 3 , and Ring A 4 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2 , 5-diyl group, 1,3-dioxane-2,5-diyl group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine- 2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or 2,6-naphthylene group, the 1,4-phenylene group, 1,2,3,4 -Tetrahydronaphthalene-2,6-diyl group or 2,6-naphthylene group is unsubstituted or has one or more fluorine atoms, chlorine atoms, CF 3 groups, OCF 3 groups or CH as substituents Can have 3 groups,
Z 1, Z 2, and Z 3 are each independently a single bond, -COO -, - OCO -, - CH 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH -, - CF═CF—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, or —C≡C— is represented. At least one liquid crystal compound represented by
As the second component, the general formula (II-1)
（式中、Ｘ１は水素原子、又はメチル基であり、Ｚ７は単結合、メチレン基、エチレン基、又はプロピレン基であり、Ｚ７中の一つ以上の非隣接の−ＣＨ２−は酸素原子が相互に直接結合しないものとして、酸素原子、−ＣＯＯ−、−ＯＣＯ−、又は−ＣＯ−で置換されていても良く、Ａ７は一般式（ＩＩ−２）〜（ＩＩ−５）であり、 (In the formula, X 1 is a hydrogen atom or a methyl group, Z 7 is a single bond, a methylene group, an ethylene group, or a propylene group, and one or more non-adjacent —CH 2 — in Z 7 is As those in which oxygen atoms are not directly bonded to each other, they may be substituted with oxygen atoms, —COO—, —OCO—, or —CO—, and A 7 is represented by the general formulas (II-2) to (II-5). And
（式中、１つ以上の−ＣＨ２−は、互いに独立して、酸素原子、硫黄原子、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−で置換されていても良いが、一般式（ＩＩ−２）〜（ＩＩ−５）中に酸素原子及び／又は硫黄原子が合計２個以上存在する場合には、これらは−Ｏ−Ｏ−、−Ｏ−Ｓ−又は−Ｓ−Ｓ−のようにお互い同士結合することは無く、又一つ以上の−ＣＨ２−ＣＨ２−は、−ＣＨ＝ＣＨ−基に置換されていても良い。）
で表される非液晶性の重合性化合物を少なくとも１種含有し、
第３成分として、多官能の（メタ）アクリレート化合物、又は（メタ）アクリレートオリゴマーを少なくとも１種含有し、
第４成分として、光重合開始剤を少なくとも１種含有する高分子分散型液晶素子用液晶組成物を用いると、上記課題が解決できることが判明した。
(In the formula, one or more —CH 2 — may be independently substituted with an oxygen atom, a sulfur atom, —COO—, —OCO—, or —CO—, but may have the general formula (II— 2) to (II-5), when a total of two or more oxygen atoms and / or sulfur atoms are present, these are as in —O—O—, —O—S— or —S—S—. And they are not bonded to each other, and one or more —CH 2 —CH 2 — may be substituted with —CH═CH— group.)
Containing at least one non-liquid crystalline polymerizable compound represented by:
As a third component, at least one polyfunctional (meth) acrylate compound or (meth) acrylate oligomer is contained,
It has been found that the above problem can be solved by using a liquid crystal composition for a polymer dispersed liquid crystal element containing at least one photopolymerization initiator as the fourth component.
本発明の高分子分散型液晶素子用液晶組成物、及び高分子分散型液晶素子により、フィルム基板との密着性に優れ、曲げた状態でも白濁性を維持し、且つ低電圧動作が可能である高分子分散型液晶素子を得ることができた。特に、調光用フィルムに有用な高分子分散型液晶素子用液晶組成物、及び高分子分散型液晶素子である。 The liquid crystal composition for polymer dispersed liquid crystal element and the polymer dispersed liquid crystal element of the present invention have excellent adhesion to a film substrate, maintain white turbidity even in a bent state, and can operate at a low voltage. A polymer dispersed liquid crystal device could be obtained. In particular, they are a liquid crystal composition for polymer dispersed liquid crystal elements and a polymer dispersed liquid crystal element useful for a light control film.
以下に本発明について説明する。
本発明の高分子分散型液晶表示素子用液晶組成物は、第１成分として、一般式（Ｉ−１）
The present invention will be described below.
The liquid crystal composition for polymer dispersed liquid crystal display element of the present invention has the general formula (I-1) as the first component.
（式中、Ｒ１は、炭素原子数１〜１０のアルキル基を表し、該アルキル基中の非隣接の１つ又は２つ以上の非隣接の−ＣＨ２−は酸素原子、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−で置き換えられていてもよく、
Ｒ２は、フッ素原子、塩素原子、シアノ基、ＣＦ３基、ＯＣＦ３基、ＯＣＨＦ２基、ＮＣＳ基、又は炭素原子数１〜１０のアルキル基を表し、該アルキル基中の非隣接の１つ又は２つ以上の−ＣＨ２−は酸素原子、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−で置き換えられていてもよく、
環Ａ１、環Ａ２、環Ａ３、及び環Ａ４は、それぞれ独立して、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又は2,6-ナフチレン基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又は2,6-ナフチレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、塩素原子、ＣＦ３基、ＯＣＦ３基又はＣＨ３基を有することができ、
Ｚ１、Ｚ２、及びＺ３は、それぞれ独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ２−ＣＨ２−、−ＣＦ２−ＣＦ２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ２Ｏ−、−ＯＣＨ２−、−ＣＦ２Ｏ−、−ＯＣＦ２−、又は−Ｃ≡Ｃ−を表す。）で表される液晶化合物を少なくとも１種含有し、
第２成分として、一般式（ＩＩ−１）
(In the formula, R 1 represents an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent —CH 2 — in the alkyl group represents an oxygen atom, —CH═CH -, -COO-, -OCO- may be substituted,
R 2 represents a fluorine atom, a chlorine atom, a cyano group, a CF 3 group, an OCF 3 group, an OCHF 2 group, an NCS group, or an alkyl group having 1 to 10 carbon atoms, and the non-adjacent 1 in the alkyl group One or more —CH 2 — may be replaced by an oxygen atom, —CH═CH—, —COO—, —OCO—,
Ring A 1 , Ring A 2 , Ring A 3 , and Ring A 4 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2 , 5-diyl group, 1,3-dioxane-2,5-diyl group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine- 2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or 2,6-naphthylene group, the 1,4-phenylene group, 1,2,3,4 -Tetrahydronaphthalene-2,6-diyl group or 2,6-naphthylene group is unsubstituted or has one or more fluorine atoms, chlorine atoms, CF 3 groups, OCF 3 groups or CH as substituents Can have 3 groups,
Z 1, Z 2, and Z 3 are each independently a single bond, -COO -, - OCO -, - CH 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH -, - CF═CF—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, or —C≡C— is represented. At least one liquid crystal compound represented by
As the second component, the general formula (II-1)
（式中、Ｘ１は水素原子、又はメチル基であり、Ｚ７は単結合、メチレン基、エチレン基、又はプロピレン基であり、Ｚ７中の一つ以上の非隣接の−ＣＨ２−は酸素原子が相互に直接結合しないものとして、酸素原子、−ＣＯＯ−、−ＯＣＯ−、又は−ＣＯ−で置換されていても良く、Ａ７は一般式（ＩＩ−２）〜（ＩＩ−５）であり、 (In the formula, X 1 is a hydrogen atom or a methyl group, Z 7 is a single bond, a methylene group, an ethylene group, or a propylene group, and one or more non-adjacent —CH 2 — in Z 7 is As those in which oxygen atoms are not directly bonded to each other, they may be substituted with oxygen atoms, —COO—, —OCO—, or —CO—, and A 7 is represented by the general formulas (II-2) to (II-5). And
（式中、１つ以上の−ＣＨ２−は、互いに独立して、酸素原子、硫黄原子、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−で置換されていても良いが、一般式（ＩＩ−２）〜（ＩＩ−５）中に酸素原子及び／又は硫黄原子が合計２個以上存在する場合には、これらは−Ｏ−Ｏ−、−Ｏ−Ｓ−又は−Ｓ−Ｓ−のようにお互い同士結合することは無く、又一つ以上の−ＣＨ２−ＣＨ２−は、−ＣＨ＝ＣＨ−基に置換されていても良い。）
で表される非液晶性の重合性化合物を少なくとも１種含有し、
第３成分として、多官能の（メタ）アクリレート化合物、又は（メタ）アクリレートオリゴマーを少なくとも１種含有し、
第４成分として、光重合開始剤を少なくとも１種含有する含有することに特徴を有する。
(In the formula, one or more —CH 2 — may be independently substituted with an oxygen atom, a sulfur atom, —COO—, —OCO—, or —CO—, but may have the general formula (II— 2) to (II-5), when a total of two or more oxygen atoms and / or sulfur atoms are present, these are as in —O—O—, —O—S— or —S—S—. And they are not bonded to each other, and one or more —CH 2 —CH 2 — may be substituted with —CH═CH— group.)
Containing at least one non-liquid crystalline polymerizable compound represented by:
As a third component, at least one polyfunctional (meth) acrylate compound or (meth) acrylate oligomer is contained,
The fourth component is characterized by containing at least one photopolymerization initiator.
この中でも、特に特徴的なことは、第１成分と第２成分を含有することである。高分子分散型液晶素子は、一般的に紫外線硬化によって、液晶とポリマーの相分離を引き起こし、ポリマーの３次元ネットワーク構造中に液晶組成物が連続層をなす構造、液晶組成物のドロップレットがポリマー中に分散している構造、又は両者が混在する構造をとっている。第２成分である一般式（ＩＩ−１）の化合物は、可撓性に優れる材料であり、曲げに対しては強いが伸び率はそれほど大きくないため、曲げた状態でも液晶組成物に応力がかかりにくく、結果として、この化合物を含有する組成物で作製された高分子分散型液晶素子フィルムは曲げた状態でも白濁性を維持することができる。また、環状構造基と窒素原子の存在により、基板への密着性も向上する。また、第２成分である一般式（ＩＩ−１）の化合物は、比較的親水性の強い化合物であり、一方、第１成分である一般式（Ｉ−１）の化合物は、疎水性の強い化合物であり、一般的に両者の相溶性は良くない。実際に第１成分である一般式（Ｉ−１）の化合物を含む液晶組成物に、第２成分である一般式（ＩＩ−１）の化合物を含む重合性組成物を添加していく場合と、第２成分である一般式（ＩＩ−１）の化合物を含まない重合性組成物を添加していく場合とを比較すると、高分子分散型液晶素子用液晶組成物のＴｎｍは、第２成分である一般式（ＩＩ−１）の化合物を含む重合性組成物を添加していく時の方が、Ｔｎｍの低下が小さい。これは、第１成分である一般式（Ｉ−１）の化合物と第２成分である一般式（ＩＩ−１）の化合物の相溶性が悪いために起こる現象である。ちなみに、第２成分である一般式（ＩＩ−１）の化合物の変わりに、水酸基を持つようなより親水性の高い化合物を添加した場合は、ほとんど相溶せず、第２成分である一般式（ＩＩ−１）の化合物程度の親水性が第１成分である一般式（Ｉ−１）の化合物を含む液晶組成物と相溶できる限界に近いことが理解できる。 Among these, what is particularly characteristic is that it contains the first component and the second component. In general, polymer-dispersed liquid crystal elements cause phase separation between the liquid crystal and the polymer by UV curing, a structure in which the liquid crystal composition forms a continuous layer in the three-dimensional network structure of the polymer, and the droplets of the liquid crystal composition are polymer. It has a structure in which it is dispersed or a structure in which both are mixed. The compound of the general formula (II-1), which is the second component, is a material having excellent flexibility, and is strong against bending, but has a low elongation rate. Therefore, even in the bent state, the liquid crystal composition is stressed. As a result, the polymer-dispersed liquid crystal element film made of the composition containing this compound can maintain white turbidity even in a bent state. In addition, due to the presence of the cyclic structure group and the nitrogen atom, the adhesion to the substrate is also improved. The compound of the general formula (II-1) as the second component is a relatively hydrophilic compound, while the compound of the general formula (I-1) as the first component is highly hydrophobic. It is a compound, and generally the compatibility of both is not good. When the polymerizable composition containing the compound of the general formula (II-1) as the second component is added to the liquid crystal composition actually containing the compound of the general formula (I-1) as the first component; In comparison with the case where the polymerizable composition not containing the compound of the general formula (II-1), which is the second component, is added, the Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements is the second component When the polymerizable composition containing the compound of the general formula (II-1) is added, the decrease in Tnm is small. This is a phenomenon that occurs because the compatibility of the compound of general formula (I-1) as the first component and the compound of general formula (II-1) as the second component is poor. Incidentally, in the case where a more hydrophilic compound having a hydroxyl group is added instead of the compound of the general formula (II-1) as the second component, the compound of the general formula as the second component is hardly compatible. It can be understood that the hydrophilicity of the compound of the formula (II-1) is close to the limit compatible with the liquid crystal composition containing the compound of the general formula (I-1) as the first component.
ここで、第１成分である一般式（Ｉ−１）の化合物を含む液晶組成物に、第２成分である一般式（ＩＩ−１）の化合物を含む重合性組成物を添加していった場合、高分子分散型液晶素子用液晶組成物のＴｎｍが高めになるということは、液晶組成物自身のＴｎｉが低めのものを用いないと、高分子分散型液晶素子用液晶組成物のＴｎｍを室温以下にできないと言うことになり、それに伴い高分子分散型液晶素子とした際の動作温度範囲も低めになってしまうと考えられるが、実際にはそうはならない。第１成分である一般式（Ｉ−１）の化合物を含む液晶組成物と、第２成分である一般式（ＩＩ−１）の化合物を含まない重合性組成物を用いた組成の場合、紫外線を照射して得られた高分子分散型液晶素子のＴｎｐ（高分子分散型液晶素子のネマチック−アイソトロピック転移点）は、用いている液晶組成物自身のＴｎｉより少し低めになる。これは、液晶組成物中の液晶化合物がポリマー中に取り込まれてしまうため起こる現象である。一方、第１成分である一般式（Ｉ−１）の化合物を含む液晶組成物と、第２成分である一般式（ＩＩ−１）の化合物を含む重合性組成物を用いた組成の場合は、紫外線を照射して得られた高分子分散型液晶素子のＴｎｐは、用いている液晶組成物自身のＴｎｉよりも高くなる。高くなる度合いは、第１成分である一般式（Ｉ−１）の化合物の極性や添加量に左右され、極性が低く、添加量が多い場合は、約３０℃以上も元の液晶組成物のＴｎｉよりも高くなる。これは第１成分である一般式（Ｉ−１）の化合物を含む液晶組成物と、第２成分である一般式（ＩＩ−１）の化合物との相溶性が悪いため、紫外線照射による重合相分離過程で、一般式（Ｉ−１）の化合物が優先的に相分離を起こし、ポリマー中に取り込まれる液晶化合物がその組成中でも極性の高い低分子量の化合物（一般式（ＶＩ−１）や（ＶＩＩ−１）で表される化合物等）に限定されるため、残った液晶組成物は結果として、一般式（Ｉ−１）の化合物がリッチな液晶組成物となるためである。さらに、この一般式（Ｉ−１）の化合物が優先的に相分離を起こすという効果により、相分離速度が速くなり、ネットワーク構造、又は液晶ドロップレット粒径の大きな構造が得られることとなり、駆動電圧を低下させることができる。 Here, the polymerizable composition containing the compound of the general formula (II-1) as the second component was added to the liquid crystal composition containing the compound of the general formula (I-1) as the first component. In this case, the Tnm of the liquid crystal composition for the polymer dispersed liquid crystal element is increased. This means that the Tnm of the liquid crystal composition for the polymer dispersed liquid crystal element is not increased unless the liquid crystal composition itself has a low Tni. It can be said that the temperature cannot be lowered to room temperature or less, and it is considered that the operating temperature range when the polymer dispersed liquid crystal element is made lower accordingly, but this is not actually the case. In the case of a composition using a liquid crystal composition containing the compound of general formula (I-1) as the first component and a polymerizable composition not containing the compound of general formula (II-1) as the second component, The Tnp (nematic-isotropic transition point of the polymer dispersed liquid crystal element) of the polymer dispersed liquid crystal element obtained by irradiating is slightly lower than the Tni of the liquid crystal composition itself used. This is a phenomenon that occurs because the liquid crystal compound in the liquid crystal composition is taken into the polymer. On the other hand, in the case of a composition using a liquid crystal composition containing the compound of general formula (I-1) as the first component and a polymerizable composition containing the compound of general formula (II-1) as the second component The Tnp of the polymer-dispersed liquid crystal element obtained by irradiating ultraviolet rays is higher than the Tni of the liquid crystal composition itself used. The degree of increase depends on the polarity and addition amount of the compound of the general formula (I-1) as the first component. When the polarity is low and the addition amount is large, the original liquid crystal composition has a temperature of about 30 ° C. or more. It becomes higher than Tni. This is because the compatibility between the liquid crystal composition containing the compound of the general formula (I-1) as the first component and the compound of the general formula (II-1) as the second component is poor. In the separation process, the compound of the general formula (I-1) preferentially causes phase separation, and the liquid crystal compound incorporated in the polymer is a low-molecular weight compound (general formula (VI-1) or ( This is because the compound of the general formula (I-1) becomes a rich liquid crystal composition as a result of the remaining liquid crystal composition. Furthermore, due to the effect that the compound of general formula (I-1) preferentially causes phase separation, the phase separation speed is increased, and a network structure or a structure having a large liquid crystal droplet particle size is obtained. The voltage can be reduced.
上述のことから、第１成分である一般式（Ｉ−１）の化合物中のＲ２は、低極性化合物となるよう、炭素原子数１〜１０のアルキル基（該アルキル基中の非隣接の１つ又は２つ以上のＣＨ２基は酸素原子、及び／又は−ＣＨ＝ＣＨ−によって置き換えられていてもよい）が好ましく、炭素原子数１〜１０のアルキル基、又はアルコキシ基であることがより好ましく、より低極性化合物とするため炭素原子数４〜１０のアルキル基であることが更により好ましい。 From the above, R 2 in the compound of the general formula (I-1) as the first component is an alkyl group having 1 to 10 carbon atoms (non-adjacent in the alkyl group) so as to be a low polarity compound. One or two or more CH 2 groups may be replaced by an oxygen atom and / or —CH═CH—), preferably an alkyl group having 1 to 10 carbon atoms, or an alkoxy group. More preferably, an alkyl group having 4 to 10 carbon atoms is even more preferable in order to obtain a lower polar compound.
Ｒ１としては、炭素原子数１〜１０のアルキル基、又はアルコキシ基であることが好ましく、環Ａ１〜環Ａ４としては、それぞれ独立して、１−４フェニレン基、又は１−４シクロへキシレン基（該１−４フェニレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、メチル基を有することができる。）であることが好ましく、Ｚ１、Ｚ２、及びＺ３としては、それぞれ独立して、単結合、−ＣＯＯ−、−ＯＣＯ−又は−ＣＨ２−ＣＨ２−であることが好ましい。 R 1 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group, and each of ring A 1 to ring A 4 is independently a 1-4 phenylene group or 1-4 cyclo It is preferably a hexylene group (the 1-4 phenylene group is unsubstituted or can have one or more fluorine atoms or methyl groups as substituents), and Z 1 and Z 2 , And Z 3 are each independently preferably a single bond, —COO—, —OCO— or —CH 2 —CH 2 —.
また、高分子分散型液晶素子用液晶組成物に用いられる液晶組成物のΔｎは高い方が好ましく、Δεも高い方が好ましいことから、液晶組成物中に一般式（Ｉ−１）の化合物に加えて、一般式（ＶＩ−１） In addition, since the Δn of the liquid crystal composition used in the liquid crystal composition for a polymer dispersed liquid crystal element is preferably higher and Δε is also higher, the compound of the general formula (I-1) is preferably included in the liquid crystal composition. In addition, general formula (VI-1)
（式中、Ｒ４は、炭素原子数１〜１０のアルキル基を表し、該アルキル基中の非隣接の１つ又は２つ以上の−ＣＨ２−は互いに独立して酸素原子、−ＣＯＯ−又は−ＯＣＯ−で置き換えられていてもよく、１つ以上の−ＣＨ２−は−ＣＨ＝ＣＨ−によって置き換えられていてもよく、
環Ａ６は、1,4-フェニレン基、1,4-シクロヘキシレン基、1,3-ジオキサン-2,5-ジイル基、ピリジン-2,5-ジイル基、又はピリミジン-2,5-ジイル基を表し、該1,4-フェニレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、塩素原子、ＣＦ３基、ＯＣＦ３基、又はメチル基を有することができ、
Ｙ２、Ｙ３、Ｙ４、及びＹ５は、それぞれ独立して、水素原子、フッ素原子、塩素原子、ＣＦ３基、又はＯＣＦ３基を表し、
Ｚ５、及びＺ６は、それぞれ独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、ＣＨ２−、−ＣＨ＝ＣＨ−、−ＣＦ２Ｏ−、又は−Ｃ≡Ｃ−を表し、
ｎは０又は１を表す。ただしｎが０の場合、Ｙ２又はＹ３の少なくともどちらか一方は水素原子を表す。）
で表される液晶性化合物を含有することが好ましく、Ｒ４は炭素原子数１〜１０のアルキル基、又はアルコキシ基であることがより好ましく、環Ａ６は、１，４−フェニレン基又は１，４−シクロへキシレン基（該１，４−フェニレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子を有することができる。）であることがより好ましく、Ｙ１〜Ｙ４は、それぞれ独立して、水素原子、フッ素原子であることがより好ましく、Ｚ５、Ｚ６は、それぞれ独立して、単結合、−ＣＯＯ−、−ＯＣＯ−又は−ＣＨ２−ＣＨ２−であることがより好ましい。具体的には以下の（ＶＩ−１１）〜（ＶＩ−２８）の化合物が好ましい。
(Wherein R 4 represents an alkyl group having 1 to 10 carbon atoms, and one or two or more non-adjacent —CH 2 — in the alkyl group are each independently an oxygen atom, —COO— or it may be replaced by -OCO-, 1 or more -CH 2 - may be replaced by -CH = CH-,
Ring A 6 is a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,3-dioxane-2,5-diyl group, a pyridine-2,5-diyl group, or a pyrimidine-2,5-diyl group The 1,4-phenylene group can be unsubstituted or have one or more fluorine, chlorine, CF 3 , OCF 3 or methyl groups as substituents. ,
Y 2 , Y 3 , Y 4 , and Y 5 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a CF 3 group, or an OCF 3 group,
Z 5 and Z 6 each independently represent a single bond, —COO—, —OCO—, CH 2 —, —CH═CH—, —CF 2 O—, or —C≡C—,
n represents 0 or 1. However, when n is 0, at least one of Y 2 and Y 3 represents a hydrogen atom. )
It is preferable that R 4 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group, and ring A 6 is a 1,4-phenylene group or 1 , 4-cyclohexylene group (the 1,4-phenylene group may be unsubstituted or may have one or more fluorine atoms as a substituent), and Y 1 to Y 4 each independently represent a hydrogen atom, more preferably a fluorine atom, Z 5, Z 6 are each independently a single bond, -COO -, - OCO- or -CH 2 -CH 2- is more preferable. Specifically, the following compounds (VI-11) to (VI-28) are preferred.
（式中Ｒ４１は炭素原子数１〜１０のアルキル基、又はアルコキシ基を表し、Ｙ１１〜Ｙ５０は、それぞれ独立して水素原子、又はフッ素原子を表す。）
第１成分である一般式（Ｉ−１）の化合物を用いた組成物は、液晶組成物自身のＴｎｉが高めになり、前述の高分子分散型液晶素子用液晶組成物のＴｎｍを室温以下にするためには、液晶組成物自身のＴｎｉを低めにする必要がある、この様な場合には、一般式（ＶＩＩ−１）
(In the formula, R 41 represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group, and Y 11 to Y 50 each independently represent a hydrogen atom or a fluorine atom.)
In the composition using the compound of the general formula (I-1) which is the first component, the Tni of the liquid crystal composition itself is increased, and the Tnm of the liquid crystal composition for a polymer dispersed liquid crystal element is reduced to room temperature or lower. In order to achieve this, it is necessary to lower the Tni of the liquid crystal composition itself. In such a case, the general formula (VII-1)
（式中、Ｒ３は炭素原子数１〜１０のアルキル基を表し、該アルキル基中の非隣接の１つ又は２つ以上の−ＣＨ２−はそれぞれ独立して酸素原子、−ＣＯＯ−、又は−ＯＣＯ−で置き換えられていてもよく、１つ以上のメチレン基は−ＣＨ＝ＣＨ−によって置き換えられていてもよく、
Ｙ１はフッ素原子、塩素原子、シアノ基、ＣＦ３基、ＯＣＦ３基、ＯＣＨＦ２基、又はＮＣＳ基を表し
Ｚ４は、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ２−ＣＨ２−、−ＣＦ２Ｏ−、又は−Ｃ≡Ｃ−を表し、
環Ａ５は、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又は2,6-ナフチレン基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、塩素原子、ＣＦ３基、ＯＣＦ３基又はＣＨ３基を有することができる。）
で表される、外挿Ｔｎｉが低い液晶性化合物を添加し、液晶組成物自身のＴｎｉを調整することが好ましい。
(Wherein R 3 represents an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent —CH 2 — in the alkyl group are each independently an oxygen atom, —COO—, Or -OCO- and one or more methylene groups may be replaced by -CH = CH-
Y 1 is a fluorine atom, a chlorine atom, a cyano group, CF 3 group, OCF 3 group, Z 4 represents OCHF 2 group, or an NCS group, a single bond, -COO -, - OCO -, - CH 2 -CH 2 -, -CF 2 O-, or -C≡C-
Ring A 5 are 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group Decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene- Represents a 2,6-diyl group or a 2,6-naphthylene group, and the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and 2,6-naphthylene group are It can be unsubstituted or have one or more fluorine, chlorine, CF 3 , OCF 3 or CH 3 groups as substituents. )
It is preferable to adjust the Tni of the liquid crystal composition itself by adding a liquid crystal compound having a low extrapolation Tni represented by:
一般式（ＶＩＩ−１）の中でも、Ｙ１がシアノ基、又はフッ素原子であることが好ましく、高Δεが必要であればシアノ基がより好ましい。Ｒ３としては炭素原子数１〜１０のアルキル基、又はアルコキシ基であることが好ましく、低Ｔｎｉとするため炭素原子数２〜５のアルキル基、又はアルコキシ基であることがより好ましい。Ｚ４は、単結合、又は−ＣＯＯ−であることが好ましく、環Ａ５としては、1,4-フェニレン基、1,4-シクロヘキシレン基（（該1,4-フェニレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子を有することができる）であることが好ましい。具体的には下記（ＶＩＩ−１１）〜（ＶＩＩ−２６）の化合物が好ましい。 Among general formulas (VII-1), Y 1 is preferably a cyano group or a fluorine atom, and a cyano group is more preferable if high Δε is required. R 3 is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group, and more preferably an alkyl group having 2 to 5 carbon atoms or an alkoxy group in order to achieve low Tni. Z 4 is preferably a single bond or —COO—, and ring A 5 includes a 1,4-phenylene group, a 1,4-cyclohexylene group (wherein the 1,4-phenylene group is unsubstituted) Or it may have one or more fluorine atoms as a substituent.) Specifically, the following compounds (VII-11) to (VII-26) are preferable.
（式中Ｒ３１は炭素原子数２〜５までのアルキル基、又はアルコキシ基を表す。）
高分子分散型液晶に用いる液晶組成物の屈折率異方性（Δｎ）は一般に高い方が好ましく、Δｎは０．１６以上が好ましく、０．１８以上がより好ましく、０．２０以上が更により好ましく、０．２２以上が最も好ましい。これらのΔｎを持つ液晶組成物の常光屈折率（ｎｏ）は通常１．５０〜１．５４程度である。高分子分散型液晶素子に電圧を印加し、透明状態とした場合、この液晶組成物のｎｏとネットワーク構造を形成しているポリマーの屈折率（ｎｐ）がほぼ一致していると、高い透明性を得ることができる。しかし、モノマー及びオリゴマーがＵＶ照射等によってポリマー化する際に、一部の液晶組成物を抱き込んだ形で硬化するため、実際のポリマーの屈折率は純粋なものよりも高くなる。そのため、モノマー及びオリゴマーの屈折率は１．５より低い方が好ましく、１．４８以下がより好ましく、１．４７以下が更により好ましい。
(In the formula, R 31 represents an alkyl group having 2 to 5 carbon atoms or an alkoxy group.)
In general, the refractive index anisotropy (Δn) of the liquid crystal composition used for the polymer-dispersed liquid crystal is preferably higher. Δn is preferably 0.16 or more, more preferably 0.18 or more, and even more preferably 0.20 or more. 0.22 or more is most preferable. The ordinary light refractive index (no) of these liquid crystal compositions having Δn is usually about 1.50 to 1.54. When a voltage is applied to the polymer-dispersed liquid crystal element to make it transparent, high transparency is obtained when the refractive index (np) of the polymer forming the network structure and the no of the liquid crystal composition are substantially the same. Can be obtained. However, when the monomers and oligomers are polymerized by UV irradiation or the like, the refractive index of the actual polymer is higher than that of the pure polymer because the monomer and oligomer are cured in such a way that some liquid crystal compositions are included. Therefore, the refractive index of the monomer and oligomer is preferably lower than 1.5, more preferably 1.48 or less, and even more preferably 1.47 or less.
第２成分の重合性の化合物である、一般式（ＩＩ−１）の化合物は、前述の通り、可撓性に優れる材料であり、この化合物を用いると、曲げた状態でも白濁性を維持することができる。また、環状構造基と窒素原子の存在により、基板への密着性も向上させることができる。一般式（ＩＩ−１）の化合物の中でも、一般式（ＩＩ−６） The compound of the general formula (II-1), which is the polymerizable compound of the second component, is a material having excellent flexibility as described above, and when this compound is used, the cloudiness is maintained even in a bent state. be able to. In addition, the presence of the cyclic structure group and the nitrogen atom can also improve the adhesion to the substrate. Among the compounds of the general formula (II-1), the general formula (II-6)
（式中、１つ以上の−ＣＨ２−は、互いに独立して、酸素原子、硫黄原子、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−で置換されていても良いが、酸素原子及び／又は硫黄原子が合計２個以上存在する場合には、これらは−Ｏ−Ｏ−、−Ｏ−Ｓ−又は−Ｓ−Ｓ−のようにお互い同士結合することは無い。）
であることが好ましく、式（ＩＩ−７）
(In the formula, one or more —CH 2 — may be independently substituted with an oxygen atom, a sulfur atom, —COO—, —OCO— or —CO—, but an oxygen atom and / or When two or more sulfur atoms are present in total, they are not bonded to each other like —O—O—, —O—S— or —S—S—.)
It is preferable that it is Formula (II-7)
で表される化合物であることが更により好ましい。 It is still more preferable that it is a compound represented by these.
第３成分の多官能（メタ）アクリレート化合物、又は多官能（メタ）アクリレートオリゴマーは、ポリマーのネットワーク構造中に架橋構造を導入するために必要な化合物である。多官能（メタ）アクリレート化合物、又は多官能（メタ）アクリレートオリゴマーの中でも、２官能アクリレート、２官能アクリレートオリゴマーが好ましい。さらに、基板との密着性を重視するには、ウレタン系、又はポリエステル系アクリレートオリゴマーであることが好ましく、ウレタンアクリレートオリゴマーであることが更により好ましい。ウレタンアクリレートオリゴマーにはポリエステル系、ポリエーテル系などがあるが、ポリエーテル系の方が好ましい。分子量としては2000〜30000が好ましく、5000〜20000がより好ましく、7000〜15000が更により好ましい。これは、あまり分子量が小さいと硬化収縮のため密着性が悪化してしまい、逆にあまり分子量が大きいと架橋間距離が長くなるため、隙間が大きくなり、液晶を取り込みやすくなるからである。すなわち高温下での環境に放置すると、ポリマーが液晶を吸収してしまい、特性が大きく変化してしまうためである。また、分子量が大きいと重合性化合物添加による高分子分散型液晶の転移点Ｔｎｍの低下度合いが小さくなり、Ｔｎｍを室温以下にするには、液晶組成物自身のＴｎｉが低い材料を用いなければならなくなるため、結果的に動作温度範囲が狭くなってしまう問題も生じてしまう。 The third component polyfunctional (meth) acrylate compound or polyfunctional (meth) acrylate oligomer is a compound necessary for introducing a cross-linked structure into the network structure of the polymer. Among the polyfunctional (meth) acrylate compound or the polyfunctional (meth) acrylate oligomer, a bifunctional acrylate and a bifunctional acrylate oligomer are preferable. Furthermore, in order to attach importance to the adhesion to the substrate, a urethane-based or polyester-based acrylate oligomer is preferable, and a urethane acrylate oligomer is still more preferable. Urethane acrylate oligomers include polyesters and polyethers, with polyethers being preferred. The molecular weight is preferably 2000 to 30000, more preferably 5000 to 20000, and even more preferably 7000 to 15000. This is because if the molecular weight is too small, the adhesiveness deteriorates due to curing shrinkage, and conversely if the molecular weight is too large, the distance between crosslinks becomes long, so that the gap becomes large and it becomes easy to take in the liquid crystal. That is, if the polymer is left in an environment at a high temperature, the polymer absorbs the liquid crystal and the characteristics are greatly changed. In addition, when the molecular weight is large, the degree of decrease in the transition point Tnm of the polymer dispersed liquid crystal due to the addition of the polymerizable compound becomes small, and in order to make Tnm below room temperature, a material having a low Tni of the liquid crystal composition itself must be used. As a result, there is a problem that the operating temperature range becomes narrow as a result.
多官能のウレタン（メタ）アクリレートオリゴマーは、水酸基含有アクリレートと、ポリオール、ポリイソシアネートを反応させて得られる。ポリオールとしては、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール等があげられ、ポリエーテルポリオールとしては、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等があげられる。ポリイソシアネートとしては、２，４−および２、６−トリレンジイソシアネート（ＴＤＩ）、オルトトルイジンジイソシアネート（ＴＯＤＩ）、ナフチレンジイソシアネート（ＮＤＩ）、キシリレンジイソシアネート（ＸＤＩ）、４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）、イソホロンジイソシアネート、およびカルボジイミド変成ＭＤＩ、ポリメチレンポリフェニルイソシアネート、ポリメリックポリイソシアネート等があげられる。水酸基含有アクリレートとしては、ヒドロキシエチルアクリレート、ヒドロキシブチルアクリレート、１，４−シクロヘキサンジメタノールモノアクリレート等があげられる。 A polyfunctional urethane (meth) acrylate oligomer is obtained by reacting a hydroxyl group-containing acrylate with a polyol and a polyisocyanate. Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, and polybutadiene polyol. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the polyisocyanate include 2,4- and 2,6-tolylene diisocyanate (TDI), orthotoluidine diisocyanate (TODI), naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), 4,4′-diphenylmethane diisocyanate ( MDI), isophorone diisocyanate, carbodiimide modified MDI, polymethylene polyphenyl isocyanate, polymeric polyisocyanate, and the like. Examples of the hydroxyl group-containing acrylate include hydroxyethyl acrylate, hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate and the like.
具体的には、以下の一般式（ＶＩＩＩ−１）の化合物が好ましい。 Specifically, the compound of the following general formula (VIII-1) is preferable.
（式中、Ｘ９は水素原子、又はメチル基を表し、Ｂ１は炭素原子数１〜４までのアルキル基を表し、該アルキル基中の一つ以上の−ＣＨ２−は酸素原子、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−で置換されていても良く、bは１〜２０を表し、Ｂ２は、下記（ＶＩＩＩ−２）、又は（ＶＩＩＩ−３） (In the formula, X 9 represents a hydrogen atom or a methyl group, B 1 represents an alkyl group having 1 to 4 carbon atoms, and one or more —CH 2 — in the alkyl group represents an oxygen atom, — CO -, - COO -, - may be substituted with OCO-, b represents 1 to 20, B 2 is the following (VIII-2), or (VIII-3)
を表し、Ｂ３は下記（ＶＩＩＩ−４） B 3 represents the following (VIII-4)
（式中、Ｘ１０は水素原子、又はメチル基を表し、ｔは２０〜３００を表す）
を表す。）
より低電圧で駆動させるためには、重合性化合物として、一般式（Ｖ−１）、及び一般式（Ｖ−２）
(Wherein X 10 represents a hydrogen atom or a methyl group, and t represents 20 to 300)
Represents. )
In order to drive at a lower voltage, as the polymerizable compound, general formula (V-1) and general formula (V-2)
（式中、Ｘ２は水素原子、又はメチル基を表し、Ｚ８は単結合、炭素数１〜２４までのアルキレン基であり、該アルキレン基中１つ以上の非隣接の−ＣＨ２−は酸素原子、−ＣＯ−、−ＣＯＯ−、又は−ＯＣＯ−で置換されていても良く、Ａ８は環状基が１〜３個までの環式化合物基であり、Ｚ８と直接結合する環状基の結合原子は窒素原子ではなく、
Ｒ５、及びＲ６は、それぞれ独立して水素原子、又は炭素原子数１〜１２までのアルキル基を表すが、該アルキル基中１つ以上の非隣接の−ＣＨ２−は互いに独立して酸素原子、−ＣＯ−、−ＣＯＯ−、又は−ＯＣＯ−で置換されていても良く、
Ｚ９は水素原子、又は炭素数１〜２４までのアルキル基を表すが、該アルキル基中の１つ以上の非隣接の−ＣＨ２−は互いに独立して酸素原子、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、又は一般式（Ｖ−３）
(Wherein X 2 represents a hydrogen atom or a methyl group, Z 8 is a single bond or an alkylene group having 1 to 24 carbon atoms, and one or more non-adjacent —CH 2 — in the alkylene group is May be substituted with an oxygen atom, —CO—, —COO—, or —OCO—, and A 8 is a cyclic compound group having 1 to 3 cyclic groups, and a cyclic group directly bonded to Z 8 Is not a nitrogen atom,
R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and one or more non-adjacent —CH 2 — in the alkyl group are independently from each other. May be substituted with an oxygen atom, -CO-, -COO-, or -OCO-,
Z 9 represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, and one or more non-adjacent —CH 2 — in the alkyl group are each independently an oxygen atom, —CO—, —COO. -, -OCO-, or general formula (V-3)
（Ｒ７は、水素原子、又は炭素原子数１〜１２までのアルキル基を表すが、該アルキル基中１つ以上の非隣接の−ＣＨ２−は互いに独立して酸素原子、−ＣＯ−、−ＣＯＯ−、又は−ＯＣＯ−で置換されていても良い。）
で置換されていても良く、且つ直鎖であっても分岐していても良く、
ａは０又は１、ｂは０、１、２又は３である。）
で表される化合物群から選ばれる少なくとも１種の重合性化合物を加えることが好ましい。
(R 7 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and one or more non-adjacent —CH 2 — in the alkyl group are each independently an oxygen atom, —CO—, (It may be substituted with -COO- or -OCO-)
And may be linear or branched,
a is 0 or 1, and b is 0, 1, 2 or 3. )
It is preferable to add at least one polymerizable compound selected from the group of compounds represented by:
このとき、低電圧駆動と密着性向上の中でより密着性向上に重きを置く場合は、一般式（Ｖ−１）の化合物の中でも、一般式（Ｖ−２１）、 At this time, in the case where the emphasis is on the improvement of the adhesion in the low voltage driving and the improvement of the adhesion, among the compounds of the general formula (V-1), the general formula (V-21),
（式中、Ｘ３は水素原子、又はメチル基を表し、Ｚ１０は単結合、炭素数１〜４までのアルキレン基を表し、該アルキレン基中１つ以上の非隣接の−ＣＨ２−は、お互いに独立して酸素原子、−ＣＯ−、−ＣＯＯ−、又は−ＯＣＯ−で置換されていても良く、Ａ１０は、一般式（Ｖ−２２）から（Ｖ−３１） (Wherein X 3 represents a hydrogen atom or a methyl group, Z 10 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and one or more non-adjacent —CH 2 — in the alkylene group is , Independently of one another, may be substituted with an oxygen atom, —CO—, —COO—, or —OCO—, and A 10 is a group represented by the general formulas (V-22) to (V-31):
（式中、一つ以上の−ＣＨ２−ＣＨ２−は−ＣＨ＝ＣＨ−によって置き換えられていてもよく、１つ以上の−ＣＨ２−は、互いに独立して、酸素原子、硫黄原子、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−で置換されていても良いが、一般式（Ｖ−２２）〜（Ｖ−３１）中に酸素原子及び／又は硫黄原子が合計２個以上存在する場合には、これらは−Ｏ−Ｏ−、−Ｏ−Ｓ−又は−Ｓ−Ｓ−のようにお互い同士結合することは無く、式（Ｖ−２２）〜（Ｖ−３１）中の水素原子は、炭素原子数１〜８までのアルキル基で置換されていてもよく、該アルキル基中の一つ以上の非隣接の−ＣＨ２−は酸素原子、−ＣＯ−、−ＣＯＯ−、又は−ＯＣＯ−で置換されていても良く、且つ直鎖であっても分岐していてもよい。）である化合物が好ましく、
より具体的には、下記の（Ｖ−５１）から（Ｖ−７１）の化合物が好ましい。
(In the formula, one or more —CH 2 —CH 2 — may be replaced by —CH═CH—, and one or more —CH 2 — are independently of each other an oxygen atom, a sulfur atom, -COO-, -OCO-, or -CO- may be substituted, but in the general formulas (V-22) to (V-31), there are a total of two or more oxygen atoms and / or sulfur atoms Are not bonded to each other like —O—O—, —O—S— or —S—S—, and the hydrogen atoms in the formulas (V-22) to (V-31) are The alkyl group having 1 to 8 carbon atoms may be substituted, and one or more non-adjacent —CH 2 — in the alkyl group may be an oxygen atom, —CO—, —COO—, or —OCO. A compound which may be substituted with-and may be linear or branched).
More specifically, the following compounds (V-51) to (V-71) are preferable.
（式中Ｘ５は水素原子、又はメチル基を表す。）
構造式（Ｖ−５１）〜（Ｖ−７１）の中でも、（Ｖ−５４）、（Ｖ−５５）、（Ｖ−５６）、（Ｖ−５７）、（Ｖ−５８）、（Ｖ−６３）、（Ｖ−６５）、（Ｖ−６７）がより好ましい。
(In the formula, X 5 represents a hydrogen atom or a methyl group.)
Among structural formulas (V-51) to (V-71), (V-54), (V-55), (V-56), (V-57), (V-58), (V-63) ), (V-65), and (V-67) are more preferable.
一方、密着性よりも低電圧駆動を重視するのであれば、一般式（Ｖ−１）の化合物の中でも、一般式（Ｖ−２）、及び一般式（Ｖ−６１） On the other hand, if importance is attached to low voltage driving rather than adhesion, among the compounds of general formula (V-1), general formula (V-2) and general formula (V-61)
（式中、Ｘ２及び、Ｘ４はそれぞれ独立して水素原子、又はメチル基を表し、
Ｒ５、及びＲ６はそれぞれ独立して水素原子、又は炭素原子数１〜１２までのアルキル基を表すが、該アルキル基中１つ以上の非隣接の−ＣＨ２−は互いに独立して酸素原子、−ＣＯ−、−ＣＯＯ−、又は−ＯＣＯ−で置換されていても良く、
Ａ１１は、炭素原子数１〜２４までのアルキル基であり、該アルキル基中１つ以上の非隣接の−ＣＨ２−は酸素原子、窒素原子、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、又は一般式（Ｖ−３）
(Wherein X 2 and X 4 each independently represent a hydrogen atom or a methyl group,
R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and one or more non-adjacent —CH 2 — in the alkyl group are each independently oxygen May be substituted with an atom, -CO-, -COO-, or -OCO-,
A 11 is an alkyl group having 1 to 24 carbon atoms, and one or more non-adjacent —CH 2 — in the alkyl group is an oxygen atom, a nitrogen atom, —CO—, —COO—, —OCO—. Or general formula (V-3)
（Ｒ７は、水素原子、又は炭素原子数１〜１２までのアルキル基を表し、該アルキル基中１つ以上の非隣接の−ＣＨ２−は酸素原子、窒素原子、−ＣＯ−、−ＣＯＯ−、又は−ＯＣＯ−で置換されていても良い。）
で置換されていても良く、且つ分岐鎖を持っていても良い。）であることが好ましい。
(R 7 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and one or more non-adjacent —CH 2 — in the alkyl group is an oxygen atom, a nitrogen atom, —CO—, —COO. -Or -OCO- may be substituted.)
It may be substituted with and may have a branched chain. ) Is preferable.
具体的には、以下の化合物が好ましい。 Specifically, the following compounds are preferable.
イソアミル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、イソステアリル（メタ）アクリレート、２エチルヘキシル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、イソデシル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、エトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、エトキシポリプロピレングリコール（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、２−エチルヘキシル−ジグリコール（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジエチルアクリルアミド。 Isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, 2 ethylhexyl (meth) acrylate, isobutyl (meth) acrylate , T-butyl (meth) acrylate, isodecyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, butoxyethyl ( (Meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, octyl (meth) acrylate, Sil (meth) acrylate, N, N-dimethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-diethyl acrylamide.
このうち、より低電圧駆動をするためには、アルキルタイプのアクリレート化合物が好ましく、低電圧と密着性のバランスをとるには、アルキル基中１つ以上の−ＣＨ２−が一般式（Ｖ−３） Among these, in order to drive at a lower voltage, an alkyl type acrylate compound is preferable. To balance low voltage and adhesion, one or more —CH 2 — in the alkyl group is represented by the general formula (V— 3)
（Ｒ７は、水素原子、又は炭素原子数１〜１２のアルキル基を表す。）
に置換されている化合物が好ましい。
(R 7 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)
Compounds substituted with are preferred.
密着性と低電圧駆動のバランスを取るため、一般式（Ｖ−２１）と、一般式（Ｖ−２）及び一般式（Ｖ−６１）の化合物を併用することも可能である。 In order to balance adhesion and low-voltage driving, it is also possible to use the compounds of general formula (V-21), general formula (V-2) and general formula (V-61) together.
第４成分である、光重合開始剤としては、３３０ｎｍ以上に光吸収域を有する化合物が好ましく、具体的には以下の化合物が好ましい。 As the photopolymerization initiator which is the fourth component, a compound having a light absorption region at 330 nm or more is preferable, and specifically, the following compounds are preferable.
ジフェニル−（２，４，６−トリメチルベンゾイル）フォスフィンオキシド、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシーシクロヘキシル−フェニル−ケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、ベンゾフェノン、１−[４−（２−ヒドロキシエトキシ）−フェニル]−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒドロキシ−１−｛４−[４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル]−フェニル｝−２−メチル−プロパン−１−オン、フェニルグリオキシリックアシッドメチルエステル、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、２−ジメチルアミノ−２−（４−メチル−ベンジル）−１−（４−モルフォリン−４−イル−フェニル）−ブタン−１−オン、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、１，２−オクタンジオン，１−［４−（フェニルチオ）−，２−（Ｏ−ベンゾイルオキシム）］、エタノン，１−[９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル]−，１−（Ｏ−アセチルオキシム）、ベンゾフェノン、メチルベンゾイルフォーメート、オリゴ｛２−ヒドロキシ−２−メチル−１−[４−（１−メチルビニル）フェニル]プロパノン、２，４，６トリメチルベンゾフェノン、４−メチルベンゾフェノン、２−エトキシ−１，２−ジフェニルエタン−１−オン、２−（１−メチルエトキシ）−１，２−ジフェニルエタン−１−オン、２−イソブトキシ−２−フェニルアセトフェノン。 Diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl -1-phenyl-propan-1-one, benzophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morph Olinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2,4,6 -Trimethylbenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl) Oxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), benzophenone, methylbenzoylformate, oligo { 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 2,4,6 trimethylbenzophenone 4-methylbenzophenone, 2-ethoxy-1,2-diphenylethane-1-one, 2- (1-methylethoxy) -1,2-diphenylethane-1-one, 2-isobutoxy-2-phenylacetophenone.
特にこの中でも、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オンがより好ましい。 Among these, 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-hydroxy-2-methyl-1-phenyl-propan-1-one are more preferable.
より密着性を重視した組成のためには、一般式（ＶＩＩＩ−１） For a composition that emphasizes adhesion, the general formula (VIII-1)
で表される基を有する化合物を添加することが好ましい。具体的には下記の化合物を添加することが好ましい。 It is preferable to add the compound which has group represented by these. Specifically, it is preferable to add the following compound.
（式中Ｘ６、Ｘ７、及びＸ８はそれぞれ独立して水素原子、又はメチル基を表し、ｑ、ｒ、及びｓは１から４を表す。）
一般式（ＶＩＩＩ−１）で表される基を有する化合物の添加量としては、０．００５〜２質量％であることが好ましく、０．０１〜０．５質量％であることがより好ましく、０．０１〜０．２質量％であることが更に好ましい。
また、先に述べたとおり、一般式（Ｉ−１）で表される化合物と、一般式（ＩＩ−１）で表される化合物とは相溶性がよくない。この相溶性の悪さを利用して、速い相分離を引き起こし、ポリマーネットワークサイズ、又は液晶ドロップレットサイズ等を大きめに作製することが、本発明のポイントであるが、そもそも両者が混ざり合わなければ、実用的には意味をなさない。そのような場合には、界面活性剤を添加することで解決できる。界面活性剤としては、ＨＬＢ値が１０以下のものが好ましく、６以下がより好ましい。添加量としては、０．００１〜０．５質量％が好ましく、０．０１〜０．２質量％であることが更に好ましい。
(Wherein X 6 , X 7 , and X 8 each independently represent a hydrogen atom or a methyl group, and q, r, and s represent 1 to 4).
The amount of the compound having a group represented by the general formula (VIII-1) is preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, More preferably, it is 0.01-0.2 mass%.
Further, as described above, the compound represented by the general formula (I-1) and the compound represented by the general formula (II-1) are not compatible. Utilizing this poor compatibility, causing rapid phase separation and making the polymer network size or liquid crystal droplet size larger is the point of the present invention, but if both are not mixed in the first place, It doesn't make sense practically. In such a case, it can be solved by adding a surfactant. The surfactant preferably has an HLB value of 10 or less, more preferably 6 or less. As addition amount, 0.001-0.5 mass% is preferable, and it is still more preferable that it is 0.01-0.2 mass%.
また、界面活性剤の変わりに、下記一般式（ＩＸ−１） Further, instead of the surfactant, the following general formula (IX-1)
（式中、Ｒ６は炭素原子数１〜１０のアルキル基、又はアルコキシ基を表し、環Ａ１２は1,4-フェニレン基、又は1,4-シクロヘキシレン基を表し、Ｘ１３はシアノ基、又はフッ素原子を表し、Ｘ１１、及びＸ１２は、それぞれ独立して、水素原子、又はフッ素原子を表す。）であらわされる液晶化合物を含有することも効果的である。この化合物は極性の強い構造と、非極性の構造を併せ持ち、両者をつなぎ止める役割をする。 (Wherein R 6 represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group, ring A 12 represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and X 13 represents a cyano group. Or a fluorine atom, and X 11 and X 12 each independently represent a hydrogen atom or a fluorine atom). This compound has both a strong polar structure and a nonpolar structure, and plays a role in tying them together.
重合性化合物側では、両親媒性という特徴を持つ、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジエチルアクリルアミドを添加することが相溶性改善に効果的である。 On the polymerizable compound side, the addition of N, N-dimethylacrylamide, N, N-dimethylaminoethyl acrylate, and N, N-diethylacrylamide, which are amphiphilic, is effective in improving compatibility.
本発明の高分子分散型液晶組成物中の液晶性の化合物の濃度としては、ポリマーネットワーク構造、又は液晶ドロップレット構造の大きさの観点、及び高分子分散型液晶組成物のＴｎｉの観点から、５５〜９０質量％であることが好ましく、７０〜８０質量％がより好ましく、非液晶性の化合物の濃度は１０〜４５質量％が好ましく、２０〜３０質量％であることがより好ましい。これは、あまり液晶性の化合物の濃度が高いと、高分子分散型液晶組成物のＴｎｉを室温以下にするためには、液晶組成物のＴｎｉを低めに設定しなければならず、結果として動作温度範囲が狭くなってしまうためであり、更に液晶性の化合物の濃度があまりに高いと、ポリマーネットワーク構造、又は液晶ドロップレット構造の大きさ大きくなり、結果として光散乱性能が低下してしまうためである。また、あまりに液晶性の化合物の濃度が低いと、ポリマーネットワーク構造、又は液晶ドロップレット構造の大きさが小さくなりすぎて、駆動電圧が高くなってしまうためである。なお、液晶性の化合物とは液晶組成物に添加した際にその液晶性を極端に低下させない化合物であり、棒状の分子形状を持つ化合物であり、非液晶性の化合物とは液晶組成物に添加した際にその液晶性を極端に低下させる化合物であり、それ自体液晶相をさない化合物である。これら高分子分散型液晶素子用液晶組成物に含まれる液晶性を示す化合物の組成物を液晶組成物と記載し、重合性基を有する化合物を重合性化合物と高分子分散型液晶素子用液晶組成物に含まれる重合性化合物の組成物を重合性組成物と記載する。 As the concentration of the liquid crystalline compound in the polymer dispersed liquid crystal composition of the present invention, from the viewpoint of the size of the polymer network structure or the liquid crystal droplet structure, and from the viewpoint of Tni of the polymer dispersed liquid crystal composition, It is preferably 55 to 90% by mass, more preferably 70 to 80% by mass, and the concentration of the non-liquid crystalline compound is preferably 10 to 45% by mass, and more preferably 20 to 30% by mass. This is because if the concentration of the liquid crystal compound is too high, the Tni of the liquid crystal composition must be set low in order to keep the Tni of the polymer dispersion type liquid crystal composition below room temperature, resulting in operation. This is because the temperature range becomes narrow, and if the concentration of the liquid crystal compound is too high, the size of the polymer network structure or the liquid crystal droplet structure increases, resulting in a decrease in light scattering performance. is there. Further, when the concentration of the liquid crystal compound is too low, the polymer network structure or the liquid crystal droplet structure becomes too small, and the drive voltage becomes high. A liquid crystal compound is a compound that does not drastically reduce liquid crystal properties when added to a liquid crystal composition, is a compound having a rod-like molecular shape, and a non-liquid crystal compound is added to a liquid crystal composition. It is a compound that drastically lowers its liquid crystallinity and does not itself have a liquid crystal phase. The composition of the compound exhibiting liquid crystallinity contained in these liquid crystal compositions for polymer dispersed liquid crystal elements is referred to as a liquid crystal composition, and the compound having a polymerizable group is a polymerizable compound and the liquid crystal composition for polymer dispersed liquid crystal elements. The composition of the polymerizable compound contained in the product is referred to as a polymerizable composition.
高分子分散型液晶素子用液晶組成物に含まれる液晶性の化合物中の一般式（Ｉ−１）で表される化合物の濃度としては、１〜２０質量％であることが好ましく、２〜１０質量％であることがより好ましい。高分子分散型液晶素子用液晶組成物に含まれる重合性基を有する化合物中の一般式（ＩＩ−１）で表される化合物の濃度としては、３０〜９０質量％であることが好ましく、４０〜６０質量％であることがより好ましい。 The concentration of the compound represented by the general formula (I-1) in the liquid crystalline compound contained in the liquid crystal composition for polymer dispersed liquid crystal elements is preferably 1 to 20% by mass, and preferably 2 to 10%. More preferably, it is mass%. As a density | concentration of the compound represented by general formula (II-1) in the compound which has a polymeric group contained in the liquid crystal composition for polymer dispersion-type liquid crystal elements, it is preferable that it is 30-90 mass%, 40 More preferably, it is -60 mass%.
また、第１〜第９成分以外にも必要であれば、他の成分を含有することも当然可能であり、着色のため色素等を入れることもできる。 Further, if necessary in addition to the first to ninth components, other components can naturally be contained, and a dye or the like can be added for coloring.
次に、この高分子分散型液晶組成物を用いた調光フィルムについて説明する。
少なくとも一方が透明の２枚の基板間に、本発明の高分子分散型液晶組成物を狭持した後、熱、又は活性エネルギー線を照射することによって重合性化合物を重合させ、液晶組成物との相分離を誘発させることにより、液晶組成物と透明性高分子物質からなる調光層が形成されることによって調光フィルムが得られる。２枚の基板としては、ガラスであっても良いが、プラスチックフィルムであることが好ましく、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥＳ（芳香族ポリエーテルスルフォン）、ＰＭＭＡ（アクリル樹脂）、ＰＣ（ポリカーボネート）、脂環式ポリオレフィン樹脂、環状オレフィン系樹脂、ＰＡＲ（ポリアリレート）、ＰＥＥＫ（芳香族ポリエーテルケトン）等が好ましい。一般的に駆動のため表面表面には透明電極が付いている。また、重合する手段としては、紫外線照射で行うことが好ましい。またガラス基板表面にはポリイミド、ＳｉＯ２等によるコーティングを施すこともできる。
Next, a light control film using the polymer dispersed liquid crystal composition will be described.
After sandwiching the polymer-dispersed liquid crystal composition of the present invention between two substrates, at least one of which is transparent, the polymerizable compound is polymerized by irradiating heat or active energy rays, and the liquid crystal composition By inducing phase separation, a light control film is obtained by forming a light control layer composed of a liquid crystal composition and a transparent polymer substance. The two substrates may be glass, but are preferably plastic films, PET (polyethylene terephthalate), PES (aromatic polyether sulfone), PMMA (acrylic resin), PC (polycarbonate), fat Cyclic polyolefin resin, cyclic olefin resin, PAR (polyarylate), PEEK (aromatic polyether ketone) and the like are preferable. Generally, a transparent electrode is attached to the surface for driving. Moreover, it is preferable to carry out by ultraviolet irradiation as a means for polymerizing. The glass substrate surface can be coated with polyimide, SiO 2 or the like.
２枚の基板間には、周知の液晶デバイスと同様、間隔保持用のスペーサーを介在させることができる。基板間の厚み、すなわち調光層の厚みは、２から５０μｍが好ましく、５から２０μｍがより好ましい。スペーサーは事前に基板上に散布しても良いが、高分子分散型液晶組成物中にあらかじめ混入しておき、高分子分散型液晶組成物と同時に基板上に塗布しても良い。 A spacer for maintaining a gap can be interposed between the two substrates, as in a known liquid crystal device. The thickness between the substrates, that is, the thickness of the light control layer is preferably 2 to 50 μm, and more preferably 5 to 20 μm. The spacer may be dispersed on the substrate in advance, but may be mixed in advance in the polymer dispersed liquid crystal composition and applied onto the substrate simultaneously with the polymer dispersed liquid crystal composition.
２枚の基板間に高分子分散型液晶組成物を狭持させるに方法は、通常の真空注入法でも良いが、ＯＤＦ法等滴下又は塗布で行うことが好ましい。この滴下又は塗布から重合性組成物が重合するまで間、高分子分散型液晶組成物は均一なアイソトロピック状態であることが好ましい。 A method for sandwiching the polymer-dispersed liquid crystal composition between the two substrates may be a normal vacuum injection method, but is preferably performed by dropping or coating such as an ODF method. It is preferable that the polymer-dispersed liquid crystal composition is in a uniform isotropic state from the dropping or coating until the polymerizable composition is polymerized.
滴下又は塗布を行い場合、２枚の基板で高分子分散型液晶組成物を挟みこむ方法としては、２枚の基板をラミネーター等で挟み込む方法で行うことができる。 When dropping or coating, the method of sandwiching the polymer dispersed liquid crystal composition between two substrates can be performed by sandwiching the two substrates with a laminator or the like.
重合性組成物を重合させる方法としては、紫外線照射が好適である。紫外線を発生させるランプとしては、メタルハライドランプ、高圧水銀ランプ、超高圧水銀ランプ等を用いることができる。また、照射する紫外線の波長としては、高分子分散型液晶組成物に含有されている光重合開始剤の吸収波長領域であり、且つ含有されている液晶組成物の吸収波長域でない波長領域の紫外線を照射することが好ましく、具体的には、メタルハライドランプ、高圧水銀ランプ、超高圧水銀ランプを使用して３３０ｎｍ以下の紫外線をカットして使用することが好ましい。また、単一波長を照射できるＵＶ−ＬＥＤランプを用いることも好ましい。 As a method for polymerizing the polymerizable composition, ultraviolet irradiation is suitable. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. In addition, the wavelength of ultraviolet rays to be irradiated is an ultraviolet wavelength in a wavelength region that is an absorption wavelength region of a photopolymerization initiator contained in the polymer-dispersed liquid crystal composition and that is not an absorption wavelength region of the contained liquid crystal composition. More specifically, it is preferable to use a metal halide lamp, a high-pressure mercury lamp, or an ultrahigh-pressure mercury lamp after cutting off ultraviolet rays of 330 nm or less. It is also preferable to use a UV-LED lamp that can emit a single wavelength.
照射する紫外線の強度は、目的とする調光層を得るため適宜調整することができるが、１から２００ｍｗ／ｃｍ２が好ましく、５から５０ｍｗ／ｃｍ２がより好ましい。紫外線を照射する時間は照射する紫外線強度により適宜選択されるが、１０から３００秒が好ましい。 Although the intensity | strength of the ultraviolet-ray to irradiate can be suitably adjusted in order to obtain the target light control layer, 1 to 200 mw / cm < 2 > is preferable and 5 to 50 mw / cm < 2 > is more preferable. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiated ultraviolet rays, but is preferably 10 to 300 seconds.
また、紫外線照射の時の温度は、調光層の特性を決める重要な要素となるが、高分子分散型液晶組成物のアイソトロピック−ネマティック転移点よりわずかに高い温度が好ましく、具体的には転移点＋０．１から３．０℃が好ましい。
上述の手法、又はそれ以外の手法で作製された、高分子分散型液晶素子内の調光層は、液晶組成物が透明性高分子物質でカプセル状に閉じ込められた構造、液晶組成物の連続相中に透明性高分子物質の３次元ネットワーク構造が形成された構造、又は両者が混在した構造等を有しているが、液晶組成物の連続相中に透明性高分子物質の３次元ネットワーク構造が形成された構造であることが好ましく、紫外線照射によって、液晶組成物の連続相中に透明性高分子物質の３次元ネットワーク構造が形成された構造がより好ましい。
The temperature at the time of ultraviolet irradiation is an important factor that determines the characteristics of the light control layer, but is preferably slightly higher than the isotropic-nematic transition point of the polymer-dispersed liquid crystal composition. The transition point +0.1 to 3.0 ° C. is preferred.
The light control layer in the polymer-dispersed liquid crystal device manufactured by the above-described method or other methods has a structure in which the liquid crystal composition is encapsulated with a transparent polymer substance, and the liquid crystal composition is continuous. It has a structure in which a three-dimensional network structure of a transparent polymer substance is formed in the phase, or a structure in which both are mixed, but a three-dimensional network of a transparent polymer substance in the continuous phase of the liquid crystal composition A structure in which a structure is formed is preferable, and a structure in which a three-dimensional network structure of a transparent polymer substance is formed in a continuous phase of a liquid crystal composition by ultraviolet irradiation is more preferable.
ネットワーク構造の平均空隙間隔は高分子分散型液晶表示素子の特性に大きく影響し、平均空隙間隔としては、０．２から２μｍが好ましく、０．２から１μｍがより好ましく、０．３から０．７μｍが最も好ましい。 The average gap spacing of the network structure greatly affects the characteristics of the polymer dispersion type liquid crystal display element, and the average gap spacing is preferably 0.2 to 2 μm, more preferably 0.2 to 1 μm, and 0.3 to 0.00. Most preferred is 7 μm.
このようにして作製された調光用フィルムは、この状態のままで、プロジェクターのスクリーン用途等に用いることもできるが、２枚のガラス基板ではさんで、調光ガラスとして用いることもできる。 The light control film thus produced can be used for projector screens or the like in this state, but can also be used as light control glass between two glass substrates.
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。
実施例中の高分子分散型液晶表示素子は以下の方法で作製した。
液晶組成物、重合性化合物、光重合開始剤からなる高分子分散型液晶組成物に１５μｍのスペーサーを入れ、ＩＴＯ付きＰＥＴフィルムに塗布し、もう一枚のフィルムと張り合わせた。この時、高分子分散型液晶組成物が常に均一状態となるよう、温度をコントロールした。高分子分散型液晶組成物のアイソトロピック−ネマチック転移点より1から２℃高い温度にコントロールし、紫外線カットフィルターとして、１０ｍｍ厚の青板ガラスを用いて照射強度が１０ｍｗ／ｃｍ２となるように調整された高圧水銀ランプを６０秒間照射して、高分子分散型液晶素子を得た。
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%”.
The polymer dispersion type liquid crystal display elements in the examples were produced by the following method.
A 15 μm spacer was placed in a polymer dispersed liquid crystal composition comprising a liquid crystal composition, a polymerizable compound, and a photopolymerization initiator, applied to a PET film with ITO, and bonded to another film. At this time, the temperature was controlled so that the polymer dispersed liquid crystal composition was always in a uniform state. The temperature is controlled to be 1 to 2 ° C. higher than the isotropic-nematic transition point of the polymer dispersed liquid crystal composition, and an ultraviolet cut filter is used to adjust the irradiation intensity to 10 mw / cm 2 using 10 mm-thick blue plate glass. The high pressure mercury lamp was irradiated for 60 seconds to obtain a polymer dispersed liquid crystal element.
実施例中に示される液晶組成物、高分子分散型液晶組成物の特性の略号、及び意味は以下の通りである。 Abbreviations and meanings of characteristics of the liquid crystal compositions and polymer dispersion type liquid crystal compositions shown in the examples are as follows.
Tｎｉ（ＬＣ） ：液晶組成物のネマチック相-等方性液体相転移温度（℃）
Δn ：液晶組成物の２５℃における屈折率異方性
Tｎｍ（ＰＮＭ） ：高分子分散型液晶組成物のネマチック相-等方性液体相転移温度（℃）
Ｔｎｐ ：高分子分散型液晶素子のネマチック相-等方性液体相転移温度（℃）
Ｔ０：セル厚１５μm、２５℃において、何もない（空気）の時の光量を１００％とした場合の高分子分散型液晶素子の電圧ＯＦＦ時の透過率（％）
V９０ ：セル厚１５μm、２５℃において、電圧無印加時の高分子分散型液晶素子の光透過率（Ｔ０）を０％とし、印加電圧を増加させていき光透過率がほとんど変化しなくなった時の光透過率（Ｔ１００）を１００％とした時、光透過率が９０％となる印加電圧値。（Ｖ）
評価方法は以下の通りである。
Tni (LC): Nematic phase-isotropic liquid phase transition temperature of liquid crystal composition (° C.)
Δn: refractive index anisotropy of liquid crystal composition at 25 ° C.
Tnm (PNM): Nematic phase-isotropic liquid phase transition temperature (° C) of polymer dispersed liquid crystal composition
Tnp: Nematic phase-isotropic liquid phase transition temperature of polymer dispersed liquid crystal element (° C.)
T0: Transmittance (%) when the voltage of the polymer dispersed liquid crystal element is OFF when the light quantity when there is nothing (air) at a cell thickness of 15 μm and 25 ° C.
V90: When the light transmittance (T0) of the polymer-dispersed liquid crystal element when no voltage is applied is 0% at a cell thickness of 15 μm and 25 ° C., the applied voltage is increased and the light transmittance hardly changes. The applied voltage value at which the light transmittance is 90% when the light transmittance (T100) is 100%. (V)
The evaluation method is as follows.
転移点測定には、メトラートレド社製の温度コントロールシステムＦＰ−８０、及びホットステージＦＰ８２を用いた。 For the transition point measurement, a temperature control system FP-80 and a hot stage FP82 manufactured by METTLER TOLEDO were used.
Ｖ９０、及びＴ０測定には、大塚電子社製のＬＣＤ評価システムＬＣＤ−５２００を用い、Ｂレンズ、アパーチャーＳの条件にて測定した。 For V90 and T0 measurements, an LCD evaluation system LCD-5200 manufactured by Otsuka Electronics Co., Ltd. was used, and measurement was performed under the conditions of the B lens and the aperture S.
密着性評価には、エーアンドディー社製の引張試験機テンシロンＲＴＧ−１２１０を用い、サンプルの幅２５mm、引張速度３００mm/分、２３℃雰囲気下、ＩＴＯ付きＰＥＴフィルムで挟んだ片側を１８０°方向に引き剥がした時の平均強度を求めた。 For the adhesion evaluation, a tensile tester Tensilon RTG-1210 manufactured by A & D Co., Ltd. was used, and the width of the sample was 25 mm, the tensile speed was 300 mm / min. The average strength when peeled off was obtained.
湾曲させた場合の、白濁性維持については、作製した調光フィルムを曲げて、目視観察により評価した。
（実施例１）
第１成分を９％、第６成分を７３％、第７成分を１８％含有する液晶組成物（Ａ）が７４％、第３成分のウレタンアクリレートオリゴマーであるＵＮ−６３００（根上工業社製、分子量１３０００）が７．６５％、第２成分のモルフォリンアクリレートであるＡＣＭＯ（興人社製）が１７．８４％、第４成分の光重合開始剤イルガキュア６５１（チバジャパン社製）が０．５１％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
The maintenance of cloudiness when bent was evaluated by visual observation by bending the produced light control film.
Example 1
The liquid crystal composition (A) containing 9% of the first component, 73% of the sixth component and 18% of the seventh component is 74%, UN-6300 (manufactured by Negami Kogyo Co., Ltd.) which is a urethane acrylate oligomer of the third component. The molecular weight 13000) is 7.65%, the second component morpholine acrylate ACMO (manufactured by Kojin Co.) is 17.84%, and the fourth component photopolymerization initiator Irgacure 651 (manufactured by Ciba Japan) is 0.00. A liquid crystal composition for a polymer-dispersed liquid crystal element composed of 51% was prepared, and a light control film as a polymer-dispersed liquid crystal element was obtained by the above-described method. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
（実施例２）
液晶組成物（Ａ）が７４％、第３成分のＵＮ−６３００が７．６４％、第２成分のＡＣＭＯが１７．８３％、第４成分の光重合開始剤イルガキュア６５１（チバジャパン社製）が０．５１％、第８成分である２−メタクリロイロキシエチルアシッドフォスフェートであるライトエステルＰ−２Ｍ（共栄社製）が０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
（実施例３）
第１成分を９％、第６成分を７３％、第７成分を１８％含有する液晶組成物（Ｂ）が７４％、第３成分のＵＮ−６３００が７．６４％、第２成分のＡＣＭＯが１７．８３％、第４成分の光重合開始剤イルガキュア６５１が０．５１％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
(Example 2)
Liquid crystal composition (A) is 74%, third component UN-6300 is 7.64%, second component ACMO is 17.83%, fourth component photopolymerization initiator Irgacure 651 (manufactured by Ciba Japan) A liquid crystal composition for a polymer dispersion type liquid crystal device comprising 0.51% of 0.08% light ester P-2M (manufactured by Kyoeisha) which is 2-methacryloyloxyethyl acid phosphate which is the eighth component And the light control film which is a polymer dispersion-type liquid crystal element was obtained by the above-mentioned method. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 3)
The liquid crystal composition (B) containing 9% of the first component, 73% of the sixth component and 18% of the seventh component is 74%, UN-6300 of the third component is 7.64%, ACMO of the second component Is a liquid crystal composition for a polymer dispersion type liquid crystal device, comprising 17.83% of a fourth component photopolymerization initiator Irgacure 651 of 0.51% and light ester P-2M of an eighth component of 0.02%. The light control film which was a polymer dispersion type liquid crystal element by the above-mentioned method was prepared. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
（実施例４）
第１成分を９％、第６成分を７３％、第７成分を１８％含有する液晶組成物（Ｃ）が７４％、第３成分のＵＮ−６３００が７．６４％、第２成分のＡＣＭＯが１７．８３％、第４成分の光重合開始剤イルガキュア６５１が０．５１％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
Example 4
The liquid crystal composition (C) containing 9% of the first component, 73% of the sixth component and 18% of the seventh component is 74%, UN-6300 of the third component is 7.64%, ACMO of the second component Is a liquid crystal composition for a polymer dispersion type liquid crystal device, comprising 17.83% of a fourth component photopolymerization initiator Irgacure 651 of 0.51% and light ester P-2M of an eighth component of 0.02%. The light control film which was a polymer dispersion type liquid crystal element by the above-mentioned method was prepared. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
（実施例５）
液晶組成物（Ａ）が７４％、第３成分のＵＮ−６３００が７．６４％、第２成分のＡＣＭＯが１４．２６％、第５成分であるオキセタンアクリレートＯＸＥ−１０（大阪有機社製）が３．５７％、第４成分の光重合開始剤イルガキュア６５１が０．５１％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
（実施例６）
第１成分を２０％、第６成分を６０％、第７成分を２０％含有する液晶組成物（Ｄ）が７４％、第３成分のＵＮ−６３００が７．６４％、第２成分のＡＣＭＯが１４．２６％、第５成分であるＯＸＥ−１０が３．５７％、第４成分の光重合開始剤イルガキュア６５１が０．５１％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
(Example 5)
Liquid crystal composition (A) is 74%, third component UN-6300 is 7.64%, second component ACMO is 14.26%, fifth component oxetane acrylate OXE-10 (manufactured by Osaka Organic Chemical Co., Ltd.) Is a liquid crystal composition for a polymer-dispersed liquid crystal device, comprising 3.57%, the fourth component photopolymerization initiator Irgacure 651 is 0.51%, and the eighth component light ester P-2M is 0.02%. The light control film which was a polymer dispersion type liquid crystal element by the above-mentioned method was prepared. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 6)
74% of the liquid crystal composition (D) containing 20% of the first component, 60% of the sixth component, and 20% of the seventh component, 7.64% of the third component UN-6300, and ACMO of the second component 14.26%, the fifth component OXE-10 is 3.57%, the fourth component photopolymerization initiator Irgacure 651 is 0.51%, and the eighth component light ester P-2M is 0.02. % Liquid crystal composition for polymer dispersed liquid crystal element was prepared, and a light control film as a polymer dispersed liquid crystal element was obtained by the above-described method. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
（実施例７）
第１成分を５％、第６成分を８５％、第７成分を１０％含有する液晶組成物（Ｅ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分であるＯＸＥ−１０が３．６０％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
(Example 7)
74% of the liquid crystal composition (E) containing 5% of the first component, 85% of the sixth component and 10% of the seventh component, 7.72% of the third component UN-6300, ACMO of the second component Is 14.40%, the fifth component OXE-10 is 3.60%, the fourth component photopolymerization initiator Irgacure 651 is 0.26%, and the eighth component light ester P-2M is 0.02. % Liquid crystal composition for polymer dispersed liquid crystal element was prepared, and a light control film as a polymer dispersed liquid crystal element was obtained by the above-described method. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
（実施例８）
第１成分を５％、第６成分を８５％、第７成分を１０％含有する液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分であるＯＸＥ−１０が３．６０％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
(Example 8)
74% of the liquid crystal composition (F) containing 5% of the first component, 85% of the sixth component and 10% of the seventh component, 7.72% of the third component UN-6300, ACMO of the second component Is 14.40%, the fifth component OXE-10 is 3.60%, the fourth component photopolymerization initiator Irgacure 651 is 0.26%, and the eighth component light ester P-2M is 0.02. % Liquid crystal composition for polymer dispersed liquid crystal element was prepared, and a light control film as a polymer dispersed liquid crystal element was obtained by the above-described method. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
（実施例９）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１３．６３％、第５成分であるＯＸＥ−１０が４．３７％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
（実施例１０）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１５．４３％、第５成分であるラウリルアクリレートＳＲ３３５（サートマー社製）が２．５７％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
（実施例１１）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１５．４３％、第５成分であるイソオクチルアクリレートＳＲ４４０（サートマー社製）が２．５７％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
（実施例１２）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分であるアダマンチル骨格を持つアクリレートＥｔＡＤＡ（大阪有機社製）が３．６０％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
（実施例１３）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分の単官能メタクリレートであるＣＨＤＯＬ３０（大阪有機社製）が３．６０％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
（実施例１４）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分の単官能アクリレートであるＭＥＤＯＬ１０（大阪有機社製）が３．６０％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表１に示す。
（実施例１５）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分の単官能アクリレートであるＣＨＤＯＬ１０（大阪有機社製）が３．６０％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（実施例１６）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分のテトラヒドロフルフリルアクリレートであるＳＲ２８５（サートマー社製）が３．６０％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（実施例１７）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分のジメチルアミノエチルアクリレートであるＤＭＡＥＡ（興人社製）が３．６０％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（実施例１８）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分のジエチルアクリルアミドであるＤＥＡＡ（興人社製）が３．６０％、第４成分の光重合開始剤イルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（実施例１９）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分のＯＸＥ−１０が２．５７％、エトキシ−ジエチレングリコールアクリレート（共栄社製）が１．０３％、第４成分の光重合開始剤であるイルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（実施例２０）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分のＯＸＥ−１０が３．６０％、第４成分の光重合開始剤であるセイクオールＢＥＥ（精工化学社製）が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（実施例２１）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分のシクロヘキシルアクリレートであるブレンマーＣＨＡ（日油社製）が３．６０％、第４成分の光重合開始剤であるイルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（実施例２２）
液晶組成物（Ｆ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１４．４０％、第５成分の３，３，５トリメチルシクロヘキサンアクリレートであるＣＤ４２０（サートマー社製）が３．６０％、第４成分の光重合開始剤であるイルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（実施例２３）
第１成分を５％、第６成分を８５％、第７成分を１０％含有する液晶組成物（Ｇ）が７４％、第３成分のＵＮ−６３００が７．７２％、第２成分のＡＣＭＯが１８．０％、第４成分の光重合開始剤であるイルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
Example 9
The liquid crystal composition (F) was 74%, the third component UN-6300 was 7.72%, the second component ACMO was 13.63%, the fifth component OXE-10 was 4.37%, A liquid crystal composition for a polymer dispersion type liquid crystal device comprising 0.26% of the component photopolymerization initiator Irgacure 651 and 0.02% of the eighth component light ester P-2M was prepared, The light control film which is a molecular dispersion type liquid crystal element was obtained. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 10)
The liquid crystal composition (F) is 74%, the third component UN-6300 is 7.72%, the second component ACMO is 15.43%, and the fifth component is lauryl acrylate SR335 (manufactured by Sartomer). 57%, a fourth component photopolymerization initiator Irgacure 651 is 0.26%, and the eighth component light ester P-2M is 0.02%. The light control film which is a polymer dispersion type liquid crystal element was obtained by the above-mentioned method. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 11)
The liquid crystal composition (F) is 74%, the third component UN-6300 is 7.72%, the second component ACMO is 15.43%, and the fifth component isooctyl acrylate SR440 (Sartomer) is 2. A liquid crystal composition for a polymer dispersion type liquid crystal element comprising 57%, 0.26% of the fourth component photopolymerization initiator Irgacure 651 and 0.02% of the eighth component light ester P-2M was prepared. The light control film which is a polymer dispersion type liquid crystal element was obtained by the above-mentioned method. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 12)
Liquid crystal composition (F) is 74%, third component UN-6300 is 7.72%, second component ACMO is 14.40%, and the fifth component is an acrylate EtADA having an adamantyl skeleton (manufactured by Osaka Organic Chemical Co., Ltd.) ) Is 3.60%, the fourth component photopolymerization initiator Irgacure 651 is 0.26%, and the eighth component light ester P-2M is 0.02%. The light control film which is a polymer dispersion type liquid crystal element was obtained by the above-mentioned method. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 13)
The liquid crystal composition (F) is 74%, the third component UN-6300 is 7.72%, the second component ACMO is 14.40%, and the fifth component monofunctional methacrylate CHDOL30 (manufactured by Osaka Organic Chemical Co., Ltd.) Is a liquid crystal composition for a polymer dispersion type liquid crystal device, comprising: 3.60%, photopolymerization initiator Irgacure 651 of the fourth component 0.26%, and light ester P-2M of the eighth component 0.02%. The light control film which was a polymer dispersion type liquid crystal element by the above-mentioned method was prepared. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 14)
The liquid crystal composition (F) is 74%, the third component UN-6300 is 7.72%, the second component ACMO is 14.40%, and the fifth component monofunctional acrylate MEDOL10 (manufactured by Osaka Organic Chemical Co., Ltd.) Is a liquid crystal composition for a polymer dispersion type liquid crystal device, comprising: 3.60%, photopolymerization initiator Irgacure 651 of the fourth component 0.26%, and light ester P-2M of the eighth component 0.02%. The light control film which was a polymer dispersion type liquid crystal element by the above-mentioned method was prepared. Table 1 shows the transition point Tni and refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 15)
The liquid crystal composition (F) is 74%, the third component UN-6300 is 7.72%, the second component ACMO is 14.40%, and the fifth component monofunctional acrylate CHDOL10 (manufactured by Osaka Organic Chemical Co., Ltd.) Is a liquid crystal composition for a polymer dispersion type liquid crystal device, comprising: 3.60%, photopolymerization initiator Irgacure 651 of the fourth component 0.26%, and light ester P-2M of the eighth component 0.02%. The light control film which was a polymer dispersion type liquid crystal element by the above-mentioned method was prepared. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 16)
The liquid crystal composition (F) is 74%, the third component UN-6300 is 7.72%, the second component ACMO is 14.40%, and the fifth component tetrahydrofurfuryl acrylate SR285 (manufactured by Sartomer) Is a liquid crystal composition for a polymer dispersion type liquid crystal device, comprising: 3.60%, photopolymerization initiator Irgacure 651 of the fourth component 0.26%, and light ester P-2M of the eighth component 0.02%. The light control film which was a polymer dispersion type liquid crystal element by the above-mentioned method was prepared. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 17)
Liquid crystal composition (F) is 74%, third component UN-6300 is 7.72%, second component ACMO is 14.40%, fifth component dimethylaminoethyl acrylate DMAEA (manufactured by Kojin Co., Ltd.) ) Is 3.60%, the fourth component photopolymerization initiator Irgacure 651 is 0.26%, and the eighth component light ester P-2M is 0.02%. The light control film which is a polymer dispersion type liquid crystal element was obtained by the above-mentioned method. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 18)
The liquid crystal composition (F) is 74%, the third component UN-6300 is 7.72%, the second component ACMO is 14.40%, and the fifth component diethylacrylamide DEAA (manufactured by Kojin Co., Ltd.) is 3. Preparation of liquid crystal composition for polymer dispersion type liquid crystal device comprising 3.60%, photopolymerization initiator Irgacure 651 4th component 0.26%, light ester P-2M 8th component 0.02% And the light control film which is a polymer dispersion-type liquid crystal element was obtained by the above-mentioned method. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 19)
Liquid crystal composition (F) is 74%, third component UN-6300 is 7.72%, second component ACMO is 14.40%, fifth component OXE-10 is 2.57%, ethoxy-diethylene glycol Polymer dispersion type consisting of 1.03% acrylate (manufactured by Kyoeisha), 0.26% Irgacure 651 as the photopolymerization initiator of the fourth component, and 0.02% of light ester P-2M as the eighth component A liquid crystal composition for a liquid crystal element was prepared, and a light control film which was a polymer dispersed liquid crystal element was obtained by the above-described method. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 20)
Liquid crystal composition (F) is 74%, third component UN-6300 is 7.72%, second component ACMO is 14.40%, fifth component OXE-10 is 3.60%, fourth component A liquid crystal composition for a polymer dispersion type liquid crystal element comprising 0.26% of Sequol BEE (manufactured by Seiko Chemical Co., Ltd.) as a photopolymerization initiator and 0.02% of light ester P-2M as an eighth component is prepared. And the light control film which is a polymer dispersion-type liquid crystal element was obtained by the above-mentioned method. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 21)
The liquid crystal composition (F) is 74%, the third component UN-6300 is 7.72%, the second component ACMO is 14.40%, and the fifth component cyclohexyl acrylate, Blemmer CHA (manufactured by NOF Corporation). Liquid crystal composition for polymer dispersion type liquid crystal element, comprising 3.60% of Irgacure 651 which is the photopolymerization initiator of the fourth component and 0.22% of light ester P-2M which is the eighth component. The light control film which is a polymer dispersion-type liquid crystal element was obtained by the above-mentioned method. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 22)
The liquid crystal composition (F) was 74%, the third component UN-6300 was 7.72%, the second component ACMO was 14.40%, and the fifth component CD420 (3,3,5 trimethylcyclohexane acrylate) Sartomer Co., Ltd.) 3.60%, fourth component photopolymerization initiator Irgacure 651 0.26%, eighth component light ester P-2M 0.02% polymer dispersed liquid crystal A liquid crystal composition for an element was prepared, and a light control film which was a polymer-dispersed liquid crystal element was obtained by the method described above. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 23)
74% of the liquid crystal composition (G) containing 5% of the first component, 85% of the sixth component, and 10% of the seventh component, 7.72% of the third component UN-6300, ACMO of the second component Is 18.0%, Irgacure 651 which is the photopolymerization initiator of the fourth component is 0.26%, and Light Ester P-2M which is the eighth component is 0.02%. The light control film which is a polymer dispersion-type liquid crystal element was obtained by the above-mentioned method. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
（実施例２４）
液晶組成物（Ｇ）が７４％、第３成分のＵＮ−６３００が７．７１％、第２成分のＡＣＭＯが１７．９８％、第４成分の光重合開始剤であるイルガキュア６５１が０．２６％、第８成分であるライトエステルＰ−２Ｍが０．０２％、第９成分である界面活性剤ニューコール３−８０（日本乳化剤社製）０．０３％がからなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（実施例２５）
液晶組成物（Ｆ）が５０％、第３成分のＵＮ−６３００が１４．８４％、第２成分のＡＣＭＯが２７．７０％、第５成分のＯＸＥ−１０が６．９２％、第４成分の光重合開始剤であるイルガキュア６５１が０．４９％、第８成分であるライトエステルＰ−２Ｍが０．０５％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（比較例１）
第６成分１００％からなる液晶組成物（Ｈ）が７４％、第３成分のＵＮ−６３００が７．６４％、第２成分のＡＣＭＯが１７．８３％、第４成分の光重合開始剤イルガキュア６５１（チバジャパン社製）が０．５１％、第８成分である２−メタクリロイロキシエチルアシッドフォスフェートであるライトエステルＰ−２Ｍ（共栄社製）が０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
(Example 24)
The liquid crystal composition (G) was 74%, the third component UN-6300 was 7.71%, the second component ACMO was 17.98%, and the fourth component photopolymerization initiator Irgacure 651 was 0.26. %, 8% light ester P-2M 0.02%, 9th component surfactant Newcol 3-80 (manufactured by Nippon Emulsifier Co., Ltd.) 0.03% polymer dispersed liquid crystal element A liquid crystal composition was prepared, and a light control film as a polymer dispersed liquid crystal element was obtained by the above-described method. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Example 25)
Liquid crystal composition (F) 50%, third component UN-6300 14.84%, second component ACMO 27.70%, fifth component OXE-10 6.92%, fourth component A liquid crystal composition for a polymer dispersed liquid crystal device comprising 0.49% of Irgacure 651 as a photopolymerization initiator and 0.05% of light ester P-2M as an eighth component was prepared by the above-described method. The light control film which is a polymer dispersion type liquid crystal element was obtained. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Comparative Example 1)
74% liquid crystal composition (H) composed of 100% of the sixth component, 7.64% of the third component UN-6300, 17.83% of the second component ACMO, Irgacure of the fourth component photopolymerization initiator Polymer dispersed liquid crystal in which 651 (Ciba Japan Co., Ltd.) is 0.51%, and 8-ester 2-methacryloyloxyethyl acid phosphate, light ester P-2M (Kyoei Co., Ltd.) is 0.02%. A liquid crystal composition for an element was prepared, and a light control film which was a polymer-dispersed liquid crystal element was obtained by the method described above. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
（比較例２）
液晶組成物（Ａ）が７４％、第３成分のＵＮ−６３００が７．６１％、第５成分のＯＸＥ−１０が１７．７６％、第４成分の光重合開始剤イルガキュア６５１（チバジャパン社製）が０．５１％、第８成分である２−メタクリロイロキシエチルアシッドフォスフェートであるライトエステルＰ−２Ｍ（共栄社製）が０．０３％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
（比較例３）
液晶組成物（Ｆ）が７４％、第２成分のＡＣＭＯが１７．８３％、第５成分のＯＸＥ−１０が７．６４％、第４成分の光重合開始剤イルガキュア６５１（チバジャパン社製）が０．５１％、第８成分である２−メタクリロイロキシエチルアシッドフォスフェートであるライトエステルＰ−２Ｍ（共栄社製）が０．０２％からなる高分子分散型液晶素子用液晶組成物を調合し、前述の手法で高分子分散型液晶素子である調光フィルムを得た。用いた液晶組成物の転移点Ｔｎｉと屈折率異方性Δｎ、高分子分散型液晶素子用液晶組成物の転移点Ｔｎｍ、及び得られた調光フィルムの特性を表２に示す。
(Comparative Example 2)
Liquid crystal composition (A) is 74%, third component UN-6300 is 7.61%, fifth component OXE-10 is 17.76%, fourth component photopolymerization initiator Irgacure 651 (Ciba Japan) Made of 0.51%, and light ester P-2M (manufactured by Kyoeisha) which is 2-methacryloyloxyethyl acid phosphate as the eighth component is 0.03%. The light control film which is a polymer dispersion type liquid crystal element was obtained by the above-mentioned method. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
(Comparative Example 3)
Liquid crystal composition (F) is 74%, second component ACMO is 17.83%, fifth component OXE-10 is 7.64%, fourth component photopolymerization initiator Irgacure 651 (manufactured by Ciba Japan) A liquid crystal composition for a polymer dispersion type liquid crystal device comprising 0.51% of 0.08% light ester P-2M (manufactured by Kyoeisha) which is 2-methacryloyloxyethyl acid phosphate which is the eighth component And the light control film which is a polymer dispersion-type liquid crystal element was obtained by the above-mentioned method. Table 2 shows the transition point Tni and the refractive index anisotropy Δn of the liquid crystal composition used, the transition point Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements, and the characteristics of the obtained light control film.
実施例１と実施例２の比較で、第８成分の存在で密着性がより向上していることが理解でき、実施例５と７の比較で、第１成分の添加量が増すと、駆動電圧が低下することが理解でき、実施例７と８、及び実施例２と３の比較で、第１成分中にアルキル鎖の長い化合物を用いた方が低電圧効果が高いことが理解できる。実施例８と９の比較では、第５成分の添加量が多いほど低電圧効果は高くなり、実施例７、８と実施例９、１０の比較より、第５成分に一般式（Ｖ−６１）の化合物を用いた方が低電圧効果が高いことも理解できる。 It can be understood from the comparison between Example 1 and Example 2 that the adhesion is further improved by the presence of the eighth component, and when the addition amount of the first component is increased in the comparison between Examples 5 and 7, driving is performed. It can be understood that the voltage decreases, and it can be understood from the comparison between Examples 7 and 8 and Examples 2 and 3 that the low voltage effect is higher when a compound having a long alkyl chain is used in the first component. In comparison between Examples 8 and 9, the lower the voltage addition effect, the higher the amount of the fifth component added. From the comparison between Examples 7 and 8 and Examples 9 and 10, the fifth component has the general formula (V-61 It can also be understood that the use of the compound (1) has a higher low voltage effect.
実施例５と６を比較すると、第１成分を代えても同様の低電圧効果が見られるが、極性基の付いていない化合物を用いている実施例５の方が、より低い添加濃度で低電圧化されていることが理解でき、実施例５〜２２を見ると、第５成分を代えても同様に低電圧の効果が見られることが理解できる。 Comparing Examples 5 and 6, the same low voltage effect can be seen even if the first component is changed, but Example 5 using a compound without a polar group is lower at a lower addition concentration. It can be understood that the voltage is applied, and when Examples 5 to 22 are seen, it can be understood that the effect of the low voltage can be similarly seen even if the fifth component is changed.
比較例１の高分子分散型液晶素子の転移点（Ｔｎｐ）は８３℃であり、実施例７のＴｎｐは８０℃、実施例５のＴｎｐは７８℃であった。それぞれの使用している液晶組成物のＴｎｉとの差異（Ｔｎｐ−Ｔｎｉ）は、比較例１で−１．９℃、実施例７で１０．１℃、実施例５で１８．５℃であり、第１成分の添加量が増すと使用している液晶組成物のＴｎｉよりＴｎｐの転移点のほうが高くなる傾向が大きくなることが理解できる。 The transition point (Tnp) of the polymer dispersed liquid crystal element of Comparative Example 1 was 83 ° C., Tnp of Example 7 was 80 ° C., and Tnp of Example 5 was 78 ° C. The difference (Tnp-Tni) between each liquid crystal composition used and Tni is −1.9 ° C. in Comparative Example 1, 10.1 ° C. in Example 7, and 18.5 ° C. in Example 5. It can be understood that the Tnp transition point tends to be higher than the Tni of the liquid crystal composition used as the amount of the first component added increases.
また、実施例２３の高分子分散型液晶素子用液晶組成物を１０℃で２４時間放置すると、析出成分が見られたが、実施例２４の高分子分散型液晶素子用液晶組成物の場合は、０℃で２４時間放置しても析出は見られなかった、これより、界面活性剤の添加で相溶性が改善されたことが理解できる。 Further, when the liquid crystal composition for polymer dispersion type liquid crystal element of Example 23 was allowed to stand at 10 ° C. for 24 hours, a deposited component was observed. In the case of the liquid crystal composition for polymer dispersion type liquid crystal element of Example 24, No precipitation was observed even when allowed to stand at 0 ° C. for 24 hours. From this, it can be understood that the compatibility was improved by the addition of the surfactant.
Claims (15)
Ｒ２は、フッ素原子、塩素原子、シアノ基、ＣＦ３基、ＯＣＦ３基、ＯＣＨＦ２基、ＮＣＳ基、又は炭素原子数１〜１０のアルキル基を表し、該アルキル基中の非隣接の１つ又は２つ以上の−ＣＨ２−は酸素原子、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−で置き換えられていてもよく、
環Ａ１、環Ａ２、環Ａ３、及び環Ａ４は、それぞれ独立して、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又は2,6-ナフチレン基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又は2,6-ナフチレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、塩素原子、ＣＦ３基、ＯＣＦ３基又はＣＨ３基を有することができ、
Ｚ１、Ｚ２、及びＺ３は、それぞれ独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ２−ＣＨ２−、−ＣＦ２−ＣＦ２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＨ２Ｏ−、−ＯＣＨ２−、−ＣＦ２Ｏ−、−ＯＣＦ２−、又は−Ｃ≡Ｃ−を表す。）で表される液晶化合物を少なくとも１種含有し、
第２成分として、式（ＩＩ−７）
第３成分として、多官能のウレタン（メタ）アクリレートオリゴマーを少なくとも１種含有し、
第４成分として、光重合開始剤を少なくとも１種含有する高分子分散型液晶素子用液晶組成物。 As the first component, the general formula (I-1)
R 2 represents a fluorine atom, a chlorine atom, a cyano group, a CF 3 group, an OCF 3 group, an OCHF 2 group, an NCS group, or an alkyl group having 1 to 10 carbon atoms, and the non-adjacent 1 in the alkyl group One or more —CH 2 — may be replaced by an oxygen atom, —CH═CH—, —COO—, —OCO—,
Ring A 1 , Ring A 2 , Ring A 3 , and Ring A 4 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2 , 5-diyl group, 1,3-dioxane-2,5-diyl group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine- 2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or 2,6-naphthylene group, the 1,4-phenylene group, 1,2,3,4 -Tetrahydronaphthalene-2,6-diyl group or 2,6-naphthylene group is unsubstituted or has one or more fluorine atoms, chlorine atoms, CF 3 groups, OCF 3 groups or CH as substituents Can have 3 groups,
Z 1, Z 2, and Z 3 are each independently a single bond, -COO -, - OCO -, - CH 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH -, - CF═CF—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, or —C≡C— is represented. At least one liquid crystal compound represented by
As the second component, the formula (II-7)
As a third component, at least one polyfunctional urethane (meth) acrylate oligomer is contained,
A liquid crystal composition for a polymer-dispersed liquid crystal element containing at least one photopolymerization initiator as a fourth component.
Ｒ５、及びＲ６は、それぞれ独立して水素原子、又は炭素原子数１〜１２までのアルキル基を表すが、該アルキル基中非隣接の１つ以上の−ＣＨ２−は互いに独立して酸素原子、−ＣＯ−、−ＣＯＯ−、又は−ＯＣＯ−で置換されていても良く、
Ａ８は環状基が１〜３個の環式化合物基を表すが、Ｚ８と直接結合する環状基の結合原子は窒素原子ではなく、
Ｚ９は水素原子、又は炭素数１〜２４までのアルキル基を表すが、該アルキル基中の１つ以上の−ＣＨ２−は互いに独立して酸素原子、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、又は一般式（Ｖ−３）
で置換されていても良く、且つ直鎖であっても分岐していても良く、
ａは０又は１、ｂは０、１、２又は３を表すが、ｂが２又は３を表す場合に複数存在するＺ９は同一であっても異なっていても良い。）で表される化合物群から選ばれる少なくとも１種の重合性化合物を含有する、高分子分散型液晶素子用液晶組成物。 In addition to the liquid crystal composition for polymer dispersed element according to claim 1, as a fifth component, general formula (V-1) and general formula (V-2)
R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and one or more —CH 2 — that are not adjacent to each other in the alkyl group are independently from each other. May be substituted with an oxygen atom, -CO-, -COO-, or -OCO-,
A 8 represents a cyclic compound group having 1 to 3 cyclic groups, but the bonding atom of the cyclic group directly bonded to Z 8 is not a nitrogen atom,
Z 9 represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, and one or more —CH 2 — in the alkyl group are independently of each other an oxygen atom, —CO—, —COO—, — OCO- or general formula (V-3)
And may be linear or branched,
a represents 0 or 1, and b represents 0, 1, 2 or 3, but when b represents 2 or 3, a plurality of Z 9 may be the same or different. A liquid crystal composition for a polymer-dispersed liquid crystal element, containing at least one polymerizable compound selected from the group of compounds represented by:
環Ａ６は、1,4-フェニレン基、1,4-シクロヘキシレン基、1,3-ジオキサン-2,5-ジイル基、ピリジン-2,5-ジイル基、又はピリミジン-2,5-ジイル基を表し、該1,4-フェニレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、塩素原子、ＣＦ３基、ＯＣＦ３基、又はメチル基を有することができ、
Ｙ２、Ｙ３、Ｙ４、及びＹ５は、それぞれ独立して、水素原子、フッ素原子、塩素原子、ＣＦ３基、又はＯＣＦ３基を表し、
Ｚ５、及びＺ６は、それぞれ独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ２−ＣＨ２−、−ＣＨ＝ＣＨ−、−ＣＦ２Ｏ−、又は−Ｃ≡Ｃ−を表し、
ｎは０又は１を表す。ただしｎが０の場合、Ｙ２又はＹ３の少なくともどちらか一方は水素原子を表す。）
で表される液晶性化合物を少なくとも１種含有する、高分子分散型液晶素子用液晶組成物。 In addition to the liquid crystal composition for polymer-dispersed devices according to claim 1 and 2, as a sixth component, a general formula (VI-1)
Ring A 6 is a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,3-dioxane-2,5-diyl group, a pyridine-2,5-diyl group, or a pyrimidine-2,5-diyl group The 1,4-phenylene group can be unsubstituted or have one or more fluorine, chlorine, CF 3 , OCF 3 or methyl groups as substituents. ,
Y 2 , Y 3 , Y 4 , and Y 5 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a CF 3 group, or an OCF 3 group,
Z 5, and Z 6 are each independently a single bond, -COO -, - OCO -, - CH 2 -CH 2 -, - CH = CH -, - CF 2 O-, or -C≡C- Represents
n represents 0 or 1. However, when n is 0, at least one of Y 2 and Y 3 represents a hydrogen atom. )
A liquid crystal composition for a polymer-dispersed liquid crystal element, comprising at least one liquid crystalline compound represented by the formula:
Ｙ１はフッ素原子、塩素原子、シアノ基、ＣＦ３基、ＯＣＦ３基、ＯＣＨＦ２基、又はＮＣＳ基を表し
Ｚ４は、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ２−ＣＨ２−、−ＣＦ２Ｏ−、又は−Ｃ≡Ｃ−を表し、
環Ａ５は、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、又は2,6-ナフチレン基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基は非置換であるか又は置換基として１個又は２個以上のフッ素原子、塩素原子、ＣＦ３基、ＯＣＦ３基又はＣＨ３基を有することができる。）
で表される、液晶性化合物を少なくとも１種含有する、高分子分散型液晶素子用液晶組成物。 In addition to the liquid crystal composition for polymer-dispersed devices according to claim 1, 2, and 3, as a seventh component, a general formula (VII-1)
Y 1 is a fluorine atom, a chlorine atom, a cyano group, CF 3 group, OCF 3 group, Z 4 represents OCHF 2 group, or an NCS group, a single bond, -COO -, - OCO -, - CH 2 -CH 2 -, -CF 2 O-, or -C≡C-
Ring A 5 are 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group Decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene- Represents a 2,6-diyl group or a 2,6-naphthylene group, and the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and 2,6-naphthylene group are It can be unsubstituted or have one or more fluorine, chlorine, CF 3 , OCF 3 or CH 3 groups as substituents. )
A liquid crystal composition for a polymer-dispersed liquid crystal element, containing at least one liquid crystalline compound represented by the formula:
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