CN116184553A - Laminate and method for producing same - Google Patents
Laminate and method for producing same Download PDFInfo
- Publication number
- CN116184553A CN116184553A CN202211657913.1A CN202211657913A CN116184553A CN 116184553 A CN116184553 A CN 116184553A CN 202211657913 A CN202211657913 A CN 202211657913A CN 116184553 A CN116184553 A CN 116184553A
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- Prior art keywords
- liquid crystal
- film
- cured film
- crystal cured
- group
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 820
- 150000001875 compounds Chemical class 0.000 claims abstract description 222
- 239000000203 mixture Substances 0.000 claims abstract description 151
- 239000000758 substrate Substances 0.000 claims abstract description 73
- -1 cinnamoyl group Chemical group 0.000 claims description 145
- 239000011248 coating agent Substances 0.000 claims description 57
- 238000000576 coating method Methods 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 43
- 150000008040 ionic compounds Chemical class 0.000 claims description 41
- 238000010521 absorption reaction Methods 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 26
- 229910000077 silane Inorganic materials 0.000 claims description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 8
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 765
- 239000010410 layer Substances 0.000 description 84
- 229920005989 resin Polymers 0.000 description 84
- 239000011347 resin Substances 0.000 description 83
- 125000004432 carbon atom Chemical group C* 0.000 description 51
- 239000002904 solvent Substances 0.000 description 45
- 229920001577 copolymer Polymers 0.000 description 44
- 239000002585 base Substances 0.000 description 42
- 125000004429 atom Chemical group 0.000 description 36
- 238000001035 drying Methods 0.000 description 32
- 239000004990 Smectic liquid crystal Substances 0.000 description 31
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 28
- 239000004372 Polyvinyl alcohol Substances 0.000 description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 description 25
- 125000001424 substituent group Chemical group 0.000 description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 22
- 239000003999 initiator Substances 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 22
- 239000000975 dye Substances 0.000 description 21
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 21
- 229910052753 mercury Inorganic materials 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 20
- 125000003118 aryl group Chemical group 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000004043 dyeing Methods 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- 239000003963 antioxidant agent Substances 0.000 description 14
- 235000006708 antioxidants Nutrition 0.000 description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 14
- 239000004327 boric acid Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 13
- 238000005401 electroluminescence Methods 0.000 description 13
- 125000005843 halogen group Chemical group 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000012790 adhesive layer Substances 0.000 description 12
- 125000004093 cyano group Chemical group *C#N 0.000 description 12
- 230000007547 defect Effects 0.000 description 12
- 230000001747 exhibiting effect Effects 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000011282 treatment Methods 0.000 description 12
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 11
- 125000002723 alicyclic group Chemical group 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 11
- 230000007704 transition Effects 0.000 description 11
- 230000001186 cumulative effect Effects 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 10
- 230000002441 reversible effect Effects 0.000 description 10
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000003851 corona treatment Methods 0.000 description 9
- 150000001925 cycloalkenes Chemical class 0.000 description 9
- 150000002466 imines Chemical class 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 229910052721 tungsten Inorganic materials 0.000 description 9
- 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 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 8
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000003504 photosensitizing agent Substances 0.000 description 7
- 239000011369 resultant mixture Substances 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 125000005647 linker group Chemical group 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 125000003367 polycyclic group Chemical group 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000005370 alkoxysilyl group Chemical group 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000003566 oxetanyl group Chemical group 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 4
- 150000004714 phosphonium salts Chemical group 0.000 description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- JDZOPOPDMUEZBX-UHFFFAOYSA-N 1h-pyrrole;stilbene Chemical group C=1C=CNC=1.C=1C=CC=CC=1C=CC1=CC=CC=C1 JDZOPOPDMUEZBX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000011899 heat drying method Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 3
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002892 organic cations Chemical class 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 125000000168 pyrrolyl group Chemical group 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000009751 slip forming Methods 0.000 description 3
- 235000019465 surimi Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- PXELHGDYRQLRQO-UHFFFAOYSA-N 1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1 PXELHGDYRQLRQO-UHFFFAOYSA-N 0.000 description 2
- NNLHWTTWXYBJBQ-UHFFFAOYSA-N 1-butyl-4-methylpyridin-1-ium Chemical compound CCCC[N+]1=CC=C(C)C=C1 NNLHWTTWXYBJBQ-UHFFFAOYSA-N 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- AMKUSFIBHAUBIJ-UHFFFAOYSA-N 1-hexylpyridin-1-ium Chemical compound CCCCCC[N+]1=CC=CC=C1 AMKUSFIBHAUBIJ-UHFFFAOYSA-N 0.000 description 2
- XDEQOBPALZZTCA-UHFFFAOYSA-N 1-octylpyridin-1-ium Chemical compound CCCCCCCC[N+]1=CC=CC=C1 XDEQOBPALZZTCA-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IGKWUSYWEYAUPC-UHFFFAOYSA-N 4-hexyl-1-methylpyridin-1-ium Chemical compound CCCCCCC1=CC=[N+](C)C=C1 IGKWUSYWEYAUPC-UHFFFAOYSA-N 0.000 description 2
- OSCFFOTZWZZXPR-UHFFFAOYSA-N 4-methyl-1-octylpyridin-1-ium Chemical compound CCCCCCCC[N+]1=CC=C(C)C=C1 OSCFFOTZWZZXPR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004976 Lyotropic liquid crystal Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Laminated Bodies (AREA)
- Liquid Crystal (AREA)
Abstract
The present application relates to a laminate and a method for producing the same. A laminate comprising a substrate, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film in this order, wherein the vertical alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition obtained by curing a polymerizable liquid crystal compound in a state of being aligned in a vertical direction with respect to the liquid crystal cured film plane, the horizontal alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition obtained by curing a polymerizable liquid crystal compound in a state of being aligned in a horizontal direction with respect to the liquid crystal cured film plane, the vertical alignment liquid crystal cured film comprises a vertical alignment accelerator, and the horizontal alignment film is a photo-alignment film formed of a (meth) acrylic polymer, and the total film thickness from the surface on the substrate side of the vertical alignment liquid crystal cured film to the surface on the side opposite to the horizontal alignment film of the horizontal alignment liquid crystal cured film is 10 [ mu ] m or less.
Description
The present application is a divisional application of chinese patent application No.201980011829.2 (PCT application No. PCT/JP 2019/004845) with the title of "laminate and method of manufacturing the same" on application day 2, 12, 2019.
Technical Field
The present invention relates to a laminate comprising a vertically oriented liquid crystal cured film and a horizontally oriented liquid crystal cured film, an elliptical polarizing plate comprising the laminate, and an organic EL display device. The present invention also relates to a method for producing the laminate.
Background
An elliptical polarizing plate is an optical member formed by laminating a polarizing plate and a retardation plate, and is used for preventing reflection of light at electrodes constituting an organic EL image display device or the like in a device for displaying an image in a planar state. As a retardation plate constituting the elliptical polarizing plate, a so-called λ/4 plate is generally used.
In view of the ease of exhibiting the same retardation performance in a wide wavelength range of visible light, a retardation plate exhibiting reverse wavelength dispersibility is preferable as a retardation plate constituting the elliptical polarizing plate. As such a retardation plate, a retardation plate formed of a horizontally oriented liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility in a state of being oriented in a horizontal direction with respect to the plane of the retardation plate is known. Further, it is known that by further incorporating a vertical alignment liquid crystal cured film into an elliptical polarizing plate having a horizontal alignment liquid crystal cured film, it is possible to suppress a change in the oblique hue when the elliptical polarizing plate is used for black display in an organic EL display device, and patent document 1 describes a laminate including a vertical alignment liquid crystal cured film formed on the vertical alignment film and a horizontal alignment liquid crystal cured film formed on the horizontal alignment film.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2015-163935
Disclosure of Invention
Problems to be solved by the invention
However, a laminate including a vertical alignment liquid crystal cured film and a horizontal alignment liquid crystal cured film as described in the above patent document has been conventionally manufactured in many cases by the following methods: after the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are separately prepared, the two films are bonded by an adhesive or the like. In addition, conventionally, in the production of a vertical alignment liquid crystal cured film, a vertical alignment film for aligning a polymerizable liquid crystal compound in a vertical direction is required, and it is necessary to form the vertical alignment film before forming the vertical alignment liquid crystal cured film. Therefore, the conventional laminate including the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film is liable to have complicated manufacturing steps, and there is a problem that productivity is liable to be lowered.
Accordingly, an object of the present invention is to provide a novel solution to the above-described problem, namely, to provide a laminate capable of forming a vertically oriented liquid crystal cured film without forming a vertically oriented film and further continuously forming a horizontally oriented liquid crystal cured film, and a method for producing the laminate.
In addition, as a result of the studies of the inventors of the present application on the means of solving the above problems, it has been found that when a vertical alignment liquid crystal cured film is formed without forming a vertical alignment film, the liquid crystal alignment property tends to be lowered, and when a horizontal liquid crystal cured film is formed on the vertical alignment liquid crystal cured film via the horizontal alignment film, the adhesion between the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film tends to be lowered as compared with a laminate obtained by bonding the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film with an adhesive layer.
Accordingly, another object of the present invention is to improve the liquid crystal alignment properties of a laminate including a horizontally oriented liquid crystal cured film laminated on a vertically oriented liquid crystal cured film formed without a vertically oriented film, and to improve the adhesion between the vertically oriented liquid crystal cured film and the horizontally oriented liquid crystal cured film formed on the vertically oriented liquid crystal cured film via the horizontally oriented film.
Means for solving the problems
The inventors of the present application have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention includes the following modes.
[1] A laminate comprising a substrate, a vertically oriented liquid crystal cured film, a horizontally oriented film, and a horizontally oriented liquid crystal cured film in this order,
The vertical alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in a state of being aligned in a vertical direction with respect to the plane of the liquid crystal cured film, the horizontal alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in a state of being aligned in a horizontal direction with respect to the plane of the liquid crystal cured film,
the vertical alignment liquid crystal cured film contains a vertical alignment accelerator, the horizontal alignment film is a photo-alignment film formed from a (meth) acrylic polymer,
the total film thickness from the surface of the substrate side of the vertical alignment liquid crystal cured film to the surface of the horizontal alignment liquid crystal cured film opposite to the horizontal alignment film is 10 [ mu ] m or less.
[2] The laminate according to the above [1], wherein the substrate is a releasable substrate.
[3] The laminate according to the above [1] or [2], wherein the substrate, the vertically oriented liquid crystal cured film, the horizontally oriented film, and the horizontally oriented liquid crystal cured film are present adjacently in this order.
[4] The laminate according to any one of the above [1] to [3], wherein the film thickness of the horizontal alignment film is 10 to 5000nm.
[5] The laminate according to any one of the above [1] to [4], wherein the horizontal alignment film is a photo-alignment film formed of a polymer having an azo group or a cinnamoyl group.
[6] The laminate according to any one of the above [1] to [5], wherein the horizontally oriented liquid crystal cured film has at least one or more maximum absorption at a wavelength of 300 to 400 nm.
[7] The laminate according to any one of the above [1] to [6], wherein the horizontally oriented liquid crystal cured film satisfies the following formula (1):
ReA(450)/ReA(550)≤1 (1)
in the formula (1), reA (450) represents an in-plane phase difference value at a wavelength of 450nm in an in-plane direction of the horizontally oriented liquid crystal cured film, and ReA (550) represents an in-plane phase difference value at a wavelength of 550nm in an in-plane direction of the horizontally oriented liquid crystal cured film.
[8] The laminate according to any one of the above [1] to [7], wherein the vertical alignment liquid crystal cured film contains a nonionic silane compound as a vertical alignment accelerator.
[9] The laminate according to any one of the above [1] to [8], wherein the homeotropic alignment liquid crystal cured film comprises a nonionic silane compound as a homeotropic alignment accelerator, and the nonionic silane compound is a silane coupling agent.
[10] The laminate according to any one of the above [1] to [9], wherein the vertically aligned liquid crystal cured film contains an ionic compound formed of a nonmetallic atom as a vertical alignment accelerator.
[11] The laminate according to any one of the above [1] to [10], wherein the vertical alignment liquid crystal cured film contains an ionic compound formed of a nonmetallic atom as a vertical alignment accelerator, and the molecular weight of the ionic compound is 100 or more and 10,000 or less.
[12] The laminate according to any one of the above [1] to [11], wherein the vertical alignment liquid crystal cured film comprises a nonionic silane compound and an ionic compound formed of a nonmetallic atom as a vertical alignment accelerator.
[13] The laminate according to any one of [1] to [12], wherein the horizontally oriented liquid crystal cured film is a liquid crystal cured film obtained by curing a polymerizable liquid crystal compound having at least one radical polymerizable group in a state of being horizontally oriented with respect to the in-plane direction of the liquid crystal cured film, and the vertically oriented liquid crystal cured film is a liquid crystal cured film obtained by curing a polymerizable liquid crystal compound having at least one radical polymerizable group in a state of being vertically oriented with respect to the in-plane direction of the liquid crystal cured film.
[14] The laminate according to any one of the above [1] to [13], wherein the vertically oriented liquid crystal cured film has at least one maximum absorption at a wavelength of 300 to 400 nm.
[15] The laminate according to any one of the above [1] to [14], wherein the vertically aligned liquid crystal cured film satisfies the following formula (2):
RthC(450)/RthC(550)≤1 (2)
in the formula (2), rthC (450) represents a phase difference value in the thickness direction at a wavelength of 450nm of the vertical alignment liquid crystal cured film, and RthC (550) represents a phase difference value in the thickness direction at a wavelength of 550nm of the vertical alignment liquid crystal cured film.
[16] An elliptical polarizing plate comprising the laminate of any one of [1] to [15] and a polarizing film.
[17] An elliptical polarizing plate comprising a laminate obtained by removing the base material from the laminate of any one of the above [1] to [15], and a polarizing film.
[18] The elliptical polarizing plate of the above [16] or [17], wherein an angle between a slow axis of a horizontally oriented liquid crystal cured film constituting the laminate and an absorption axis of the polarizing film is 45.+ -. 5 °.
[19] An organic EL display device comprising the elliptical polarizing plate of any one of [16] to [18 ].
[20] The method for producing a laminate according to any one of the above [1] to [15], comprising the following steps in order:
a step of forming a coating film of a polymerizable liquid crystal composition for forming a cured film of a homeotropic liquid crystal, the coating film containing a polymerizable liquid crystal compound;
forming a coating film of the composition for forming a horizontal alignment film, and forming a horizontal alignment film from the coating film; the method comprises the steps of,
and a step of forming a coating film of the polymerizable liquid crystal composition for forming a cured film of a horizontally oriented liquid crystal containing the polymerizable liquid crystal compound, and forming a cured film of a horizontally oriented liquid crystal from the coating film.
[21] The production method according to the above [20], wherein the step of forming a vertically oriented liquid crystal cured film, the step of forming a horizontally oriented film, and the step of forming a horizontally oriented liquid crystal cured film are sequentially carried out.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a laminate which can form a vertical alignment liquid crystal cured film without forming a vertical alignment film, and further continuously form a horizontal alignment liquid crystal cured film on the vertical alignment liquid crystal cured film via a horizontal alignment film, and a method for producing the laminate. In addition, in the laminate, the liquid crystal alignment properties can be improved, and the adhesion between the vertically oriented liquid crystal cured film and the horizontally oriented liquid crystal cured film formed on the vertically oriented liquid crystal cured film via the horizontally oriented film can be improved.
Drawings
FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the laminate of the present invention.
FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the laminate of the present invention.
FIG. 3 is a schematic cross-sectional view showing an example of the layer structure of the laminate of the present invention.
Detailed Description
The laminate of the present invention comprises a substrate, a vertically oriented liquid crystal cured film, a horizontally oriented film, and a horizontally oriented liquid crystal cured film in this order. An example of the layer structure of the laminate of the present invention will be described below with reference to fig. 1 to 3, but the laminate of the present invention is not limited to these modes.
The laminate 11 shown in fig. 1 is formed by laminating a base material 1, a vertical alignment liquid crystal cured film 2, a horizontal alignment film 3, and a horizontal alignment liquid crystal cured film 4 in this order. In the laminate 11 shown in fig. 1, the homeotropic liquid crystal cured film 2 is directly formed on the substrate 1 without a layer having a homeotropic alignment controlling force (hereinafter, also referred to as a "homeotropic film"), and the substrate 1 is present adjacent to the homeotropic liquid crystal cured film 2. The laminate of the present invention may further include other layers in addition to the base material, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film, as long as the effects of the present invention are not affected. Examples of the other layer include a cured resin layer such as a protective layer and a hard coat layer, a further horizontally oriented liquid crystal cured film, and an adhesive layer for bonding the laminate of the present invention to a polarizing film or the like.
As a laminate including other layers, for example, in a laminate 11 shown in fig. 2 as another embodiment of the present invention, a base material 1 and a vertically oriented liquid crystal cured film 2 are laminated via a cured resin layer 5, and a horizontally oriented film 3 and a horizontally oriented liquid crystal cured film 4 are laminated on the vertically oriented liquid crystal cured film 2. In the laminate 11 shown in fig. 3, which is another embodiment of the present invention, the base material 1 and the vertical alignment liquid crystal cured film 2 are laminated via the cured resin layer 5, the vertical alignment liquid crystal cured film 2 and the horizontal alignment film 3 are laminated via the cured resin layer 5, and the horizontal alignment liquid crystal cured film 4 is laminated on the horizontal alignment film 3. By bonding the laminate 11 to the polarizing film via the adhesive layer, an elliptical polarizing plate can be obtained. At this time, any side of the vertically oriented liquid crystal cured film 2 and the horizontally oriented liquid crystal cured film 4 of the laminate 11 may be bonded to the polarizing film, for example, the vertically oriented liquid crystal cured film 2 may be bonded to the polarizing film via an adhesive layer after the base material 1 of the laminate 11 of fig. 1 is peeled off, or the horizontally oriented liquid crystal cured film 4 of the laminate 11 of fig. 1 may be bonded to the polarizing film via an adhesive layer. In the following description, the smallest layer structure among the layer structures of the laminate of the present invention, which sequentially includes the base material, the vertically oriented liquid crystal cured film, the horizontally oriented film, and the horizontally oriented liquid crystal cured film, is also referred to as "basic layer structure (I)". That is, for example, in the case where the laminate of the present invention is composed of a base material, a vertically oriented liquid crystal cured film, a horizontally oriented liquid crystal cured film 1, and a horizontally oriented liquid crystal cured film 2, the base layer structure (I) of the laminate of the present invention is formed from the base material to the horizontally oriented liquid crystal cured film located closest to the base material (in this case, the horizontally oriented liquid crystal cured film 1).
In the laminate of the present invention, the total film thickness (the thickness between a and b in fig. 1 to 3, hereinafter also referred to as "total film thickness T1") from the surface of the cured film of the vertically oriented liquid crystal on the substrate side to the surface of the cured film of the horizontally oriented liquid crystal on the opposite side to the horizontally oriented film is 10 μm or less. Since the laminate of the present invention is obtained by directly forming the horizontal alignment liquid crystal cured film on the vertical alignment liquid crystal cured film via the horizontal alignment film, the total film thickness T1 can be made thinner than a conventional laminate obtained by bonding the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film with an adhesive or an adhesive after separately manufacturing them. The thinning of the total film thickness T1 of the laminate can also contribute to the thinning of the entire laminate, an elliptical polarizing plate including the laminate, and the like. The total film thickness T1 in the laminate of the present invention is preferably 7 μm or less, more preferably 5 μm or less. The lower limit of the total film thickness T1 is not particularly limited, but is usually 1 μm or more, for example, 1.5 μm or more. In the case where the laminate of the present invention further includes a vertical alignment liquid crystal cured film and/or a horizontal alignment liquid crystal cured film on the side of the horizontal alignment liquid crystal cured film of the base layer structure (I) opposite to the horizontal alignment film, the total film thickness T1 is the total film thickness from the surface on the substrate side of the vertical alignment liquid crystal cured film constituting the base layer structure (I) to the surface on the side of the horizontal alignment liquid crystal cured film opposite to the horizontal alignment film.
In the laminate of the present invention, the homeotropic alignment liquid crystal cured film may be formed on the substrate or on a layer having no homeotropic alignment controlling force provided on the substrate, not via the homeotropic alignment film. In the laminate of the present invention, the vertical alignment liquid crystal cured film can be formed without a vertical alignment film, and therefore, the number of manufacturing steps of the laminate is reduced, and the laminate can be manufactured with good productivity. That is, in one embodiment of the laminate of the present invention, the substrate and the vertical alignment liquid crystal cured film are laminated without interposing the vertical alignment film therebetween, and in a more preferred embodiment, the laminate of the present invention is formed by the substrate, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film being sequentially adjacent to each other. In the laminate of the present invention having such a layer structure, since the vertical alignment liquid crystal cured film can be formed on the substrate without the vertical alignment film, and the horizontal alignment liquid crystal cured film can be further continuously formed on the vertical alignment liquid crystal cured film via the horizontal alignment film, the laminate can be produced with a better productivity.
Hereinafter, each structure of the laminate of the present invention will be described in detail.
[ vertical alignment liquid Crystal cured film ]
The vertical alignment liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in a state of being aligned in a vertical direction with respect to the plane of the liquid crystal cured film. In the present invention, the homeotropic alignment liquid crystal cured film contains a homeotropic alignment accelerator. That is, in the present invention, the polymerizable liquid crystal composition for forming a cured film of a homeotropic alignment accelerator is contained. In the present invention, the vertical alignment accelerator means a material that promotes the alignment of liquid crystals of the polymerizable liquid crystal compound in a vertical direction with respect to the film plane. By including the homeotropic alignment accelerator in the homeotropic alignment liquid crystal cured film, the homeotropic alignment liquid crystal cured film can be formed without the homeotropic alignment film. In this way, in the laminate of the present invention, there is no need to form a vertically oriented liquid crystal cured film, and the process for producing the laminate is simplified, so that the laminate can be produced with good productivity. When a horizontal alignment film and a horizontal alignment liquid crystal cured film are formed on the vertical alignment liquid crystal cured film, the alignment property of the horizontal alignment liquid crystal cured film tends to be easily deteriorated. The reason is not definite, but it is presumed that: the surface energy is reduced by additives such as leveling agents contained in the vertically oriented liquid crystal cured film, and the alignment properties of the liquid crystal compound are easily impaired when the horizontally oriented liquid crystal cured film is formed on the upper layer. In particular, since the alignment accelerator is further contained in the case of forming the homeotropic liquid crystal cured film in such a manner that the homeotropic alignment film is not formed, the influence thereof becomes more remarkable.
Examples of the vertical alignment accelerator that promotes the alignment of the polymerizable liquid crystal compound in the vertical direction include nonionic silane compounds and ionic compounds composed of nonmetallic atoms. The vertical alignment liquid crystal cured film preferably contains at least 1 of a nonionic silane compound and an ionic compound formed of a nonmetallic atom, more preferably contains both a nonionic silane compound and an ionic compound formed of a nonmetallic atom.
When the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film contains a nonionic silane compound, the nonionic silane compound lowers the surface tension of the polymerizable liquid crystal composition, and the nonionic silane compound tends to be biased at the interface between the dry coating film and air in the dry coating film formed from the polymerizable liquid crystal composition, so that the vertical alignment control force for the polymerizable liquid crystal compound is improved, and the polymerizable liquid crystal compound in the dry coating film tends to be aligned in the vertical direction with respect to the film plane. This can form a liquid crystal cured film while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned.
The nonionic silane compound is a nonionic compound containing an Si element. Examples of the nonionic silane compound include a silicone polymer such as polysilane, a silicone resin such as silicone oil and silicone resin, and an organic inorganic silane compound (more specifically, a silane coupling agent or the like) such as a silicone oligomer, silsesquioxane and alkoxysilane.
These nonionic silane compounds may be used alone or in combination of 2 or more. Among them, a silane coupling agent is preferable from the viewpoint of further improving adhesion to the adjacent layer.
The nonionic silane compound may be of the organosilicon monomer type or of the organosilicon oligomer (polymer) type. When the silicone oligomer is represented in the form of a (monomer) - (monomer) copolymer, there may be mentioned: mercaptopropyl-containing copolymers such as 3-mercaptopropyl trimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyl trimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyl triethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyl triethoxysilane-tetraethoxysilane copolymer; mercaptomethyl trimethoxysilane-tetramethoxysilane copolymer, mercaptomethyl trimethoxysilane-tetraethoxysilane copolymer, mercaptomethyl triethoxysilane-tetramethoxysilane copolymer, and mercaptomethyl triethoxysilane-tetraethoxysilane copolymer; methacryloxypropyl group-containing copolymers such as 3-methacryloxypropyl trimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyl trimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyl triethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyl methyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyl methyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyl methyldiethoxysilane-tetramethoxysilane copolymer, and 3-methacryloxypropyl methyldiethoxysilane-tetraethoxysilane copolymer; 3-acryloxypropyl trimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyl trimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropyl triethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyl triethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropyl methyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyl methyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropyl methyldiethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyl methyldiethoxysilane-tetraethoxysilane copolymer, and 3-acryloxypropyl methyldiethoxysilane-tetraethoxysilane copolymer; vinyl-containing copolymers such as vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, and vinylmethyldiethoxysilane-tetraethoxysilane copolymer; amino group-containing copolymers such as 3-aminopropyl trimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyl trimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyl triethoxysilane-tetramethoxysilane copolymer, 3-aminopropyl methyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyl methyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropyl methyldiethoxysilane-tetraethoxysilane copolymer.
The silane coupling agent is a compound containing an Si element and having at least one functional group selected from the group consisting of a vinyl group, an epoxy group, a styryl group, a methacryloyl group, an acryl group, an amino group, an isocyanurate group, a urea group, a mercapto group, an isocyanate group, a carboxyl group, and a hydroxyl group, and at least one alkoxysilyl group or silanol group at the terminal end. By properly selecting these functional groups, excellent effects such as improvement in mechanical strength of the homeotropic liquid crystal cured film, surface modification of the homeotropic liquid crystal cured film, and improvement in adhesion to a layer adjacent to the homeotropic liquid crystal cured film can be imparted. From the viewpoint of adhesion, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (for example, the above-mentioned functional group). The silane coupling agent is further preferably a silane coupling agent having an alkoxysilyl group and a polar group. When the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, the vertical alignment property of the polymerizable liquid crystal compound tends to be further improved, and a vertical alignment promoting effect tends to be remarkably obtained. Examples of the polar group include an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxyl group, and a hydroxyl group. In order to control the reactivity of the silane coupling agent, the polar group may have a substituent or a protecting group as appropriate.
Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl dimethoxymethylsilane and 3-glycidoxypropyl ethoxydimethylsilane.
Examples of commercially available silane coupling agents include those manufactured by the Xinyue chemical industry (strain) such as KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007.
When the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film contains a nonionic silane compound, the content thereof is usually preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. When the content of the nonionic silane compound is within the above range, the vertical alignment of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coatability of the polymerizable liquid crystal composition.
When the polymerizable liquid crystal composition forming the vertically oriented liquid crystal cured film contains an ionic compound formed of a nonmetallic atom, a vertical orientation control force for the polymerizable liquid crystal compound is exhibited by electrostatic interaction in a dry coating film formed of the polymerizable liquid crystal composition, and the polymerizable liquid crystal compound in the dry coating film tends to be oriented in a vertical direction with respect to the film plane. This can form a liquid crystal cured film while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned.
Examples of the ionic compound formed from a nonmetallic atom include onium salts (more specifically, quaternary ammonium salts having a positive charge on a nitrogen atom, tertiary sulfonium salts, quaternary phosphonium salts having a positive charge on a phosphorus atom, and the like). Among these onium salts, quaternary onium salts are preferable from the viewpoint of further improving the vertical alignment of the polymerizable liquid crystal compound, and quaternary phosphonium salts or quaternary ammonium salts are more preferable from the viewpoint of improving the availability and mass productivity. The onium salt may have 2 or more quaternary onium salt sites in the molecule, and may be an oligomer or a polymer.
The molecular weight of the ionic compound formed of a nonmetallic atom is preferably 100 or more and 10,000 or less. When the molecular weight is within the above range, the vertical alignment of the polymerizable liquid crystal compound is easily improved while the coatability of the polymerizable liquid crystal composition is ensured. The molecular weight of the ionic compound formed of a nonmetallic atom is more preferably 5000 or less, and still more preferably 3000 or less.
Examples of the cationic component of the ionic compound formed from a nonmetallic atom include inorganic cations and organic cations. Among them, organic cations are preferable in view of the difficulty in generating alignment defects of the polymerizable liquid crystal compound. Examples of the organic cation include an imidazolium cation, a pyridinium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation.
Ionic compounds formed from nonmetallic atoms typically have a counter anion. Examples of the anionic component serving as a counter ion of the cationic component include inorganic anions and organic anions. Among them, organic anions are preferred in view of the difficulty in generating alignment defects of the polymerizable liquid crystal compound. It is to be noted that the cations and anions do not necessarily have to correspond one-to-one.
Specific examples of the anionic component include the following anions.
Chloride anions [ Cl ] - 〕、
Bromine anion [ Br ] - 〕、
Iodine anion [ I ] - 〕、
Tetrachloroaluminate anions [ AlCl ] 4 - 〕、
Heptachlorodialuminate anion [ Al 2 Cl 7 - 〕、
Tetrafluoroborate anion [ BF ] 4 - 〕、
Hexafluorophosphate anions [ PF 6 - 〕、
Perchlorate anions [ ClO ] 4 - 〕、
Nitrate anions [ NO ] 3 - 〕、
Acetate anions [ CH ] 3 COO - 〕、
Trifluoroacetate anion [ CF 3 COO - 〕、
Fluorosulfonate anions [ FSO ] 3 - 〕、
Methanesulfonate anion [ CH ] 3 SO 3 - 〕、
Trifluoro methanesulfonate anion [ CF 3 SO 3 - 〕、
Para-toluenesulfonate anion [ p-CH ] 3 C 6 H 4 SO 3 - 〕、
Bis (fluorosulfonyl) imide anions [ (FSO) 2 ) 2 N - 〕、
Bis (trifluoromethanesulfonyl) imide anion [ (CF) 3 SO 2 ) 2 N - 〕、
Tris (trifluoromethanesulfonyl) methane anion [ (CF) 3 SO 2 ) 3 C - 〕、
Hexafluoroarsenate anion [ AsF 6 - 〕、
Hexafluoroantimonate anions [ SbF 6 - 〕、
Hexafluoroniobate anions [ NbF 6 - 〕、
Hexafluorotantalate anions [ TaF 6 - 〕、
Dimethyl phosphinate anion [ (CH) 3 ) 2 POO - 〕、
(poly) hydrofluoroanions ((poly) hydrofluorofluoride anion) [ F (HF) n - (e.g., n represents an integer of 1 to 3),
Dicyandiamide anion [ (CN) 2 N - 〕、
Thiocyanate anion [ SCN - 〕、
Perfluorobutanesulfonate anion [ C 4 F 9 SO 3 - 〕、
Bis (pentafluoroethylsulfonyl) imide anions [ (C) 2 F 5 SO 2 ) 2 N - 〕、
Perfluorobutyric acid radical anion [ C ] 3 F 7 COO - A kind of electronic device with a high-pressure air-conditioning system
(trifluoromethanesulfonyl) (trifluoromethanecarbonyl) imine anion
〔(CF 3 SO 2 )(CF 3 CO)N - 〕。
Specific examples of the ionic compound formed of a nonmetallic atom may be appropriately selected from the combinations of the above cationic component and anionic component. Specific examples of the compound to be used as a combination of the cationic component and the anionic component include the following compounds.
(pyridinium salt)
N-hexylpyridinium hexafluorophosphate,
N-octyl pyridinium hexafluorophosphate,
N-methyl-4-hexylpyridinium hexafluorophosphate,
N-butyl-4-methylpyridinium hexafluorophosphate,
N-octyl-4-methylpyridinium hexafluorophosphate,
Bis (fluorosulfonyl) imide N-hexylpyridinium,
Bis (fluorosulfonyl) imide N-octyl pyridinium,
Bis (fluorosulfonyl) imide N-methyl-4-hexylpyridinium,
Bis (fluorosulfonyl) imide N-butyl-4-methylpyridinium,
Bis (fluorosulfonyl) imide N-octyl-4-methylpyridinium,
Bis (trifluoromethanesulfonyl) imide N-hexylpyridinium,
Bis (trifluoromethanesulfonyl) imide N-octylpyridinium,
Bis (trifluoromethanesulfonyl) imide N-methyl-4-hexylpyridinium,
Bis (trifluoromethanesulfonyl) imide N-butyl-4-methylpyridinium,
Bis (trifluoromethanesulfonyl) imide N-octyl-4-methylpyridinium,
N-hexylpyridinium p-toluenesulfonate,
N-octyl pyridinium p-toluenesulfonate,
N-methyl-4-hexylpyridinium p-toluenesulfonate, N-butyl-4-methylpyridinium p-toluenesulfonate, and process for producing the same
N-octyl-4-methylpyridinium p-toluenesulfonate.
(imidazolium salt)
1-ethyl-3-methylimidazolium hexafluorophosphate,
Bis (fluorosulfonyl) imide 1-ethyl-3-methylimidazolium, bis (trifluoromethanesulfonyl) imide 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-butyl-3-methylimidazolium methanesulfonate, and the like.
(pyrrolidinium salt)
N-butyl-N-methylpyrrolidinium hexafluorophosphate, bis (fluorosulfonyl) imide N-butyl-N-methylpyrrolidinium, bis (trifluoromethanesulfonyl) imide N-butyl-N-methylpyrrolidinium, N-butyl-N-methylpyrrolidinium p-toluenesulfonate, and the like.
(ammonium salt)
Tetrabutylammonium hexafluorophosphate,
Bis (fluorosulfonyl) imide tetrabutylammonium,
Bis (fluorosulfonyl) imide tetrahexylammonium,
Bis (fluorosulfonyl) imide trioctyl methyl ammonium, bis (fluorosulfonyl) imide (2-hydroxyethyl) trimethyl ammonium, bis (trifluoromethylsulfonyl) imide tetrabutyl ammonium, bis (trifluoromethylsulfonyl) imide tetrahexyl ammonium, bis (trifluoromethylsulfonyl) imide trioctyl methyl ammonium, bis (trifluoromethylsulfonyl) imide (2-hydroxyethyl) trimethyl ammonium, tetrabutyl ammonium p-toluenesulfonate,
Tetrahexylammonium p-toluenesulfonate,
Trioctylmethylammonium p-toluenesulfonate,
Para-toluenesulfonic acid (2-hydroxyethyl) trimethylammonium,
Dimethyl phosphinic acid (2-hydroxyethyl) trimethylammonium,
Bis (trifluoromethanesulfonyl) imide 1- (3-trimethoxysilylpropyl) -1, 1-tributylammonium,
Bis (trifluoromethanesulfonyl) imide 1- (3-trimethoxysilylpropyl) -1, 1-trimethylammonium,
Bis (trifluoromethanesulfonyl) imine 1- (3-trimethoxysilylbutyl) -1, 1-tributylammonium,
Bis (trifluoromethanesulfonyl) imine 1- (3-trimethoxysilylbutyl) -1, 1-trimethylammonium,
Bis (trifluoromethanesulfonyl) imide N- { (3-triethoxysilylpropyl) carbamoyloxyethyl) } -N, N, N-trimethylammonium
Bis (trifluoromethanesulfonyl) imide N- [2- {3- (3-trimethoxysilylpropylamino) -1-oxopropoxy } ethyl ] -N, N, N-trimethylammonium.
(phosphonium salt)
Bis (trifluoromethanesulfonyl) imide tributyl (2-methoxyethyl) phosphonium,
Bis (trifluoromethanesulfonyl) iminotributylmethyl phosphonium,
Bis (trifluoromethanesulfonyl) imine 1, 1-trimethyl-1- [ (trimethoxysilyl) methyl ] phosphonium,
Bis (trifluoromethanesulfonyl) imine 1, 1-trimethyl-1- [2- (trimethoxysilyl) ethyl ] phosphonium,
Bis (trifluoromethanesulfonyl) imine 1, 1-trimethyl-1- [3- (trimethoxysilyl) propyl ] phosphonium,
Bis (trifluoromethanesulfonyl) imine 1, 1-trimethyl-1- [4- (trimethoxysilyl) butyl ] phosphonium,
Bis (trifluoromethanesulfonyl) imine 1, 1-tributyl-1- [ (trimethoxysilyl) methyl ] phosphonium,
Bis (trifluoromethanesulfonyl) imine 1, 1-tributyl-1- [2- (trimethoxysilyl) ethyl ] phosphonium, and process for preparing same
Bis (trifluoromethanesulfonyl) imine 1, 1-tributyl-1- [3- (trimethoxysilyl) propyl ] phosphonium.
These ionic compounds may be used alone or in combination of 2 or more. Among them, ionic compounds formed from phosphonium salts, pyridinium salts, and ammonium salts are preferable.
From the viewpoint of further improving the vertical alignment property of the polymerizable liquid crystal compound, the ionic compound formed of a nonmetallic atom preferably has an Si element and/or an F element in the molecular structure of the cationic site. When the ionic compound formed of a nonmetallic atom has Si element and/or F element in the molecular structure of the cationic site, the ionic compound is likely to segregate on the surface of the vertically aligned liquid crystal cured film. Among these, the following ionic compounds (i) to (iii) are preferable as the ionic compounds in which all constituent elements are nonmetallic elements.
(Ionic Compound (i))
(Ionic Compound (ii))
(Ionic Compound (iii))
For example, a method of treating the surface of a substrate with a surfactant having a long alkyl group with a certain chain length to improve the alignment property of liquid crystal (for example, see chapter 2 liquid crystal alignment and physical properties of "liquid crystal review" (issued by Wan Corp.) and the like) may be applied to further improve the vertical alignment property of a polymerizable liquid crystal compound. That is, by treating the surface of the substrate with an ionic compound having a long alkyl group with a certain degree of chain length, the vertical alignment property of the polymerizable liquid crystal compound can be effectively improved.
Specifically, the ionic compound formed of a nonmetallic atom preferably satisfies the following formula (3).
5<M<16 (3)
In the formula (3), M is represented by the following formula (4).
M= (number of covalent bonds from atom having positive charge to end of molecule of substituents having the largest number of covalent bonds to end of molecule among substituents directly bonded to atom having positive charge)/(number of atoms having positive charge) (4)
By satisfying the above (3) with an ionic compound formed of a nonmetallic atom, the vertical alignment of the polymerizable liquid crystal compound can be effectively improved.
In the case where 2 or more atoms having positive charges are present in the molecule of the ionic compound formed of a nonmetallic atom, the number of covalent bonds from the atom having positive charges to the nearest other atom having positive charges from the atom having positive charges as a base point is defined as "the number of covalent bonds from the atom having positive charges to the end of the molecular chain" described in the definition of M. In the case where the ionic compound formed of a nonmetallic atom is an oligomer or polymer having 2 or more repeating units, the constituent units are regarded as one molecule, and the above M is calculated. When an atom having a positive charge is incorporated into a ring structure, one of the number of covalent bonds between the atom having a positive charge and the atom having a positive charge through the ring structure and the number of covalent bonds between the atom and the terminal of a substituent bonded to the ring structure, which is greater than the number of covalent bonds, is defined as "the number of covalent bonds between the atom having a positive charge and the terminal of a molecular chain" in the definition of M.
When the polymerizable liquid crystal composition for forming the vertical alignment liquid crystal cured film contains an ionic compound formed of a nonmetallic atom, the content thereof is usually preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. When the content of the ionic compound formed of the nonmetallic atom is within the above range, the vertical alignment of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coatability of the polymerizable liquid crystal composition.
By including both the nonionic silane compound and the ionic compound formed from the nonmetallic atoms in the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film, vertical alignment of the polymerizable liquid crystal compound is easily further promoted by the electrostatic interaction of the ionic compound formed from the nonmetallic atoms and the surface tension reducing effect of the nonionic silane compound in the dried coating film formed from the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film. This can form a liquid crystal cured film while maintaining a state in which the polymerizable liquid crystal compound is vertically aligned with higher accuracy.
The vertical alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing the vertical alignment accelerator and at least 1 polymerizable liquid crystal compound, and is preferably a liquid crystal cured film in which a polymerizable liquid crystal compound having at least one radical polymerizable group is cured in a state of being oriented vertically to the in-plane direction of the liquid crystal cured film. In the present invention, the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film means a liquid crystal compound having a polymerizable group, and particularly preferably a liquid crystal compound having at least one radical polymerizable group. The polymerizable liquid crystal compound is not particularly limited, and for example, a polymerizable liquid crystal compound conventionally known in the field of retardation films can be used.
The polymerizable group means a group capable of participating in polymerization reaction by a living radical, an acid, or the like generated by a polymerization initiator. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, epoxyethyl, and oxetanyl groups. Among them, a radical polymerizable group is preferable, and acryloyloxy, methacryloyloxy, vinyl, and vinyloxy groups are more preferable, and acryloyloxy and methacryloyloxy groups are still more preferable. When the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are laminated via the horizontal alignment film, adhesion between the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film continuously formed via the horizontal photo-alignment film formed by using the polymer having a (meth) acryloyl group is easily improved when the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are both cured products of the polymerizable liquid crystal compound having at least one radical polymerizable group.
The liquid crystal property exhibited by the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, but is preferably a thermotropic liquid crystal in view of enabling precise film thickness control. The phase-ordered structure in the thermotropic liquid crystal may be a nematic liquid crystal or a smectic liquid crystal. The polymerizable liquid crystal compound may be used alone or in combination of two or more.
Examples of the polymerizable liquid crystal compound include a polymerizable liquid crystal compound that normally exhibits a positive wavelength dispersibility and a polymerizable liquid crystal compound that exhibits a reverse wavelength dispersibility, and either one of the polymerizable liquid crystal compounds may be used, or both of the polymerizable liquid crystal compounds may be mixed and used. From the viewpoint of a large effect of suppressing the oblique reflection hue at the time of black display when the vertical alignment liquid crystal cured film is applied to a display device, it is preferable to include a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility.
The polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is preferably a compound having the following characteristics (a) to (D).
(A) Is a compound capable of forming a nematic or smectic phase.
(B) The polymerizable liquid crystal compound has pi electrons in the long axis direction (a).
(C) Has pi electrons in a direction crossing the long axis direction (a) [ crossing direction (b) ].
(D) The pi electron density in the long axis direction (a) of the polymerizable liquid crystal compound defined by the following formula (i) by taking the total of pi electrons present in the long axis direction (a) as N (pi a) and the total of molecular weights present in the long axis direction as N (Aa):
d (pi a) =n (pi a)/N (Aa) (i), and,
The pi electron density in the cross direction (b) of the polymerizable liquid crystal compound defined by the following formula (ii) by taking the sum of pi electrons present in the cross direction (b) as N (pi b) and the sum of molecular weights present in the cross direction (b) as N (Ab):
D(πb)＝N(πb)/N(Ab) (ii)
there is a relationship of formula (iii):
0≤〔D(πa)/D(πb) 〕<1 (iii)
[ i.e., the pi electron density in the cross direction (b) is greater than the pi electron density in the long axis direction (a) ].
As described above, the polymerizable liquid crystal compound having pi electrons in the long axis and the direction intersecting the long axis has, for example, a T-shaped structure.
In the features (a) to (D), the long axis direction (a) and pi electron number N are defined as follows.
In the case of a compound having a rod-like structure, for example, the long axis direction (a) is the long axis direction of the rod.
Pi electrons that disappear by the polymerization reaction are not included in pi electron number N (pi a) existing in the long axis direction (a).
The pi electron number N (pi a) existing in the long axis direction (a) is the sum of pi electrons on the long axis and pi electrons conjugated thereto, and includes, for example, the number of pi electrons existing on a ring existing in the long axis direction (a) and satisfying the shock rule.
Pi electrons that disappear by the polymerization reaction are not included in the pi electron number N (pi b) existing in the cross direction (b).
The polymerizable liquid crystal compound has a mesogenic structure in the long axis direction. The mesogenic structure exhibits a liquid crystal phase (nematic phase, smectic phase).
The polymerizable liquid crystal compounds satisfying the above (a) to (D) are applied to a film (layer) forming a liquid crystal cured film, and heated to a temperature equal to or higher than the phase transition temperature, whereby a nematic phase or smectic phase can be formed. The nematic phase or smectic phase formed by the alignment of the polymerizable liquid crystal compound is generally aligned such that the long axis directions of the polymerizable liquid crystal compound are parallel to each other, and the long axis directions are alignment directions of the nematic phase. When such a polymerizable liquid crystal compound is formed into a film and polymerized in a nematic phase or smectic phase, a polymer film formed of a polymer polymerized in a state of being oriented in the long axis direction (a) can be formed. The polymer film absorbs ultraviolet rays by pi electrons in the long axis direction (a) and pi electrons in the cross direction (b). Here, the absorption maximum wavelength of ultraviolet light absorbed by pi electrons in the intersecting direction (b) is denoted as λbmax. The λbmax is generally 300nm to 400nm. Since pi electron density satisfies the above formula (iii), pi electron density in the cross direction (b) is higher than pi electron density in the long axis direction (a), it is a polymer film having higher absorption of linearly polarized ultraviolet light (wavelength λbmax) having a vibration plane in the cross direction (b) than that of linearly polarized ultraviolet light (wavelength λbmax) having a vibration plane in the long axis direction (a). The ratio (ratio of absorbance in the cross direction (b) of linearly polarized ultraviolet rays to absorbance in the longitudinal direction (a)) is, for example, more than 1.0, preferably 1.2 or more, and usually 30 or less, for example, 10 or less.
The polymerizable liquid crystal compounds having the above-mentioned characteristics generally exhibit inverse wavelength dispersibility in many cases. Specifically, for example, a compound represented by the following formula (X) is given.
In the formula (X), ar represents a divalent group containing an aromatic group which may have a substituent. The aromatic group herein means a group having pi electrons of the ring structure of [4n+2] in accordance with the rule of shock, and may have 2 or more Ar groups exemplified by (Ar-1) to (Ar-23) described below through a divalent linking group. Where n represents an integer. When a ring structure is formed by including a heteroatom such as-n=, -S-, etc., the case where the aromatic property is obtained by including a pair of noncovalent electrons on these heteroatoms while satisfying the shock rule is included. The aromatic group preferably contains at least 1 or more of a nitrogen atom, an oxygen atom, and a sulfur atom. The number of aromatic groups contained in the divalent group Ar may be 1 or 2 or more. When the number of aromatic groups is 1, the divalent group Ar may be a divalent aromatic group which may have a substituent. When the number of aromatic groups contained in the divalent group Ar is 2 or more, 2 or more aromatic groups may be bonded to each other by a divalent bonding group such as a single bond, -CO-O-, -O-.
G 1 G (G) 2 Each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and the carbon atoms constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom.
L 1 、L 2 、B 1 B (B) 2 Each independently is a single bond or a divalent linking group.
k. l each independently represents an integer of 0 to 3, satisfying the relation 1.ltoreq.k+l. Here, in the case where 2.ltoreq.k+l, B 1 B (B) 2 、G 1 G (G) 2 Each of which may be the same as or different from each other.
E 1 E and E 2 Each independently represents an alkanediyl group having 1 to 17 carbon atoms (alkanediyl), and more preferably an alkanediyl group having 4 to 12 carbon atoms. In addition, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and the-CH contained in the alkanediyl group 2 Can be replaced by-O-, -S-, -SiH 2 -C (=o) -substitution.
P 1 P 2 Independently of each other, a polymerizable group or a hydrogen atom, at least one of which is a polymerizable group.
G 1 G (G) 2 Each independently is preferably a 1, 4-phenylenediyl group (phenylenediyl) which may be substituted with at least 1 substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, a 1, 4-cyclohexanediyl group which may be substituted with at least 1 substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably a 1, 4-phenylenediyl group substituted with a methyl group, an unsubstituted 1, 4-phenylenediyl group, or an unsubstituted 1, 4-trans-cyclohexanediyl group, particularly preferably an unsubstituted 1, 4-phenylenediyl group, or an unsubstituted 1, 4-trans-cyclohexanediyl group.
In addition, a plurality of G's are preferably present 1 G (G) 2 At least 1 of them is a divalent alicyclic hydrocarbon group, and further, more preferably with L 1 Or L 2 Bonded G 1 G (G) 2 At least 1 of (2) is a divalent alicyclic hydrocarbon group.
L 1 L and L 2 Each independently is preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2 -、-R a3 COOR a4 -、-R a5 OCOR a6 -、R a7 OC＝OOR a8 -、-N＝N-、-CR c ＝CR d -, or-C.ident.C-. Here, R is a1 ～R a8 Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, R c R is R d Represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L (L) 1 L and L 2 More preferably each independently is a single bond, -OR a2-1 -、-CH 2 -、-CH 2 CH 2 -、-COOR a4-1 -, or-OCOR a6-1 -. Here, R is a2-1 、R a4-1 、R a6 -1 each independently represents a single bond, -CH 2 -、-CH 2 CH 2 -any one of them. L (L) 1 L and L 2 Each independently further preferably is a single bond, -O-, -CH 2 CH 2 -、-COO-、-COOCH 2 CH 2 -, or-OCO-.
B 1 B (B) 2 Each independently is preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a9 OR a10 -、-R a11 COOR a12 -、-R a13 OCOR a14 -, or R a15 OC＝OOR a16 -. Here, R is a9 ～R a16 Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms. B (B) 1 B (B) 2 More preferably each independently is a single bond, -OR a10-1 -、-CH 2 -、-CH 2 CH 2 -、-COOR a12 -1 -, or OCOR a14-1 -. Here, R is a10-1 、R a12-1 、R a14-1 Each independently represents a single bond, -CH 2 -、-CH 2 CH 2 -any one of them. B (B) 1 B (B) 2 Each independently further preferably is a single bond, -O-, -CH 2 CH 2 -、-COO-、-COOCH 2 CH 2 -, -OCO-, or-OCOCH 2 CH 2 -。
For k and l, from the viewpoint of exhibiting inverse wavelength dispersibility, the range of 2.ltoreq.k+l.ltoreq.6 is preferable, k+l=4 is preferable, k=2 is more preferable, and l=2 is more preferable. k=2 and l=2 are preferably in a symmetrical structure.
As P 1 Or P 2 Examples of the polymerizable group include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an epoxy ethyl group, and an oxetanyl group. Among them, acryloyloxy, methacryloyloxy, vinyl and vinyloxy are preferable, and acryloyloxy and methacryloyloxy are more preferable.
Ar preferably has at least one selected from the group consisting of an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron withdrawing group. Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, and anthracene ring, and benzene ring and naphthalene ring are preferable. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring, an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, and a phenanthroline ring. Among them, a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferable, and a benzothiazolyl group is more preferable. In the case where Ar contains a nitrogen atom, the nitrogen atom preferably has pi electrons.
In the formula (X), ar represents a total number N of pi electrons contained in the divalent aromatic group π Preferably 8 or more, more preferably 10 or more, further preferably 14 or more, and particularly preferably 16 or more. The content is preferably 30 or less, more preferably 26 or less, and even more preferably 24 or less.
Examples of the aromatic group represented by Ar include the following groups.
In the formulae (Ar-1) to (Ar-23), the symbol represents a connecting portion, Z 0 、Z 1 Z is as follows 2 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an N-alkylamino group having 1 to 12 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfonyl group having 1 to 12 carbon atoms, or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms. In addition, Z 0 、Z 1 Z is as follows 2 May contain a polymerizable group.
Q 1 Q and Q 2 Each independently represents-CR 2’ R 3’ -、-S-、-NH-、-NR 2’ -, -CO-or-O-, R 2’ R is R 3’ Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
J 1 J 2 Each independently represents a carbon atom, or a nitrogen atom.
Y 1 、Y 2 Y and Y 3 Each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.
W 1 W and W 2 Each independently represents a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.
As Y 1 、Y 2 Y and Y 3 Examples of the aromatic hydrocarbon group in (a) include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl and biphenyl, and preferably phenyl and naphthyl, more preferably phenyl. Examples of the aromatic heterocyclic group include an aromatic heterocyclic group having 4 to 20 carbon atoms and containing at least 1 hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc., such as a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group, a thiazolyl group, a benzothiazolyl group, etc., and a furyl group, a thienyl group, a pyridyl group, a thiazolyl group, a benzothiazolyl group are preferable.
Y 1 、Y 2 Y and Y 3 Each independently may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted. Polycyclic aromatic hydrocarbon groups refer to fused polycyclic aromatic hydrocarbon groups or groups derived from an aromatic ring set. Polycyclic aromatic heterocyclic groups refer to fused polycyclic aromatic heterocyclic groups, or groups derived from an aromatic ring set.
Z 0 、Z 1 Z is as follows 2 Each independently is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, Z 0 Further preferable are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group and Z 1 Z is as follows 2 Further preferred are a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group and a cyano group. In addition, Z 0 、Z 1 Z is as follows 2 May contain a polymerizable group.
Q 1 Q and Q 2 preferably-NH-, -S-, -NR 2’ -、-O-，R 2’ Preferably a hydrogen atom. Wherein,, particularly preferred are-S-; -O-, -NH-.
Of the formulae (Ar-1) to (Ar-23), the formulae (Ar-6) and (Ar-7) are preferable from the viewpoint of stability of the molecule.
In the formulae (Ar-16) to (Ar-23), Y 1 Nitrogen atom and Z which can be bonded thereto 0 Together forming an aromatic heterocyclic group. As the aromatic heterocyclic group, there may be mentionedExamples of the aromatic heterocyclic ring that Ar may have include a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an indole ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring. The aromatic heterocyclic group may have a substituent. In addition, Y 1 Nitrogen atom and Z which can be bonded thereto 0 Together form the aforementioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. For example, a benzofuran ring, benzothiazole ring, benzoxazole ring, and the like can be cited.
In the present invention, as the polymerizable liquid crystal compound for forming the vertical alignment liquid crystal cured film, for example, a compound containing a group represented by the following formula (Y) (hereinafter, also referred to as "polymerizable liquid crystal compound (Y)") can be used. The polymerizable liquid crystal compound (Y) generally tends to exhibit positive wavelength dispersibility. The polymerizable liquid crystal compound may be used alone or in combination of 2 or more.
P11-B11-E11-B12-A11-B13-(Y)
In the formula (Y), P11 represents a polymerizable group.
A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group, and the hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.
B11 represents-O-, -S-; -CO-O- -O-CO-, -O-CO-O-, -CO-NR 16 -、-NR 16 -CO-, -CS-, or a single bond. R is R 16 Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B12 and B13 each independently represent-c≡c-, -ch=ch-, -CH 2 -CH 2 -、-O-、-S-、-C(＝O)-、-C(＝O)-O-、-O-C(＝O)-、-O-C(＝O)-O-、-CH＝N-、-N＝CH-、-N＝N-、-C(＝O)-NR 16 -、-NR 16 -C(＝O)-、-OCH 2 -、-OCF 2 -、-CH 2 O-、-CF 2 O-, -ch=ch-C (=o) -O-, -O-C (=o) -ch=ch-, orA single bond.
E11 represents an alkanediyl group having 1 to 12 carbon atoms, wherein the hydrogen atoms contained in the alkanediyl group are optionally substituted by alkoxy groups having 1 to 5 carbon atoms, and wherein the hydrogen atoms contained in the alkoxy groups are optionally substituted by halogen atoms. In addition, the-CH constituting the alkanediyl group 2 -may be replaced by-O-or-CO-.]
The number of carbon atoms of the aromatic hydrocarbon group and the alicyclic hydrocarbon group of a11 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, and particularly preferably 5 or 6. As A11, cyclohexane-1, 4-diyl and 1, 4-phenylene are preferred.
E11 is preferably a linear alkanediyl group having 1 to 12 carbon atoms. -CH constituting the alkanediyl group 2 -can be replaced by-O-.
Specifically, straight-chain alkanediyl having 1 to 12 carbon atoms such as methylene, ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, undecane-1, 11-diyl and dodecane-1, 12-diyl; -CH 2 -CH 2 -O-CH 2 -CH 2 -、-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -and-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -and the like.
As a result of the fact that as B11, preferably-O-, -S-; -CO-O-, -O-CO-, -and of these, -CO-O-is more preferable.
Each of B12 and B13 is independently preferably-O-, -S-, -C (=o) -O-, -O-C (=o) -O-, and, of these, is more preferably-O-or-O-C (=o) -O-.
The polymerizable group represented by P11 is preferably a radical polymerizable group or a cation polymerizable group in view of high polymerization reactivity, particularly photopolymerization reactivity, and the polymerizable group is preferably a group represented by the following formulas (P-11) to (P-15) in view of easy handling and easy production of the liquid crystal compound itself.
[ in the formulae (P-11) to (P-15),
R 17 ～R 21 each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. ]
Specific examples of the group represented by the following formulas (P-11) to (P-15) include groups represented by the following formulas (P-16) to (P-20).
P11 is preferably a group represented by the formulae (P-14) to (P-20), more preferably a vinyl group, a P-stilbene group, an epoxy group or an oxetane group.
The group represented by P11-B11-is more preferably an acryloyloxy group or a methacryloyloxy group.
Examples of the polymerizable liquid crystal compound (Y) include compounds represented by formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI).
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12(I)
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11(II)
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12(III)
P11-B11-E11-B12-A11-B13-A12-B14-A13-F11(IV)
P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12(V)
P11-B11-E11-B12-A11-B13-A12-F11(VI)
(in the formula (I),
a12 to A14 each independently have the same meaning as A11, B14 to B16 each independently have the same meaning as B12, B17 has the same meaning as B11, and E12 has the same meaning as E11.
F11 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, a hydroxymethyl group, a,Formyl, sulfo (-SO) 3 H) Carboxyl, alkoxycarbonyl having 1 to 10 carbon atoms, or halogen atom, and constitutes-CH of the alkyl group or alkoxy group 2 -can be replaced by-O-. )
Specific examples of the polymerizable liquid crystal compound (Y) include compounds having a polymerizable group among compounds described in "3.8.6 network (fully crosslinked)", "6.5.1 liquid crystal material b..polymerizable nematic liquid crystal material" of liquid crystal stool (edited by the liquid crystal stool edit committee, release of charpy (10/30) 2000), and polymerizable liquid crystals described in japanese patent application laid-open nos. 2010-31223, 2010-270108, 2011-6360 and 2011-207765.
Specific examples of the polymerizable liquid crystal compound (Y) include compounds represented by the following formulas (I-1) to (I-4), formulas (II-1) to (II-4), formulas (III-1) to (III-26), formulas (IV-1) to (IV-26), formulas (V-1) to (V-2) and formulas (VI-1) to (VI-6). In the following formula, k1 and k2 each independently represent an integer of 2 to 12. These polymerizable liquid crystal compounds (Y) are preferable in terms of ease of synthesis or ease of acquisition thereof.
By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity, a vertically oriented liquid crystal cured film having a high orientation order can be formed. In the present invention, when a polymerizable liquid crystal compound exhibiting smectic liquid crystal properties is used as the polymerizable liquid crystal compound forming the vertically aligned liquid crystal cured film, the polymerizable liquid crystal compound is more preferably a higher order smectic phase (higher order smectic state) from the viewpoint of achieving a higher alignment order. The higher order smectic phase herein means smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase and smectic L phase, and among these, smectic B phase, smectic F phase and smectic I phase are more preferable. The liquid crystal property may be a thermotropic liquid crystal or a lyotropic liquid crystal, but is preferably a thermotropic liquid crystal in view of enabling precise film thickness control. The polymerizable liquid crystal compound exhibiting smectic liquid crystallinity may be a monomer, or may be an oligomer or polymer obtained by polymerizing a polymerizable group.
The polymerizable liquid crystal compound exhibiting smectic liquid crystallinity is a liquid crystal compound having at least one polymerizable group, and is preferably a liquid crystal compound having 2 or more polymerizable groups from the viewpoint of improving the heat resistance of the vertically aligned liquid crystal cured film. Examples of the polymerizable group include (meth) acryloyloxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, epoxyethyl, and oxetanyl, and among them, (meth) acryloyloxy is preferably contained in view of ease of production, ease of improvement of heat resistance of the vertically oriented liquid crystal cured film, ease of adjustment and improvement of adhesion of the vertically oriented liquid crystal cured film to a horizontally oriented film formed of a polymer having a (meth) acryloyl group, and adhesion to the horizontally oriented liquid crystal cured film via the horizontally oriented film.
Examples of the polymerizable liquid crystal compound exhibiting smectic liquid crystallinity include a compound represented by the following formula (Z) (hereinafter, sometimes referred to as "polymerizable liquid crystal compound (Z)").
U 1z -V 1z -W 1z -(X 1z -Y 1z -) nz -X 2z -W 2z -V 2z -U 2z (Z)
[ in formula (Z), X 1z X is X 2z Independently of each other, a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein a hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and a carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom. Wherein X is 1z X is X 2z At least one of them is a 1, 4-phenylene group which may have a substituent or a cyclohexane-1, 4-diyl group which may have a substituent.
Y 1z Is a single bond or a divalent linking group.
In the case where nz is 1 to 3 and nz is 2 or more, a plurality of X' s 1z May be the same as or different from each other. X is X 2z Can be combined with a plurality of X 1z Either one or all of them may be the same or different. When nz is 2 or more, a plurality of Y' s 1z May be the same as or different from each other. From the viewpoint of liquid crystal property, nz is preferably 2 or more.
U 1z Represents a hydrogen atom or a (meth) acryloyloxy group.
U 2z Represents a polymerizable group.
W 1z W and W 2z Independently of one another, a single bond or a divalent linking group.
V 1z V (V) 2z Independently of each other, may have a substituentAn alkanediyl group having 1 to 20 carbon atoms, and a-CH constituting the alkanediyl group 2 -can be replaced by-O-, -CO-, -S-or NH-.]
In the polymerizable liquid crystal compound (Z), X 1z X is X 2z Independently of one another, 1, 4-phenylene which may have substituents or cyclohexane-1, 4-diyl which may have substituents, X 1z X is X 2z At least one of them is a 1, 4-phenylene group which may have a substituent, or a cyclohexane-1, 4-diyl group which may have a substituent, and is preferably a trans-cyclohexane-1, 4-diyl group. Examples of the substituent which may be optionally contained in the 1, 4-phenylene group which may have a substituent or the cyclohexane-1, 4-diyl group which may have a substituent include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a butyl group, a cyano group, a chlorine atom, a fluorine atom and other halogen atoms. Preferably unsubstituted.
In addition, the polymerizable liquid crystal compound (Z) is preferably a moiety represented by the formula (Z1) in the formula (Z) [ hereinafter referred to as a partial structure (Z1) ] in view of easy occurrence of smectic liquid crystallinity. Is of an asymmetric structure.
-(X 1z -Y 1z -) nz -X 2z -(Z1)
[ in the formula, X 1z 、Y 1z 、X 2z And nz each represents the same meaning as described above. A kind of electronic device
As the polymerizable liquid crystal compound (Z) having an asymmetric partial structure (Z1), for example, there may be mentioned those having nz of 1 and 1X 1z And X is 2z Polymerizable liquid crystal compounds (Z) having different structures from each other. In addition, there may be mentioned 2 as nz and 2Y 1z 2X are compounds of the same structure as each other 1z Is of the same structure as each other, and 1X 2z And 2X 1z A polymerizable liquid crystal compound (Z) having a different structure; 2X 1z W and W in (b) 1z Bonded X 1z With another X 1z X is X 2z Is of a different structure, and another X 1z And X is 2z A polymerizable liquid crystal compound (Z) having the same structure as each other. Further, as nz, 3Y's are mentioned 1z 3X are compounds of the same structure as each other 1z 1X 2z Any 1 of the other 3 is a polymerizable liquid crystal compound (Z) having a structure different from that of the other 3.
Y 1z preferably-CH 2 CH 2 -、-CH 2 O-、-CH 2 CH 2 O-, -COO-, -OCOO-, a single bond, -N=N-, -CR az ＝CR bz -、-C≡C-、-CR az =n-or-CO-NR az -。R az R is R bz Independently of each other, represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y is Y 1z More preferably-CH 2 CH 2 -, -COO-or a single bond, with a plurality of Y's present 1z In the case of (2), with X 2z Bonded Y 1z More preferably-CH 2 CH 2 -or CH 2 O-。X 1z X is X 2z In the case of the same structure, it is preferable that there are at least 2Y's having different bonding modes 1z . There are plural Y's having different bonding modes from each other 1z In the case of (2), the structure is asymmetric, and therefore, the smectic liquid crystallinity tends to be easily exhibited.
U 2z Is the aforementioned polymerizable group. U (U) 1z Is a hydrogen atom or a polymerizable group. The polymerizable group is preferably a (meth) acryloyloxy group in terms of ease of production, ease of improvement of heat resistance of the cured film of a homeotropic alignment liquid crystal, ease of adjustment and improvement of adhesion of the cured film of a homeotropic alignment liquid crystal to the cured film of a homeotropic alignment liquid crystal. The polymerizable group may be polymerized or unpolymerized, and is preferably unpolymerized.
As V 1z V (V) 2z Examples of the alkanediyl group include methylene, ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, decane-1, 10-diyl, tetradecane-1, 14-diyl and eicosane-1, 20-diyl. V (V) 1z V (V) 2z The alkanediyl group having 2 to 12 carbon atoms is preferable, and the alkanediyl group having 6 to 12 carbon atoms is more preferable.
Examples of the substituent optionally contained in the alkanediyl group include a cyano group and a halogen atom, and the alkanediyl group is preferably unsubstituted, more preferably unsubstituted, linear alkanediyl group.
W 1z W and W 2z Independently of one another, preferably a single bond, -O-, -S-, -COO-or OCOO-, more preferably a single bond or-O-.
The polymerizable liquid crystal compound (Z) preferably has a molecular structure asymmetric to the molecular structure, and more specifically, preferably has a partial structure of the following (a-a) to (a-i). From the viewpoint of easy display of high-order smectic liquid crystal property, it is more preferable to have a partial structure of (A-a), (A-b) or (A-c). In the following (a-a) to (a-i), a bond (single bond) is represented.
Specific examples of the polymerizable liquid crystal compound (Z) include compounds represented by the formulae (A-1) to (A-25). When the polymerizable liquid crystal compound (Z) has a cyclohexane-1, 4-diyl group, the cyclohexane-1, 4-diyl group is preferably a trans-form.
Among them, at least 1 selected from the group consisting of the compounds represented by the formula (A-2), the formula (A-3), the formula (A-4), the formula (A-5), the formula (A-6), the formula (A-7), the formula (A-8), the formula (A-13), the formula (A-14), the formula (A-15), the formula (A-16) and the formula (A-17) is preferable. As the polymerizable liquid crystal compound (Z), 1 kind may be used alone, or 2 or more kinds may be used in combination.
The polymerizable liquid crystal compound (Z) can be produced by a known method described in, for example, lub et al, recl.Trav.Chim.Pays-Bas,115, 321-328 (1996), or Japanese patent No. 4719156.
In the present invention, the homeotropic alignment liquid crystal cured film preferably has at least one maximum absorption between wavelengths 300 to 400nm, and the polymerizable liquid crystal compound forming the homeotropic alignment liquid crystal cured film preferably has a maximum absorption wavelength between wavelengths 300 to 400 nm. When the photopolymerization initiator is contained in the polymerizable liquid crystal composition, there is a possibility that the polymerization reaction and gelation of the polymerizable liquid crystal compound may proceed during long-term storage. However, when the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400nm, the generation of reactive species derived from the photopolymerization initiator and the progress of polymerization and gelation of the polymerizable liquid crystal compound due to the reactive species can be effectively suppressed even when exposed to ultraviolet light in a vessel. Therefore, the polymerizable liquid crystal composition is advantageous in terms of long-term stability, and the alignment property and uniformity of film thickness of the obtained liquid crystal cured film can be improved. The maximum absorption wavelength of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer. The solvent is a solvent capable of dissolving the polymerizable liquid crystal compound, and examples thereof include chloroform.
In the laminate in which the vertically oriented liquid crystal cured film and the horizontally oriented liquid crystal cured film are bonded with an adhesive layer, it is considered that the energy ray curable adhesive is advantageous over the pressure sensitive adhesive from the viewpoints of thickness reduction, improvement in bendability, and the like of the laminate. However, when the vertical alignment liquid crystal cured film is formed of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a wavelength of 300 to 400nm and having a very large absorption wavelength, the vertical alignment liquid crystal cured film exhibits absorption in the above-mentioned wavelength region during formation of a laminate containing the vertical alignment liquid crystal cured film, and therefore, it is difficult to laminate the vertical alignment liquid crystal cured film and other layers such as a horizontal alignment liquid crystal cured film with high adhesion by using an ultraviolet curable adhesive curable by light (ultraviolet light) in the above-mentioned wavelength region. The present invention can continuously form a vertically oriented liquid crystal cured film and a horizontally oriented liquid crystal cured film without an adhesive layer, and therefore is advantageous not only in terms of thickness reduction of a laminate, but also in terms of the formation of a laminate, since a polymerizable liquid crystal compound having a large absorption in a wavelength region of 300 to 400nm and exhibiting so-called reverse wavelength dispersibility can be used in the formation of a laminate, and is also advantageous in terms of obtaining a thin laminate having high optical characteristics.
The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition for forming the vertical alignment liquid crystal cured film is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film. In the present invention, the solid content of the polymerizable liquid crystal composition means all components obtained by removing volatile components such as an organic solvent from the polymerizable liquid crystal composition.
The polymerizable liquid crystal composition for forming a homeotropic alignment cured film may further contain additives such as solvents, polymerization initiators, leveling agents, antioxidants, photosensitizers, and the like, in addition to the homeotropic alignment promoters and the polymerizable liquid crystal compounds. These components may be used alone in combination of 1 kind or 2 or more kinds.
The polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film is usually applied to a substrate or the like in a state of being dissolved in a solvent, and therefore, preferably contains a solvent. The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound, and is preferably a solvent inactive to the polymerization reaction of the polymerizable liquid crystal compound. Examples of the solvent include alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ -butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1, 3-dimethyl-2-imidazolidinone. These solvents may be used singly or in combination of two or more. Among them, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents are preferable.
The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content is preferably 2 to 50 parts by mass based on 100 parts by mass of the polymerizable liquid crystal composition. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition becomes low, and thus the film thickness becomes substantially uniform, and unevenness tends to be less likely to occur. The above solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.
The polymerization initiator is a compound which generates a reactive species by heat or light contribution and can initiate polymerization reaction of a polymerizable liquid crystal compound or the like. Examples of the reactive species include reactive species such as a radical, a cation, and an anion. Among them, a photopolymerization initiator that generates radicals by light irradiation is preferable from the viewpoint of easy control of the reaction.
Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzil ketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, oxime compounds, triazine compounds, iodonium salts, and sulfonium salts. Specifically, irgacure 184, irgacure 651, irgacure 819, irgacure 250, irgacure 369, irgacure 379, irgacure 127, irgacure 2959, irgacure 754, irgacure 379EG (manufactured by BASF Japan Co., ltd.), SEIKUOL BZ, SEIKUOL BEE (manufactured by Seikon Chemical Co., ltd.), kayacure BP100 (manufactured by Japanese Chemical Co., ltd.), kayacure I-6992 (manufactured by DOW Co., ltd.), ADEKA OPTOMER SP-152, ADA OPMER SP-170, ADEKA OPMER N-1717, ADEKA OPMER 191N-379, ADP-25, and TAN-3524 (manufactured by Takara Co., ltd.), and TAN-104 (manufactured by TAN-Kagaku Co., ltd.) may be mentioned.
The photopolymerization initiator is preferably a polymerization initiator of α -acetophenone type or an oxime type, and has a maximum absorption wavelength of 300nm to 400nm, more preferably 300nm to 380nm, in order to make full use of energy emitted from a light source and to provide excellent productivity.
Examples of the α -acetophenone compound include 2-methyl-2-morpholino-1- (4-methylthiophenyl) -1-propanone, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl-1-butanone, and 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) -1-butanone, and more preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) -1-propanone and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl-1-butanone. Examples of commercial products of the α -acetophenone compound include Irgacure 369, 379EG, 907 (from BASF Japan, inc., above) and SEIKUOL BEE (from fine chemical company).
The oxime-based photopolymerization initiator generates radicals such as phenyl radicals and methyl radicals by irradiation with light. The polymerization of the polymerizable liquid crystal compound is suitably carried out by the radical, and an oxime-type photopolymerization initiator capable of generating a methyl radical is preferable in view of high initiation efficiency of the polymerization reaction. In addition, from the viewpoint of more efficiently performing the polymerization reaction, it is preferable to use a photopolymerization initiator capable of efficiently utilizing ultraviolet rays having a wavelength of 350nm or more. The photopolymerization initiator capable of efficiently utilizing ultraviolet light having a wavelength of 350nm or more is preferably a triazine compound or a carbazole compound having an oxime structure, and more preferably a carbazole compound having an oxime ester structure from the viewpoint of sensitivity. Examples of the carbazole compound having an oxime structure include 1, 2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl oxime) ], O-acetyl-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (ethanone oxime), and the like. Examples of the commercial products of the oxime ester photopolymerization initiator include Irgacure OXE-01, irgacure OXE-02, irgacure OXE-03 (manufactured by BASF Japan Co., ltd.), ADEKA OPTOMER N-1919, ADEKA ARKLS NCI-831 (manufactured by ADEKA Co., ltd.).
The content of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the alignment of the polymerizable liquid crystal compound is not easily disturbed.
The leveling agent is an additive having a function of adjusting fluidity of the polymerizable liquid crystal composition and flattening a coating film obtained by coating the composition, and examples thereof include silicone-based, polyacrylate-based, and perfluoroalkyl-based leveling agents. As leveling agents, commercially available products can be used, and specifically, examples thereof include DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of the above are Dow Corning Toray Co., ltd), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all of which are manufactured by the surimi chemical industry, inc.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of which are manufactured by Momentive Performance Materials Japan LLC), fluorinert (which is a part of) (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, fluorinert FC-3283 (all of which are manufactured by the surimi chemical industry, inc. 3M, inc., above), MEGAFACE (registered trademark) R-08, MEGAFACE R-30, MEGAFACE R-90, MEGAFACE F-410, 39411-MEGAFACE F-443, MEGAFACE F-445, ef56-470, ef24-477, ef4-479, 4639, and (all of which are manufactured by the top) FC-43, and (all of which are manufactured by the top) are manufactured by the top (all of which are manufactured by the surimi chemical industry, inc. Co 3M, inc., top) R-08, MEGAFACE R, MEGAFACE F-90, MEGAFACE F-410, 39411, 37445-463 (registered trademark) and (registered trademark) are manufactured by the top (top) and top (top) of which are manufactured by the top (top) co. ltd), surflon (registered trademark) S-381, surflon S-382, surflon S-383, surflon S-393, surflon SC-101, surflon SC-105, KH-40, SA-100 (all AGC Seimi Chemical co., ltd., above), trade name E1830, trade name E5844 (Daikin Fine Chemical Kenkyusho, k.k.), BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all trade names: BM Chemie company). The leveling agent may be used alone or in combination of 2 or more.
The content of the leveling agent is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, it is preferable because the polymerizable liquid crystal compound is easily aligned and the resulting liquid crystal cured film tends to be smoother.
By compounding an antioxidant, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. The antioxidant may be a primary antioxidant selected from a phenol-based antioxidant, an amine-based antioxidant, a quinone-based antioxidant and a nitroso-based antioxidant, or may be a secondary antioxidant selected from a phosphorus-based antioxidant and a sulfur-based antioxidant. In order to polymerize the polymerizable liquid crystal compound without disturbing the alignment of the polymerizable liquid crystal compound, the content of the antioxidant is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. The antioxidants may be used alone or in combination of 2 or more.
In addition, by using a photosensitizing agent, the photopolymerization initiator can be made highly sensitive. Examples of the photosensitizing agent include xanthones such as xanthone and thioxanthone; anthracene and anthracene having a substituent such as an alkyl ether; phenothiazine; rubrene (rubrene). The photosensitizers may be used alone or in combination of 2 or more. The content of the photosensitizing agent is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.
The polymerizable liquid crystal composition for forming a cured film of a homeotropic alignment liquid crystal can be obtained by stirring a homeotropic alignment accelerator and a polymerizable liquid crystal compound, and a solvent, a photopolymerization initiator, and other components than the homeotropic alignment accelerator and the polymerizable liquid crystal compound at a predetermined temperature.
In the present invention, the vertically aligned liquid crystal cured film preferably satisfies the following formula (2).
RthC(450)/RthC(550)≤1 (2)
In expression (2), rthC (450) represents a phase difference in the film thickness direction of the vertically oriented liquid crystal cured film at a wavelength of 450nm, and RthC (550) represents a phase difference in the film thickness direction of the vertically oriented liquid crystal cured film at a wavelength of 550 nm. A kind of electronic device
By satisfying the above formula (2), the reduction of the short-wavelength side ellipticity can be suppressed in the laminate including the vertically-aligned liquid crystal cured film, and the oblique reflection hue at the time of black display when the vertically-aligned liquid crystal cured film is applied to a display device can be improved. The value of RthC (450)/RthC (550) in the vertical alignment liquid crystal cured film is more preferably 0.95 or less, still more preferably 0.92 or less, particularly preferably 0.9 or less, and further preferably 0.7 or more, still more preferably 0.75 or more, still more preferably 0.8 or more.
The phase difference value RthC (λ) in the film thickness direction of the vertically oriented liquid crystal cured film can be adjusted by the thickness dC of the vertically oriented liquid crystal cured film. Since the in-plane phase difference value is determined by the following equation, the three-dimensional refractive index and the film thickness dC may be adjusted to obtain the desired phase difference value RthC (λ) in the film thickness direction. The three-dimensional refractive index depends on the molecular structure and the alignment state of the polymerizable liquid crystal compound.
RthC(λ)＝((nxC(λ)+nyC(λ))/2-nzC(λ))×dC
(wherein nxC (λ) represents the in-plane principal refractive index of the vertically aligned liquid crystal cured film at wavelength λnm, nyC (λ) represents the refractive index in the direction orthogonal to nxC (λ) in the in-plane direction at wavelength λnm, nzC (λ) represents the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at wavelength λnm, and nxC (λ) may be set to the refractive index in any direction in the film surface in the case of nxC (λ) = nyC (λ), and dC represents the film thickness of the vertically aligned liquid crystal cured film)
In addition, in the present invention, the vertically oriented liquid crystal cured film is preferably oriented with a high degree of order in the vertical direction of the liquid crystal cured film. In the vertical alignment liquid crystal cured film, the polymerizable liquid crystal compound is aligned with a high degree of order, and thus, when the laminate including the vertical alignment liquid crystal cured film is assembled in an organic EL display device, there is a tendency that the effect of suppressing the change in the oblique reflection hue at the time of black display is excellent. As an index indicating a high alignment state of the polymerizable liquid crystal compound in the vertically aligned liquid crystal cured film and indicating a degree of the oblique optical compensation effect at the time of black display, the vertically aligned liquid crystal cured film preferably satisfies the following formula (5).
-120nm≤RthC(550)≤-30nm (5)
In the formula (5), rthC (550) has the same meaning as described above. The retardation value RthC (550) in the film thickness direction of the vertically oriented liquid crystal cured film is more preferably-100 nm or more, still more preferably-90 nm or more, particularly preferably-80 nm or more, still more preferably-40 nm or less, still more preferably-50 nm or less, from the viewpoint of further improving the oblique reflection hue at the time of black display.
[ horizontal alignment liquid Crystal cured film ]
The horizontally oriented liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in a state of being oriented in a horizontal direction with respect to the plane of the liquid crystal cured film, and is preferably a liquid crystal cured film in which a polymerizable liquid crystal compound having at least one radical polymerizable group is cured in a state of being oriented in a horizontal direction with respect to the in-plane direction of the liquid crystal cured film. In the present invention, the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film means a liquid crystal compound having a polymerizable group, and particularly preferably a liquid crystal compound having at least one radical polymerizable group. When the horizontally oriented liquid crystal cured film is laminated on the vertically oriented liquid crystal cured film via a horizontally oriented film formed using a polymer having a (meth) acryloyl group, the adhesion between the vertically oriented liquid crystal cured film and the horizontally oriented liquid crystal cured film continuously formed via the horizontally oriented film is easily improved if the vertically oriented liquid crystal cured film and the horizontally oriented liquid crystal cured film are both cured with a polymerizable liquid crystal compound having at least one radical polymerizable group. In particular, since the adhesiveness between the cured horizontal alignment liquid crystal film and the cured vertical alignment liquid crystal film tends to be further improved, it is preferable that the polymerizable liquid crystal compound constituting the cured horizontal alignment liquid crystal film and the polymerizable liquid crystal compound constituting the cured vertical alignment liquid crystal film each have a polymerizable group similar to or the same as that of the polymer forming the cured horizontal alignment film, and it is more preferable that the cured horizontal alignment liquid crystal film and the cured vertical alignment liquid crystal film each be composed of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a (meth) acryloyl group.
The polymerizable liquid crystal compound constituting the horizontally oriented liquid crystal cured film is not particularly limited, and for example, a polymerizable liquid crystal compound conventionally known in the field of retardation films can be used. Specifically, a compound represented by the formula (X), (Y) or (Z) exemplified as a polymerizable liquid crystal compound that can be used for forming a vertically aligned liquid crystal cured film can be used, and among them, a polymerizable liquid crystal compound that exhibits so-called reverse wavelength dispersibility is preferable, and for example, a compound represented by the formula (X) described above can be preferably used. In the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film, the polymerizable liquid crystal compound may be used alone or in combination of 2 or more.
The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition for forming the horizontally oriented liquid crystal cured film is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film.
The polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film may further contain additives such as solvents, polymerization initiators, leveling agents, antioxidants, photosensitizers, and the like, in addition to the polymerizable liquid crystal compound. As these components, the same components as those exemplified above as components usable in the vertical alignment liquid crystal cured film may be used, and each may be used in the form of 1 or 2 or more kinds.
The polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film can be obtained by stirring a polymerizable liquid crystal compound, a solvent, a photopolymerization initiator, and other components than the polymerizable liquid crystal compound at a predetermined temperature.
In the present invention, it is preferable that the horizontally oriented liquid crystal cured film has at least one maximum absorption at a wavelength of 300 to 400nm, for the same reason that it is advantageous for the vertically oriented liquid crystal cured film to have at least one maximum absorption at a wavelength of 300 to 400 nm. In a preferred embodiment of the present invention, the vertically oriented liquid crystal cured film and the horizontally oriented liquid crystal cured film each have at least one maximum absorption at a wavelength of 300 to 400 nm.
In the present invention, the horizontally oriented liquid crystal cured film preferably satisfies the following formula (1).
ReA(450)/ReA(550)≤1 (1)
[ in formula (1), reA (λ) represents the in-plane phase difference value of the horizontally oriented liquid crystal cured film at wavelength λnm, reA (λ) = (nxA (λ) -nyA (λ)). Times.dA (in the formula, nxA (λ) represents the principal refractive index at wavelength λnm in the plane of the horizontally oriented liquid crystal cured film, nyA (λ) represents the refractive index at wavelength λnm in the direction orthogonal to the direction of nxA in the same plane as nxA, dA represents the film thickness of the horizontally oriented liquid crystal cured film) ]
In the case where the horizontally oriented liquid crystal cured film satisfies the formula (1), the horizontally oriented liquid crystal cured film exhibits so-called reverse wavelength dispersibility, that is, an in-plane phase difference value at a short wavelength is smaller than an in-plane phase difference value at a long wavelength. By combining such a horizontally oriented liquid crystal cured film with the above-described vertically oriented liquid crystal cured film, a laminate excellent in improvement effect of front and oblique reflection hues at the time of black display in the case of being incorporated in an organic EL display device can be obtained. In order to improve the reverse wavelength dispersibility and further enhance the effect of improving the reflection hue in the front direction of the horizontally oriented liquid crystal cured film, the ratio of ReA (450)/ReA (550) is preferably 0.70 or more, more preferably 0.78 or more, and further preferably 0.95 or less, more preferably 0.92 or less.
The in-plane retardation value can be adjusted by the thickness dA of the horizontally oriented liquid crystal cured film. Since the in-plane phase difference value is determined by the above-mentioned ratio of re (λ) = (nxA (λ) -nyA (λ)) ×da, the three-dimensional refractive index and film thickness dA may be adjusted to obtain a desired in-plane phase difference value (re (λ): in-plane phase difference value of the horizontally oriented liquid crystal cured film at wavelength λ (nm)).
In addition, the horizontally oriented liquid crystal cured film preferably satisfies the following formula (6).
120nm≤ReA(550)≤170nm (6)
[ in formula (6), reA (lambda) has the same meaning as described above ]
When the in-plane retardation ReA (550) of the horizontally oriented liquid crystal cured film is within the range of formula (6), the effect of improving the front reflection hue in the case of applying a laminate (elliptical polarizing plate) containing the horizontally oriented liquid crystal cured film to black display in an organic EL display device becomes remarkable. A more preferred range of in-plane phase difference values is 130 nm.ltoreq.ReA (550). Ltoreq.150 nm.
[ horizontal alignment film ]
The horizontal alignment film constituting the laminate of the present invention is a photo-alignment film formed of a polymer having a (meth) acryloyl group. The horizontal alignment film has a horizontal alignment control force for aligning the polymerizable liquid crystal compound in the horizontal direction with respect to the plane of the coating film. The orientation control force can be arbitrarily adjusted by the kind of the orientation film, the surface state, the rubbing condition, etc., and the photo-orientation film formed of the photo-alignment polymer can be arbitrarily adjusted by the polarized light irradiation condition, etc. In the present invention, a vertically oriented liquid crystal cured film is formed on a substrate, and further a horizontally oriented film is formed thereon, and a horizontally oriented liquid crystal cured film is formed thereon, but in this case, there is a tendency that the orientation of the horizontally oriented liquid crystal cured film is easily deteriorated. The reason is not definite, but it is presumed that: the surface energy is reduced by additives such as leveling agents contained in the vertically oriented liquid crystal cured film, and the alignment properties of the liquid crystal compound are easily impaired when the horizontally oriented liquid crystal cured film is formed on the upper layer. In particular, in the case of forming a homeotropic alignment liquid crystal cured film in such a manner that no homeotropic alignment film is formed, an alignment accelerator is also included, and thus the influence thereof becomes more remarkable. Therefore, the liquid crystal alignment property at the time of forming the vertical alignment liquid crystal cured film is easily affected depending on the kind, thickness, and the like of the horizontal alignment film.
In the case where the horizontal alignment film has a polymerizable group similar to or the same as the polymerizable liquid crystal compound constituting the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film, the adhesion between the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film tends to be further improved through the horizontal alignment film, and therefore, it is preferable that the horizontal alignment film is formed of a polymer having a (meth) acryloyl group, and that both the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are formed of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a (meth) acryloyl group.
The photo-alignment film can be generally obtained by: a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as a "composition for forming a photoalignment film") is applied to a substrate, and after the solvent is removed, polarized light (preferably polarized UV light) is irradiated. The photo-alignment film is also advantageous in that the direction of the alignment control force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.
The photoreactive group is a group that generates liquid crystal aligning ability by irradiation with light. Specifically, examples thereof include photoreactive groups that are involved in the alignment induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, photodecomposition reaction, or the like of molecules generated by light irradiation and that are sources of liquid crystal alignment ability. Among them, a group participating in dimerization reaction or photocrosslinking reaction is preferable in view of excellent orientation. The photoreactive group is preferably a group having an unsaturated bond, particularly a double bond, and particularly preferably a group having at least one selected from the group consisting of a carbon-carbon double bond (c=c bond), a carbon-nitrogen double bond (c=n bond), a nitrogen-nitrogen double bond (n=n bond), and a carbon-oxygen double bond (c=o bond).
Examples of the photoreactive group having a c=c bond include a vinyl group, a polyalkenyl group, a stilbene azole group (stilbene azole group), a stilbene azole onium group (stilbazolium group), a chalcone group, and a cinnamoyl group. Examples of the photoreactive group having a c=n bond include a group having a structure such as an aromatic schiff base or an aromatic hydrazone. Examples of the photoreactive group having an n=n bond include an azo phenyl group, an azo naphthyl group, an aromatic heterocyclic azo group, a disazo group, a formazan (formazan) group, a group having an azobenzene oxide structure, and the like. Examples of the photoreactive group having a c=o bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, haloalkyl, and the like.
Among them, the photoreactive group involved in the photopolymerization reaction is preferable, and azo groups, cinnamoyl groups, and chalcone groups are preferable in terms of the light irradiation amount of the polarized light required for the photo-alignment is small, and the photo-alignment film excellent in thermal stability and temporal stability is easily obtained. The polymer having a photoreactive group is preferably a polymer having an azo group or a cinnamoyl group, and particularly preferably a polymer having a cinnamoyl group such that the terminal portion of the polymer side chain has a cinnamic acid structure, from the viewpoint of improving adhesion between the horizontally oriented film and the vertically oriented liquid crystal cured film and between the polymer side chain and the horizontally oriented liquid crystal cured film.
The solvent that can be contained in the composition for forming a photo-alignment film includes the same solvents as those exemplified above as solvents that can be used in the polymerizable liquid crystal composition, and may be appropriately selected according to the solubility of the polymer or monomer having a photoreactive group.
The content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film may be appropriately adjusted according to the kind of the polymer or monomer and the thickness of the photoalignment film to be targeted, and is preferably set to be at least 0.2 mass%, more preferably in the range of 0.3 to 10 mass% relative to the mass of the composition for forming a photoalignment film. The composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, and a photosensitizing agent, so long as the properties of the photo-alignment film are not significantly impaired.
The thickness of the horizontal alignment film (photo alignment film) is usually 10 to 5000nm, preferably 100 to 1000nm, more preferably 100 to 500nm, still more preferably 100 to 300nm, particularly preferably 100 to 250nm. When the thickness of the alignment film is within the above range, the alignment film has a sufficient horizontal alignment control force, and cohesive failure is less likely to occur in the alignment film in the laminate.
[ substrate ]
Examples of the substrate constituting the laminate of the present invention include a glass substrate and a film substrate, but a resin film substrate is preferable from the viewpoint of processability. Examples of the resin constituting the film base material include polyolefin such as polyethylene, polypropylene, and norbornene polymer; a cyclic olefin resin; polyvinyl alcohol; polyethylene terephthalate; a polymethacrylate; a polyacrylate; cellulose esters such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate; polyethylene naphthalate; a polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyphenylene sulfide and polyphenylene ether. Such a resin can be formed into a film by a known means such as a solvent casting method or a melt extrusion method to prepare a substrate. The surface of the substrate may be subjected to surface treatments such as a mold release treatment such as a silicone treatment, a corona treatment, and a plasma treatment.
As the base material, a commercially available product can be used. Examples of the commercially available cellulose ester substrate include cellulose ester substrates manufactured by Fuji Photo Film, such as fujittack Film; cellulose ester substrates manufactured by KONICA MINOLTA Opto corporation such as "KC8UX2M", "KC8UY", and "KC4UY", and the like. Examples of the commercially available cycloolefin resin include cycloolefin resins manufactured by Ticona corporation (Germany) such as "Topas (registered trademark)"; a cycloolefin resin manufactured by JSR corporation such as "ARTON (registered trademark)"; a cyclic olefin resin manufactured by Zeon corporation such as "ZEONOR (registered trademark)", and "ZEONEX (registered trademark)"; a cycloolefin resin such as "Apel" (registered trademark) manufactured by Mitsui chemical Co., ltd. Commercially available cycloolefin resin base materials can also be used. Examples of the commercially available cycloolefin resin base material include cycloolefin resin base materials manufactured by Seattle chemical industries, inc., such as "Escena (registered trademark)" and "SCA40 (registered trademark)"; a cycloolefin resin base material manufactured by OPTES Co., ltd. "ZEONORFILM (registered trademark)"; a cycloolefin resin base material manufactured by JSR corporation, such as "ARTONFILM (registered trademark)".
In the present invention, the substrate is preferably a substrate that can be finally peeled from the laminate of the present invention, and for example, an elliptical polarizing plate can be obtained by bonding a vertically oriented liquid crystal cured film of the laminate from which the substrate has been peeled to a polarizing film via an adhesive layer.
The thickness of the base material is usually 5 to 300. Mu.m, preferably 10 to 150. Mu.m, from the viewpoints of the thickness reduction of the laminate, the easiness of peeling of the base material, the operability of the base material, and the like.
The laminate of the present invention may contain layers other than the base material, the vertically oriented liquid crystal cured film, the horizontally oriented film, and the horizontally oriented liquid crystal cured film within a range that does not affect the effects of the present invention. Examples of such other layers include a cured resin layer, a hard coat layer, and an undercoat layer for the purpose of improving solvent resistance of a base material or improving or enhancing mechanical strength of a liquid crystal cured film. For example, the substrate and the vertical alignment liquid crystal cured film may be laminated via a layer having no vertical alignment control force, and the vertical alignment liquid crystal cured film and the horizontal alignment film may be laminated via a layer having no vertical alignment control force (excluding an adhesive layer).
The cured resin layer may be formed of, for example, an acrylic resin, a methacrylic resin, an epoxy resin, an oxetane resin, a urethane resin, a melamine resin, or the like. By providing the cured resin layer, the solvent resistance of the base material can be improved, or even if the vertically oriented liquid crystal cured film formed adjacent to the cured resin layer is a thin film, the cured resin layer can serve as a protective layer or a reinforcing layer to sufficiently compensate for the strength of the vertically oriented liquid crystal cured film.
When the laminate of the present invention includes another layer such as the cured resin layer, the thickness of the other layer may be appropriately determined according to the purpose and type of the layer to be provided, and is preferably 0.1 to 10.0 μm, more preferably 0.3 to 5.0 μm.
[ method for producing laminate ]
The laminate of the present invention can be produced, for example, by a production method comprising the following steps in order:
a step of forming a coating film of a polymerizable liquid crystal composition for forming a cured film of a homeotropic alignment liquid crystal containing a polymerizable liquid crystal compound (hereinafter, also referred to as "cured film forming step of homeotropic alignment liquid crystal");
a step of forming a coating film of the composition for forming a horizontal alignment film (hereinafter, also referred to as "horizontal alignment film forming step") from the coating film; the method comprises the steps of,
a step of forming a coating film of the polymerizable liquid crystal composition for forming a cured film of a horizontally oriented liquid crystal containing a polymerizable liquid crystal compound, and forming a cured film of a horizontally oriented liquid crystal from the coating film (hereinafter, also referred to as "cured film forming step of a horizontally oriented liquid crystal").
In the laminate of the present invention, when the vertically oriented liquid crystal cured film and the horizontally oriented liquid crystal cured film are adjacent to each other, the vertically oriented liquid crystal cured film forming step, the horizontally oriented film forming step, and the vertically oriented liquid crystal cured film forming step are preferably performed sequentially and continuously.
In the vertical alignment liquid crystal cured film forming step, the vertical alignment liquid crystal cured film can be produced, for example, by a method including the steps of:
a step of coating a substrate with a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film to obtain a coating film;
a step of drying the coating film to form a dried coating film; the method comprises the steps of,
and a step of irradiating the dried coating film with an active energy ray to form a vertically oriented liquid crystal cured film.
The formation of the coating film of the polymerizable liquid crystal composition can be performed, for example, as follows: the polymerizable liquid crystal composition for forming a cured film of a homeotropic alignment liquid crystal is applied onto a substrate, onto another layer such as a cured resin layer having no homeotropic alignment controlling force provided on the substrate, or the like.
Examples of the method of applying the polymerizable liquid crystal composition to a substrate or the like include known methods such as spin coating, extrusion, gravure coating, die coating, bar coating, coater or the like, and printing such as flexography.
Next, the solvent is removed by drying or the like to form a dried coating film. Examples of the drying method include a natural drying method, a ventilation drying method, a heat drying method, and a reduced pressure drying method. In this case, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent can be removed from the coating film by drying, and the polymerizable liquid crystal compound can be oriented in a direction perpendicular to the plane of the coating film. The heating temperature of the coating film can be appropriately determined in consideration of the material of the polymerizable liquid crystal compound used, the substrate on which the coating film is to be formed, and the like, but in order to change the phase of the polymerizable liquid crystal compound into the liquid crystal phase state, a temperature equal to or higher than the liquid crystal phase transition temperature is generally required. In order to bring the polymerizable liquid crystal compound into a homeotropic state while removing the solvent contained in the polymerizable liquid crystal composition, for example, the polymerizable liquid crystal composition may be heated to a temperature in the vicinity of or above the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition.
The liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature adjustment stage, a Differential Scanning Calorimeter (DSC), a thermogravimetric differential thermal analysis apparatus (TG-DTA), or the like. In the case where 2 or more kinds of polymerizable liquid crystal compounds are used in combination, the phase transition temperature means: the temperature of the mixture of the polymerizable liquid crystal compounds obtained by mixing all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition at the same ratio as the composition in the polymerizable liquid crystal composition was measured in the same manner as in the case of using 1 polymerizable liquid crystal compound. It is known that the following cases are also generally present: the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition is lower than that of the polymerizable liquid crystal compound monomer.
The heating time is appropriately determined depending on the heating temperature, the kind of the polymerizable liquid crystal compound to be used, the kind of the solvent, the boiling point thereof, the amount thereof, and the like, and is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.
The solvent may be removed from the coating film simultaneously with or independently from the heating at a temperature equal to or higher than the phase transition temperature of the polymerizable liquid crystal compound to the liquid crystal phase, but is preferably simultaneously from the viewpoint of improving productivity. Before heating the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature, a pre-drying step for appropriately removing the solvent in the coating film under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition is not polymerized may be provided. Examples of the drying method in the pre-drying step include a natural drying method, a ventilation drying method, a heating drying method, and a reduced pressure drying method, and the drying temperature (heating temperature) in the drying step can be appropriately determined according to the type of the polymerizable liquid crystal compound to be used, the type of the solvent, the boiling point thereof, the amount thereof, and the like.
Next, in the obtained dry coating film, the polymerizable liquid crystal compound is polymerized while maintaining the vertically aligned state of the polymerizable liquid crystal compound, thereby forming a vertically aligned liquid crystal cured film. The polymerization method may be a thermal polymerization method or a photopolymerization method, but the photopolymerization method is preferable from the viewpoint of easy control of the polymerization reaction. In photopolymerization, the light to be irradiated to the dry coating film may be appropriately selected depending on the kind of the polymerization initiator contained in the dry coating film, the kind of the polymerizable liquid crystal compound (particularly, the kind of the polymerizable group contained in the polymerizable liquid crystal compound), and the amount thereof. Specific examples thereof include 1 or more light and active electron rays selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α -rays, β -rays and γ -rays. Among them, ultraviolet light is preferable from the viewpoint of easy control of the progress of polymerization reaction and the use of a device widely used in the art as a photopolymerization device, and the types of the polymerizable liquid crystal compound and the polymerization initiator contained in the polymerizable liquid crystal composition are preferably selected in advance so that photopolymerization can be performed by ultraviolet light. In addition, in the polymerization, the polymerization temperature can be controlled by cooling the dried coating film by an appropriate cooling means and simultaneously irradiating the film with light. If the polymerization of the polymerizable liquid crystal compound is carried out at a lower temperature by using such a cooling means, a vertically aligned liquid crystal cured film can be suitably formed even if a substrate having low heat resistance is used. In addition, the polymerization reaction can be accelerated by increasing the polymerization temperature within a range where defects due to heat at the time of light irradiation (deformation of the base material due to heat, etc.) do not occur. In photopolymerization, a patterned cured film can also be obtained by masking, developing, or the like.
Examples of the light source of the active energy ray include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, an LED light source that emits light in a wavelength range of 380 to 440nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.
The intensity of the ultraviolet irradiation is usually 10 to 3,000mW/cm 2 . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activation of the photopolymerization initiator. The time for irradiation of light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and still more preferably 0.1 seconds to 1 minute. When the ultraviolet irradiation intensity is applied for 1 or more times, the cumulative light amount is 10 to 3,000mJ/cm 2 Preferably50 to 2,000mJ/cm 2 More preferably 100 to 1,000mJ/cm 2 。
The thickness of the vertically oriented liquid crystal cured film may be appropriately selected depending on the display device to be used, and is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm. The vertical alignment liquid crystal cured film is more preferably 0.2 to 1 μm in the case of positive wavelength dispersibility, and is more preferably 0.4 to 2 μm in the case of reverse wavelength dispersibility.
In the horizontal alignment film forming step, the photo-alignment film can be obtained, for example, by: the composition for forming a photo-alignment film is applied to a cured film of a homeotropic liquid crystal, and after removing the solvent, polarized light (preferably polarized UV light) is irradiated.
As a method of applying the composition for forming a photo-alignment film to a cured film of a homeotropic alignment liquid crystal, the same method as a method of applying the composition for forming a cured film of a homeotropic alignment liquid crystal to a substrate or the like can be mentioned. Examples of the method for removing the solvent from the composition for forming a coated photo-alignment film include a natural drying method, a ventilation drying method, a heat drying method, and a reduced pressure drying method.
In the case of irradiating polarized light, polarized UV light may be directly irradiated to a product obtained by removing a solvent from a coating film of the composition for forming a photo-alignment film, or polarized light may be irradiated from the side of a cured film of a vertically aligned liquid crystal (substrate side) and transmitted therethrough. In addition, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the irradiated polarized light is preferably a wavelength in a wavelength region where the photoreactive group of the polymer or monomer having the photoreactive group can absorb light energy. Specifically, UV (ultraviolet) having a wavelength in the range of 250 to 400nm is particularly preferable. Examples of the light source used for the polarized light irradiation include ultraviolet light lasers such as xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, krF, arF, and the like, and more preferably high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps. Among them, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because of the high emission intensity of ultraviolet rays having a wavelength of 313 nm. The polarized UV light can be irradiated by passing light from the aforementioned light source through an appropriate polarizer for irradiation. As the polarizer, a polarizing prism such as a polarizing filter, a gram-thompson, a gram-taylor, or a wire grid type polarizer can be used.
When the polarized light irradiation is performed, a plurality of regions (patterns) having different directions of alignment of the liquid crystal can be formed by masking.
In the horizontally oriented liquid crystal cured film forming step, the horizontally oriented liquid crystal cured film can be produced, for example, by a method including the steps of:
a step of applying a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film to the horizontal alignment film to obtain a coating film;
a step of drying the coating film to form a dried coating film; the method comprises the steps of,
and a step of irradiating the dried coating film with an active energy ray to form a horizontally oriented liquid crystal cured film.
The formation of the coating film of the polymerizable liquid crystal composition can be performed by, for example, applying the polymerizable liquid crystal composition for forming a cured film of a horizontal alignment liquid crystal onto the horizontal alignment film. The method of coating the polymerizable liquid crystal composition may be the same as that which can be used for the method of producing a vertically aligned liquid crystal cured film.
Next, the solvent is removed by drying or the like to form a dried coating film. Examples of the drying method include a natural drying method, a ventilation drying method, a heat drying method, and a reduced pressure drying method. In view of productivity, the heating and drying are preferable, and in this case, the heating temperature is preferably a temperature equal to or higher than the phase transition temperature of the polymerizable liquid crystal compound, while removing the solvent. The steps and conditions in the above-mentioned steps include the same steps and conditions as those which can be employed in the method for producing a vertically aligned liquid crystal cured film.
The obtained dry coating film is irradiated with active energy rays (more specifically, ultraviolet rays or the like), and the polymerizable liquid crystal compound is polymerized while being oriented in a horizontal direction with respect to the plane of the coating film, thereby forming a horizontally oriented liquid crystal cured film. The polymerization method may be the same as that which can be used for the production method of the vertically aligned liquid crystal cured film.
The thickness of the horizontally oriented liquid crystal cured film may be appropriately selected depending on the display device to be used, and is preferably 0.2 to 5. Mu.m, more preferably 0.2 to 4. Mu.m, still more preferably 0.2 to 3. Mu.m.
In the present invention, the homeotropic alignment liquid crystal cured film is formed of the polymerizable liquid crystal composition containing the homeotropic alignment accelerator, whereby the homeotropic alignment liquid crystal cured film having no alignment defect or few alignment defects can be obtained even if the homeotropic alignment film is not used. The laminate of the present invention including such a vertically oriented liquid crystal cured film and a horizontally oriented liquid crystal cured film tends to be excellent in optical characteristics, and particularly in the case of application to an organic EL display device, the effect of suppressing changes in front and oblique reflection hues during black display is excellent. In addition, since a process for forming a vertical alignment film is not required, the method is advantageous in terms of productivity and production cost.
[ elliptical polarizing plate ]
The present invention includes an elliptical polarizing plate comprising the laminate of the present invention and a polarizing film.
Examples of the polarizing film include a film having a polarizing function, a stretched film having a dye having absorption anisotropy adsorbed thereon, and a film containing a film coated with a dye having absorption anisotropy as a polarizer. Examples of the dye having absorption anisotropy include dichromatic dyes.
As for a film containing a stretched film to which a pigment having absorption anisotropy is adsorbed as a polarizer, it is common to manufacture a film by sandwiching at least one surface of a polarizer manufactured by the following process with a transparent protective film via an adhesive: a step of uniaxially stretching a polyvinyl alcohol resin film; a step of dyeing a polyvinyl alcohol resin film with a dichroic dye to adsorb the dichroic dye; a step of treating the polyvinyl alcohol resin film having the dichromatic pigment adsorbed thereto with an aqueous boric acid solution; and a step of washing with water after the treatment with the aqueous boric acid solution.
The polyvinyl alcohol resin is obtained by saponifying a polyvinyl acetate resin. As the polyvinyl acetate-based resin, a copolymer of vinyl acetate and other monomers copolymerizable therewith may be used in addition to polyvinyl acetate which is a homopolymer of vinyl acetate. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
The saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The polymerization degree of the polyvinyl alcohol resin is usually about 1,000 to 10,000, preferably 1,500 to 5,000.
A film made of such a polyvinyl alcohol resin can be used as a green film (japanese: raw film ) of a polarizing film. The method for forming the polyvinyl alcohol resin into a film is not particularly limited, and the film can be formed by a known method. The thickness of the polyvinyl alcohol-based green film may be, for example, about 10 to 150. Mu.m.
The uniaxial stretching of the polyvinyl alcohol resin film may be performed before dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing. In the case of uniaxial stretching after dyeing, the uniaxial stretching may be performed before boric acid treatment or may be performed in boric acid treatment. In addition, uniaxial stretching may be performed in a plurality of stages among them. In the case of uniaxial stretching, uniaxial stretching may be performed between rolls having different peripheral speeds, or uniaxial stretching may be performed using a hot roll. The uniaxial stretching may be a dry stretching in which stretching is performed in the atmosphere, or a wet stretching in which stretching is performed in a state in which a polyvinyl alcohol resin film is swollen with a solvent. The stretching ratio is usually about 3 to 8 times.
Dyeing of the polyvinyl alcohol resin film with the dichromatic pigment can be performed, for example, by immersing the polyvinyl alcohol resin film in an aqueous solution containing the dichromatic pigment.
As the dichroic dye, specifically, iodine or a dichroic organic dye can be used. Examples of the organic dye having dichroism include a dichroism direct dye formed of a disazo compound such as c.i. direct red (DIRECT RED) 39, and a dichroism direct dye formed of a compound such as trisazo or tetraazo. The polyvinyl alcohol resin film is preferably immersed in water before the dyeing treatment.
When iodine is used as the dichromatic pigment, a method of immersing a polyvinyl alcohol resin film in an aqueous solution containing iodine and potassium iodide to dye the film can be generally employed. The iodine content in the aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. The content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40 ℃. The immersion time (dyeing time) for immersing in the aqueous solution is usually about 20 to 1,800 seconds.
On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of immersing a polyvinyl alcohol resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing the film is generally employed. The content of the dichroic organic dye in the aqueous solution is usually 1×10 relative to 100 parts by mass of water -4 About 10 parts by mass, preferably 1X 10 -3 About 1 part by mass, more preferably 1X 10 -3 ～1×10 -2 Mass parts. The aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The temperature of the aqueous solution of the dichroic dye used for dyeing is usually about 20 to 80 ℃. The immersion time (dyeing time) in the aqueous solution is usually about 10 to 1,800 seconds.
Boric acid treatment after dyeing with a dichroic dye can be generally performed by immersing the dyed polyvinyl alcohol resin film in an aqueous boric acid solution. The boric acid content in the aqueous boric acid solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. When iodine is used as the dichromatic pigment, the aqueous boric acid solution preferably contains potassium iodide, and the content of potassium iodide in this case is usually about 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass, relative to 100 parts by mass of water. The immersion time in the aqueous boric acid solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid treatment is usually 50℃or higher, preferably 50 to 85℃and more preferably 60 to 80 ℃.
In general, the polyvinyl alcohol resin film after boric acid treatment may be subjected to a water washing treatment. The water-washing treatment may be performed, for example, by immersing the boric acid-treated polyvinyl alcohol resin film in water. The temperature of water in the water washing treatment is usually about 5 to 40 ℃. The immersion time is usually about 1 to 120 seconds.
The polarizer may be obtained by performing a drying process after washing with water. The drying treatment may be performed using, for example, a hot air dryer or a far infrared heater. The drying treatment temperature is usually about 30 to 100 ℃, preferably 50 to 80 ℃. The drying time is usually about 60 to 600 seconds, preferably 120 to 600 seconds. Through the drying treatment, the water ratio of the polaroid can be reduced to a practical degree. The water content is usually about 5 to 20% by mass, preferably 8 to 15% by weight. When the moisture content is less than 5% by mass, the flexibility of the polarizer is lost, and after the polarizer is dried, it may be damaged or broken. In addition, when the water content is more than 20 mass%, there is a possibility that the heat stability of the polarizer may be deteriorated.
The thickness of the polarizer obtained by uniaxially stretching the polyvinyl alcohol resin film, dyeing with a dichroic dye, boric acid treatment, washing with water, and drying as described above is preferably 5 to 40 μm.
Examples of the film coated with the dye having absorption anisotropy include a film obtained by coating a composition containing a dichroic dye having liquid crystallinity, or a composition containing a dichroic dye and a polymerizable liquid crystal. The film preferably has a protective film on one or both sides thereof. The protective film may be the same as the resin film exemplified above as a base material usable for producing the vertical alignment liquid crystal cured film.
The thinner the film coated with the pigment having absorption anisotropy is, the more preferable, but if it is too thin, the strength tends to be low, and the workability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, more preferably 0.5 to 3 μm.
The film coated with the pigment having absorption anisotropy is specifically a film described in japanese patent application laid-open No. 2012-33249.
On at least one surface of the polarizer obtained as described above, a transparent protective film may be laminated via an adhesive layer, for example. As the transparent protective film, the same transparent film as the resin film exemplified in the foregoing as a base material usable in the production of the vertical alignment liquid crystal cured film can be used.
The elliptical polarizing plate of the present invention is configured to include the laminate of the present invention, or a laminate obtained by removing a base material from the laminate of the present invention, and a polarizing film, and for example, the laminate of the present invention and the polarizing film may be laminated via an adhesive layer or the like to obtain the elliptical polarizing plate of the present invention. The elliptical polarizing plate of the present invention can be obtained by bonding a laminate obtained by removing the base material from the laminate of the present invention to a polarizing film.
In one embodiment of the present invention, when the laminate of the present invention and the polarizing film are laminated, it is preferable that the laminate be laminated such that an angle between a slow axis (optical axis) of the horizontally oriented liquid crystal cured film constituting the laminate and an absorption axis of the polarizing film is 45±5°.
The elliptical polarizing plate of the present invention may have a configuration similar to that of a conventional elliptical polarizing plate, or that of a polarizing film and a retardation film. Examples of such a structure include an adhesive layer (sheet) for bonding an elliptical polarizing plate to a display element such as an organic EL, a protective film used for protecting the surface of a polarizing film or a liquid crystal cured film from damage or contamination, and the like.
The laminate and the elliptical polarizing plate of the present invention can be used for various display devices.
The display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. Examples of the display device include a liquid crystal display device, an organic Electroluminescence (EL) display device, an inorganic Electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, an electric field emission display device (FED), a surface electric field emission display device (SED)), an electronic paper (a display device using an electronic ink, an electrophoretic element, a plasma display device, a projection display device (for example, a Grating Light Valve (GLV) display device, a display device having a Digital Micromirror Device (DMD)), and a piezoelectric ceramic display device).
Examples
Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise specified, "%" and "parts" in examples refer to mass% and mass parts, respectively.
1. Example 1
(1) Preparation of composition for Forming horizontal alignment film
5 parts by mass (weight average molecular weight: 30000) of a photo-alignment material having the following structure and 95 parts by mass of cyclopentanone (solvent) were mixed as components, and the resultant mixture was stirred at 80℃for 1 hour, thereby obtaining a composition for forming a horizontal alignment film.
(2) Preparation of polymerizable liquid Crystal Compound
The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) each having the following molecular structures were prepared. The polymerizable liquid crystal compound (X1) is produced by the method described in JP-A2010-31223. The polymerizable liquid crystal compound (X2) is produced by the method described in japanese patent application laid-open No. 2009-173893.
Polymerizable liquid crystal compound (X1)
Polymerizable liquid crystal compound (X2)
1mg of the polymerizable liquid crystal compound (X1) was dissolved in 50mL of tetrahydrofuran to obtain a solution. The solution obtained as the measurement sample was placed in a measurement cuvette having an optical path length of 1cm, the measurement sample was set in an ultraviolet-visible spectrophotometer (UV-2450 manufactured by Shimadzu corporation), and the absorption spectrum was measured, and the wavelength of the maximum absorbance was read from the obtained absorption spectrum, whereby the maximum absorption wavelength lambda was in the range of 300 to 400nm max 350nm.
(3) Preparation of polymerizable liquid Crystal composition for Forming horizontal alignment liquid Crystal cured film
For a polymerizable liquid crystal compound LC242 represented by the following formula (LC 242): paliocolar LC242 (registered trademark of BASF corporation), 0.1 part by mass of a leveling agent (product of DIC corporation "F-556") and 3 parts by mass of a polymerization initiator Irg369 were added. Further, cyclopentanone was added so that the solid content concentration became 13%, and these were mixed, thereby obtaining a polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film.
LC242: paliocolar lc242 (registered trademark of BASF corporation)
(4) Preparation of polymerizable liquid Crystal composition for Forming vertical alignment liquid Crystal cured film
To 100 parts by mass of the liquid crystal compound (X2), 0.25 part by mass of a leveling agent "F-556" (manufactured by DIC corporation), 2.0 parts by mass of an ionic compound A (molecular weight: 645) prepared with reference to Japanese patent application laid-open No. 2016-514802, 0.5 part by mass of a silane coupling agent "KBE-9103" (manufactured by Xinyue chemical industries Co., ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (BASF Japan corporation "Irgacure (registered trademark) 369 (Irg 369)") as a photopolymerization initiator were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80℃for 1 hour, thereby obtaining a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film.
Ionic compound a:
(5) Preparation of a substrate
A solution was prepared in which 50 parts by mass of dipentaerythritol hexaacrylate (multifunctional acrylate manufactured by ARONIX M-403 Toyama Synthesis Co., ltd.), 50 parts by mass of acrylate resin (Ebecryl 4858Daicel UCB Co., ltd.), 3 parts by mass of 2-methyl-1- [4- (methylsulfanyl) phenyl ] -2-morpholino-1-propanone (manufactured by Irgacure 907;Ciba Specialty Chemicals Co.) were dissolved in 250 parts by mass of isopropanol to obtain a composition for forming a cured resin layer containing an acrylate compound.
Next, the composition for forming a cured resin layer was applied to a TAC film (KC 4 UY) manufactured by KONICA MINOLTA Co., ltd.) by using a bar coater, and dried at 50℃for 1 minute. Thereafter, a high pressure mercury lamp ("Unicure VB-15201BY-A", ushio motor was usedManufactured by co., ltd.) was irradiated with ultraviolet light (cumulative light amount at 365nm wavelength under nitrogen atmosphere: 400mJ/cm 2 ) Thereby forming a cured resin layer. The film thickness of the obtained cured resin layer was measured by a contact film thickness meter and found to be 2.0. Mu.m. At this time, the retardation value Re550 of the laminate of the TAC film and the cured resin layer was measured using "KOBA-WPR" manufactured by Wako measuring instruments Co., ltd. And then the retardation value Re550 derived from the TAC film was subtracted, and as a result, the retardation value was 3nm or less, and it was confirmed that the laminate was optically isotropic.
(6) Manufacture of vertical orientation liquid crystal solidified film
The polymerizable liquid crystal composition for forming a cured film of a homeotropic alignment liquid crystal was applied onto the cured resin layer on the substrate prepared as described above using a bar coater, and heated at 120℃for 60 seconds. Next, ultraviolet rays (accumulated light amount at 365nm wavelength: 500mJ/cm under nitrogen atmosphere) were irradiated from the surface coated with the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured BY Ushio Motor Co., ltd.) while being heated to 120℃and held 2 ) Thus, a vertically oriented liquid crystal cured film was formed, and a laminate was obtained in which a base material, a cured resin layer, and a vertically oriented liquid crystal cured film were stacked in this order. The film thickness of the obtained cured film of the homeotropic alignment liquid crystal was measured using an ellipsometer (M-220 manufactured by Nippon Spectrophotometer Co., ltd.) and found to be 0.6. Mu.m.
< measurement of phase Difference value of vertical alignment liquid Crystal cured film >)
The surface of the laminate of the substrate, the cured resin layer and the vertical alignment liquid crystal cured film produced by the above steps was subjected to corona treatment, and then bonded to glass via a 25 μm pressure sensitive adhesive manufactured by LINTEC company, followed by peeling off the TAC film and the cured resin layer. For the obtained laminate composed of glass, adhesive, and vertically oriented liquid crystal cured film, KOBRA-WPR manufactured by prince measuring instruments, inc. Was used to measure a front phase difference value and a phase difference value when inclined by 40 ° about the fast axis by changing the incident angle of light to the optical property measurement sample.
The average refractive index at each wavelength was measured using an ellipsometer M-220 manufactured by Nippon Spectroscopy Co. The film thickness was measured using a Optical NanoGauge film thickness meter C12562-01 manufactured by Hamamatsu Photonics K.K. The three-dimensional refractive index was calculated from the front phase difference value, the phase difference value when inclined by 40 ° about the fast axis, the average refractive index, and the film thickness values, by referring to the prince measurement machine technical data (http:// www.oji-keisoku. Co. Jp/products/kobra/reference. Html). Based on the obtained three-dimensional refractive index, the optical characteristics of the homeotropic alignment liquid crystal cured film were calculated according to the following formula, and values of Rth (450), rth (550), and αth=rth (450)/Rth (550) were calculated. The results are shown in Table 1.
RthC(λ)＝((nxC(λ)+nyC(λ))/2-nzC(λ))×dC
Note that RthC (λ) represents a phase difference value in a film thickness direction of the vertically aligned liquid crystal cured film at a wavelength λnm. In addition, nxC (λ) represents the in-plane principal refractive index of the vertically aligned liquid crystal cured film at wavelength λnm, nyC (λ) represents the refractive index in the direction orthogonal to nxC (λ) in the in-plane direction at wavelength λnm, nzC (λ) represents the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at wavelength λnm, and nxC (λ) may be the refractive index in any direction in the film surface in the case of nxC (λ) = nyC (λ), and dC represents the film thickness of the vertically aligned liquid crystal cured film.
(7) Manufacture of horizontal orientation liquid crystal solidified film
The surface of the vertically oriented liquid crystal cured film of the laminate formed of the base material (TAC film), the cured resin layer and the vertically oriented liquid crystal cured film manufactured by the above method was subjected to corona treatment, the composition for forming the horizontally oriented film was applied using a bar coater, and dried at 80 ℃ for 1 minute. Next, using a polarized UV light irradiation device (SPOTCURE SP-9; manufactured by Ushio Motor Co., ltd.), the cumulative light amount at the wavelength of 313 nm: 100mJ/cm 2 And (3) performing polarized UV light exposure under the condition of (2) to obtain a horizontal alignment film. The film thickness of the obtained horizontal alignment film was measured by using an ellipsometer and found to be 200nm.
Then, a polymerizable liquid crystal composition for forming a cured film of a horizontally oriented liquid crystal was applied to the horizontally oriented film, and the film was heated at 120℃for 60 seconds, and then usedA high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured BY Ushio Motor Co., ltd.) was irradiated with ultraviolet rays (cumulative light amount at 365nm wavelength: 500mJ/cm under nitrogen atmosphere) from the surface coated with the polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film 2 ) Thus, a horizontally oriented liquid crystal cured film was formed, and a laminate was obtained in which a substrate, a cured resin layer, a vertically oriented liquid crystal cured film, a horizontally oriented film, and a horizontally oriented liquid crystal cured film were stacked in this order. The film thickness of the obtained horizontally oriented liquid crystal cured film was measured using an ellipsometer and found to be 1.1. Mu.m. The total film thickness T1 of the laminate from the surface of the cured vertical alignment liquid crystal film on the substrate side to the surface of the cured horizontal alignment liquid crystal film on the opposite side to the horizontal alignment film was 1.9 μm.
The laminate obtained in example 1 was a laminate having a structure of a base material (TAC film)/a cured resin layer/a vertically oriented liquid crystal cured film/a horizontally oriented liquid crystal cured film.
< determination of phase Difference of horizontal alignment liquid Crystal cured film >)
The above-mentioned laminate comprising the substrate, the cured resin layer, the cured vertical alignment liquid crystal film, the horizontal alignment film and the cured horizontal alignment liquid crystal film was subjected to corona treatment on the cured horizontal alignment liquid crystal film surface, and then was bonded to glass via a pressure-sensitive adhesive of 25 μm manufactured by LINTEC company, followed by peeling off the TAC film and the cured resin layer. For the obtained laminate of glass, adhesive, cured vertical alignment liquid crystal film, horizontal alignment film, and cured horizontal alignment liquid crystal film, re (450) and Re (550) of the cured vertical alignment liquid crystal film measured in advance by the above method were subtracted from Re (450) and Re (550) measured by KOBRA-WPR manufactured by prince measuring instruments, to calculate Re (450) and Re (550) of the cured horizontal alignment liquid crystal film, and αa=re (450)/Re (550) was further calculated. The results are shown in Table 1.
(8) Evaluation of laminate
< evaluation of orientation of laminate >)
The obtained laminate was bonded to a glass having a thickness of 5X 5cm X0.7 mm via a pressure-sensitive adhesive (25 μm) manufactured by LINTEC, and only the base material was peeled off. The obtained sample was observed under a polarizing microscope (BX-51 manufactured by Olympus Co., ltd.) at a magnification of 200 times, and the number of alignment defects in the visual field of 480. Mu.m.times.320. Mu.m was counted. Here, as the number of alignment defects, only alignment defects due to the sample for measurement are counted, and the number of defects due to environmental foreign matters or the like other than the sample is excluded from counting. Based on the observation results in the polarizing microscope, the orientation of the laminate was evaluated based on the following evaluation criteria. If true, the orientation is determined to be excellent, and if false, the orientation is determined to be such that the optical characteristics are not affected. The results are shown in Table 1.
Evaluation reference:
o (very good): the number of orientation defects is 0 to 5.
Delta (good): the number of orientation defects is 6 or more and 20 or less.
X (difference): the number of alignment defects is 21 or more, or is completely unoriented.
< test of adhesion of laminate >)
The adhesion test of the laminate was performed as follows with reference to the adhesion test (cross-cut method) of JIS K5600-5-6. First, a horizontally oriented liquid crystal cured film side of the laminate was bonded to glass having a thickness of 5×5cm×0.7mm via a pressure sensitive adhesive (25 μm) made by LINTEC, and only the base material was peeled from the laminate. On the laminate side of the obtained sample, a 1mm ≡cut mark of 100 cells was made with a cutter (cutter). The obtained 100-cell cuts were laminated with cellcap (registered trademark) (manufactured by nichiba co., ltd.) and the cellcap was peeled off, and then the number of cells peeled off between the layers in the laminate was checked, and the adhesion was determined according to the following criteria. The results are shown in Table 1.
Evaluation reference:
and (2) the following steps: after Cellotap delamination, less than 30 cells were separated between layers in the laminate.
Delta: after Cellotap peeling, the number of cells in the laminate, which have been peeled between the layers, is 30 to 59.
X: after Cellotap peeling, the number of squares in the laminate, which have been peeled off between the layers, is 60 or more.
2. Example 2
A laminate was produced by sequentially stacking a substrate, a cured resin layer, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film adjacent to each other in this order in the same manner as in example 1, except that the preparation of the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film and the formation of the horizontal alignment liquid crystal cured film were changed as described below, and the adhesion and alignment properties of the laminate were evaluated. The results are shown in Table 1.
(1) Preparation of polymerizable liquid Crystal composition for Forming horizontal alignment liquid Crystal cured film
The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed in a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the resultant mixture, 0.1 part by mass of a leveling agent "BYK-361N" (manufactured by BM Chemie Co., ltd.) and 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (manufactured by BASF Japan Co., ltd. "Irgacure (registered trademark) 369 (Irg 369)") as photopolymerization initiators were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80℃for 1 hour, thereby obtaining a polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film.
(2) Formation of horizontally oriented liquid crystal cured films
The surface of the vertically oriented liquid crystal cured film of the laminate formed of the base material (TAC film), the cured resin layer, and the vertically oriented liquid crystal cured film, which was produced by the same procedure as in example 1, was subjected to corona treatment, and the composition for forming the horizontally oriented film was applied by a bar coater, and dried at 80 ℃ for 1 minute. Next, using a polarized UV light irradiation device (SPOTCURE SP-9; manufactured by Ushio Motor Co., ltd.), the cumulative light amount at the wavelength of 313 nm: 100mJ/cm 2 And (3) performing polarized UV light exposure under the condition of (2) to obtain a horizontal alignment film. The film thickness of the obtained horizontal alignment film was measured by using an ellipsometer and found to be 200nm.
Next, in the horizontal alignment filmThe polymerizable liquid crystal composition for forming a cured film of a horizontally oriented liquid crystal was applied thereto, and after heating at 120℃for 60 seconds, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured BY Ushio electric Co., ltd.) was used to irradiate ultraviolet rays (cumulative light amount at 365 nm: 500mJ/cm under nitrogen atmosphere) from the surface to which the polymerizable liquid crystal composition for forming a cured film of a horizontally oriented liquid crystal was applied 2 ) Thus, a horizontally oriented liquid crystal cured film was formed, and a laminate was obtained in which a substrate, a cured resin layer, a vertically oriented liquid crystal cured film, a horizontally oriented film, and a horizontally oriented liquid crystal cured film were stacked in this order. The film thickness of the obtained horizontally oriented liquid crystal cured film was measured using an ellipsometer and found to be 2.2. Mu.m.
3. Example 3
A laminate was produced by stacking a substrate, a cured resin layer, a cured vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film in this order in the same manner as in example 2, except that the preparation of the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film and the formation of the vertical alignment liquid crystal cured film were changed as described below, and adhesion and alignment properties of the laminate were evaluated. The results are shown in Table 1.
(1) Preparation of polymerizable liquid Crystal composition for Forming vertical alignment liquid Crystal cured film
The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed in a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the resultant mixture, 0.25 part by mass of a leveling agent "F-556" (manufactured by DIC Co., ltd.), 2.0 parts by mass of an ionic compound A (molecular weight: 645) prepared with reference to Japanese patent application 2016-514802, 0.5 part by mass of a silane coupling agent "KBE-9103" (manufactured by Xinyue chemical Co., ltd.), and 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (BASF Japan Co., ltd. "Irgacure (registered trademark) 369 (Irg 369)") as a photopolymerization initiator were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80℃for 1 hour, thereby obtaining a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film.
(2) Manufacture of vertical orientation liquid crystal solidified film
A polymerizable liquid crystal composition for forming a cured film of a homeotropic liquid crystal was applied to a cured resin layer on a substrate prepared in the same manner as in example 1BY using a bar coater, heated at 120℃for 60 seconds, and then irradiated with ultraviolet rays (cumulative light amount at 365nm wavelength: 500mJ/cm under nitrogen atmosphere) from the surface coated with the polymerizable liquid crystal composition for forming a cured film of a homeotropic liquid crystal BY using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured BY Ushio Motor Co., ltd.) 2 ) Thereby forming a vertically oriented liquid crystal cured film. The film thickness of the obtained cured film of the homeotropic alignment liquid crystal was measured using an ellipsometer (M-220 manufactured by Nippon Spectrophotometer Co., ltd.), and found to be 1.2. Mu.m.
4. Example 4
A laminate was produced by stacking a substrate, a cured resin layer, a cured vertical alignment liquid crystal film, a cured resin layer, a horizontal alignment film and a cured horizontal alignment liquid crystal film in this order, and the adhesiveness and alignment properties of the laminate were evaluated in the same manner as in example 3, except that the formation of the cured horizontal alignment liquid crystal film was changed as described below. The results are shown in Table 1.
(1) Formation of horizontally oriented liquid crystal cured films
A solution was prepared in which 50 parts by mass of dipentaerythritol hexaacrylate (multifunctional acrylate manufactured by ARONIX M-403 Toyama Synthesis Co., ltd.), 50 parts by mass of acrylate resin (Ebecryl 4858Daicel UCB Co., ltd.), 3 parts by mass of 2-methyl-1- [4- (methylsulfanyl) phenyl ] -2-morpholino-1-propanone (manufactured by Irgacure 907;Ciba Specialty Chemicals Co.) were dissolved in 250 parts by mass of isopropanol to obtain a composition for forming a cured resin layer containing an acrylate compound.
Subsequently, corona treatment was performed on the surface of the vertically oriented liquid crystal cured film of the laminate formed of the base material (TAC film), the cured resin layer, and the vertically oriented liquid crystal cured film, and the composition for forming the cured resin layer was applied by a bar coater and dried at 50 ℃ for 1 minute. Thereafter, a high-pressure mercury lamp ("Unicure VB-15201BY-A", manufactured BY Ushio electric Co., ltd.) was used,ultraviolet ray was irradiated (cumulative light amount at 365nm wavelength: 400mJ/cm under nitrogen atmosphere) 2 ) Thereby forming a cured resin layer. The film thickness of the obtained cured resin layer was measured by a contact film thickness meter and found to be 2.0. Mu.m.
Next, the cured resin layer surface of the outermost layer of the laminate formed of the base material (TAC film), the cured resin layer, the vertically oriented liquid crystal cured film, and the cured resin layer manufactured by the above method was subjected to corona treatment, and the composition for forming a horizontally oriented film was applied using a bar coater and dried at 80 ℃ for 1 minute. Next, using a polarized UV light irradiation device (SPOTCURE SP-9; manufactured by Ushio Motor Co., ltd.), the cumulative light amount at the wavelength of 313 nm: 100mJ/cm 2 And (3) performing polarized UV light exposure under the condition of (2) to obtain a horizontal alignment film. The film thickness of the obtained horizontal alignment film was measured by using an ellipsometer and found to be 200nm.
Next, a polymerizable liquid crystal composition for forming a cured film of a horizontally oriented liquid crystal was applied onto the horizontally oriented film, and after heating at 120℃for 60 seconds, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured BY Ushio Motor Co., ltd.) was used to irradiate ultraviolet rays (accumulated light quantity at 365nm wavelength: 500mJ/cm under nitrogen atmosphere) from the surface on which the polymerizable liquid crystal composition for forming a cured film of a horizontally oriented liquid crystal was applied 2 ) Thus, a horizontally oriented liquid crystal cured film was formed, and a laminate was obtained in which a substrate, a vertically oriented liquid crystal cured film, a horizontally oriented film, and a horizontally oriented liquid crystal cured film were stacked in this order. The film thickness of the obtained horizontally oriented liquid crystal cured film was measured using an ellipsometer and found to be 2.2. Mu.m.
5. Example 5
Except that the method for producing a cured film of a homeotropic alignment liquid crystal was changed as described below, a laminate was produced by sequentially stacking a substrate, a cured film of a homeotropic alignment liquid crystal, a horizontally aligned film and a cured film of a horizontally aligned liquid crystal in this order, and adhesion and alignment properties of the laminate were evaluated in the same manner as in example 3. The results are shown in Table 1.
(1) Manufacturing a vertical alignment liquid crystal curing film:
for Japanese Zeon CoAfter corona treatment of COP film (ZF 14-23) manufactured by Kyowa Kagaku Co., ltd., a polymerizable liquid crystal composition for forming a cured film of a homeotropic alignment liquid crystal was applied by a bar coater, and heated at 120℃for 60 seconds. Next, ultraviolet rays (accumulated light amount at 365nm wavelength: 500mJ/cm under nitrogen atmosphere) were irradiated from the surface coated with the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured BY Ushio Motor Co., ltd.) while being heated to 120℃and held 2 ) Thus, a vertically oriented liquid crystal cured film was formed, and a laminate was obtained in which a base material and a vertically oriented liquid crystal cured film were stacked in order. The film thickness of the obtained cured film of the homeotropic alignment liquid crystal was measured using an ellipsometer (M-220 manufactured by Nippon Spectrophotometer Co., ltd.), and found to be 1.2. Mu.m.
6. Example 6
A laminate was produced by stacking the substrate, the cured resin layer, the vertical alignment liquid crystal cured film, the horizontal alignment film and the horizontal alignment liquid crystal cured film in this order in the same manner as in example 3, except that the preparation of the substrate was changed as described below, and the adhesion and alignment properties of the laminate were evaluated. The results are shown in Table 1.
(1) Preparation of a substrate
A solution was prepared in which 50 parts by mass of dipentaerythritol hexaacrylate (multifunctional acrylate manufactured by ARONIX M-403 Toyama Synthesis Co., ltd.), 50 parts by mass of acrylate resin (Ebecryl 4858Daicel UCB Co., ltd.), 3 parts by mass of 2-methyl-1- [4- (methylsulfanyl) phenyl ] -2-morpholino-1-propanone (manufactured by Irgacure 907;Ciba Specialty Chemicals Co.) were dissolved in 250 parts by mass of isopropanol to obtain a composition for forming a cured resin layer containing an acrylate compound.
Next, the cured resin layer-forming composition was applied to a PET film (Diafoil T140E 25) made BY Mitsubishi resin Co., ltd.) BY a bar coater, dried at 50℃for 1 minute, and irradiated with ultraviolet light (cumulative light amount at 365nm wavelength: 400mJ/cm under nitrogen atmosphere BY a high-pressure mercury lamp ("Unicure VB-15201BY-A", manufactured BY Ushio Motor Co., ltd.) 2 ) Thereby forming a cured resin layer. By means of a contact film thickness meterThe film thickness of the obtained cured resin layer was measured and found to be 2.0. Mu.m.
7. Example 7
A laminate was produced by stacking a substrate, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film in this order in the same manner as in example 5 except that the film thickness of the horizontal alignment film was changed to 30nm, and adhesion and alignment properties of the laminate were evaluated. The results are shown in Table 1.
8. Example 8
A laminate was produced by stacking a substrate, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film in this order in the same manner as in example 5 except that the film thickness of the horizontal alignment film was changed to 500nm, and adhesion and alignment properties of the laminate were evaluated. The results are shown in Table 1.
9. Example 9
A laminate was produced by stacking a substrate, a cured vertical alignment liquid crystal film, a cured horizontal alignment film and a cured horizontal alignment liquid crystal film in this order in the same manner as in example 5, except that the preparation of the polymerizable liquid crystal composition for forming a cured vertical alignment liquid crystal film was changed as described below, and the adhesiveness and orientation of the laminate were evaluated. The results are shown in Table 1.
(1) Preparation of polymerizable liquid Crystal composition for Forming vertical alignment liquid Crystal cured film
The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed in a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the resultant mixture, 0.25 part by mass of a leveling agent "F-556" (manufactured by DIC Co., ltd.), 2.0 parts by mass of an ionic compound A (molecular weight: 645) prepared with reference to Japanese patent application 2016-514802, and 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (Irgacure (registered trademark) 369 (Irg 369) manufactured by BASF Japan Co., ltd.) as a photopolymerization initiator were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80℃for 1 hour, thereby obtaining a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film.
10. Example 10
A laminate was produced by stacking a substrate, a cured vertical alignment liquid crystal film, a cured horizontal alignment film and a cured horizontal alignment liquid crystal film in this order in the same manner as in example 5, except that the preparation of the polymerizable liquid crystal composition for forming a cured vertical alignment liquid crystal film was changed as described below, and the adhesiveness and orientation of the laminate were evaluated. The results are shown in Table 1.
(1) Preparation of polymerizable liquid Crystal composition for Forming vertical alignment liquid Crystal cured film
The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed in a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the resultant mixture, 0.25 part by mass of a leveling agent "F-556" (manufactured by DIC Co., ltd.), 0.5 part by mass of a silane coupling agent "KBE-9103" (manufactured by Xinyue chemical Co., ltd.) and 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (manufactured by BASF Japan Co., ltd. "Irgacure (registered trademark) 369 (Irg 369)") as a photopolymerization initiator were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80℃for 1 hour, thereby obtaining a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film.
11. Comparative example 1
A laminate was produced by stacking a substrate, a cured vertical alignment liquid crystal film, a cured horizontal alignment film and a cured horizontal alignment liquid crystal film in this order in the same manner as in example 5, except that the preparation of the polymerizable liquid crystal composition for forming a cured vertical alignment liquid crystal film was changed as described below, and the adhesiveness and orientation of the laminate were evaluated. The results are shown in Table 1.
(1) Preparation of polymerizable liquid Crystal composition for Forming vertical alignment liquid Crystal cured film
The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed in a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the resultant mixture, 0.25 part by mass of a leveling agent "F-556" (manufactured by DIC Co., ltd.) and 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (Irgacure (registered trademark) 369 (Irg 369) manufactured by BASF Japan Co., ltd.) as a photopolymerization initiator were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80℃for 1 hour, thereby obtaining a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film.
12. Comparative example 2
Except that the process for producing the horizontally oriented liquid crystal cured film was changed as described below, a laminate was produced by sequentially stacking the base material, the vertically oriented liquid crystal cured film, the horizontally oriented film and the horizontally oriented liquid crystal cured film in adjacent relation to each other in the same manner as in example 5, and adhesion and orientation of the laminate were evaluated. The results are shown in Table 1.
(1) Preparation of polymerizable liquid Crystal composition for Forming horizontal alignment liquid Crystal cured film
The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed in a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the resultant mixture, 0.1 part by mass of a leveling agent "BYK-361N" (manufactured by BM Chemie Co., ltd.) and 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (manufactured by BASF Japan Co., ltd. "Irgacure (registered trademark) 369 (Irg 369)") as photopolymerization initiators were added. Further, cyclopentanone was added so that the solid content concentration became 13%. The mixture was stirred at 80℃for 1 hour, thereby obtaining a polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film.
(2) Formation of horizontally oriented liquid crystal cured films
Corona treatment is performed on the vertically oriented liquid crystal cured film of the laminate formed of the substrate and the vertically oriented liquid crystal cured film manufactured by the above method. Then, a 4% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako pure chemical industries, ltd.) was applied, and the resultant film was dried to form a film having a thickness of 0.2. Mu.m. Next, the surface of the obtained film was subjected to a rubbing treatment to obtain a horizontally oriented film. In the friction treatment, a semiautomatic friction device (trade name: LQ-008 type, manufactured by Chang Yang engineering Co., ltd.) was used, and a cloth (trade name: YA-20-RW, manufactured by Jichuang chemical Co., ltd.) was used at a press-in amount of 0.15mm and a rotation speed of 500rpm at 16.7 mm/s.
Next, a polymerizable liquid crystal composition for forming a cured film of a horizontally oriented liquid crystal was applied onto the horizontally oriented film, and after heating at 120℃for 60 seconds, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured BY Ushio Motor Co., ltd.) was used to irradiate ultraviolet rays (accumulated light quantity at 365nm wavelength: 500mJ/cm under nitrogen atmosphere) from the surface on which the polymerizable liquid crystal composition for forming a cured film of a horizontally oriented liquid crystal was applied 2 ) Thus, a horizontally oriented liquid crystal cured film was formed, and a laminate was obtained in which a substrate, a vertically oriented liquid crystal cured film, a horizontally oriented film, and a horizontally oriented liquid crystal cured film were stacked in this order. The film thickness of the obtained horizontally oriented liquid crystal cured film was measured using an ellipsometer and found to be 2.2. Mu.m.
TABLE 1
It was confirmed that the present invention can produce a vertical alignment liquid crystal cured film without forming a vertical alignment film, and can improve both liquid crystal alignment and adhesion (examples 1 to 10). In contrast, when the polymerizable liquid crystal composition containing no vertical alignment accelerator was used, the vertical alignment liquid crystal cured film could not be obtained without forming the vertical alignment film, and thus the phase difference value of the horizontal alignment liquid crystal cured film could not be calculated (comparative example 1). In comparative example 2 in which the horizontally oriented film is not a photo-oriented film, the adhesion between the vertically oriented liquid crystal cured film and the horizontally oriented liquid crystal cured film is poor.
Description of the reference numerals
1: substrate material
2: vertical alignment liquid crystal cured film
3: horizontally oriented film
4: horizontal alignment liquid crystal cured film
5: cured resin layer
11: laminate body
Claims (21)
1. A laminate comprising a substrate, a vertically oriented liquid crystal cured film, a horizontally oriented film, and a horizontally oriented liquid crystal cured film in this order,
the vertical alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in a state of being aligned in a vertical direction with respect to the liquid crystal cured film plane, the horizontal alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in a state of being aligned in a horizontal direction with respect to the liquid crystal cured film plane,
the vertical alignment liquid crystal cured film contains a vertical alignment accelerator, the horizontal alignment film is a photo-alignment film formed from a polymer having a (meth) acryloyl group,
the total film thickness from the surface of the vertical alignment liquid crystal cured film on the substrate side to the surface of the horizontal alignment liquid crystal cured film on the opposite side to the horizontal alignment film is 10 [ mu ] m or less.
2. The laminate of claim 1, wherein the substrate is a releasable substrate.
3. The laminate according to claim 1 or 2, wherein the substrate, the vertically oriented liquid crystal cured film, the horizontally oriented film, and the horizontally oriented liquid crystal cured film are present adjacently in this order.
4. The laminate according to any one of claims 1 to 3, wherein the film thickness of the horizontal alignment film is 10 to 5000nm.
5. The laminate according to any one of claims 1 to 4, wherein the horizontal alignment film is a photo-alignment film formed of a polymer having an azo group or a cinnamoyl group.
6. The laminate according to any one of claims 1 to 5, wherein the horizontally oriented liquid crystal cured film has at least one or more of a maximum absorption at a wavelength of 300 to 400 nm.
7. The laminate according to any one of claims 1 to 6, wherein the horizontally oriented liquid crystal cured film satisfies the following formula (1):
ReA(450)/ReA(550)≤1 (1)
in the formula (1), a (450) represents an in-plane phase difference value at a wavelength of 450nm in an in-plane direction of the horizontally oriented liquid crystal cured film, and a (550) represents an in-plane phase difference value at a wavelength of 550nm in an in-plane direction of the horizontally oriented liquid crystal cured film.
8. The laminate according to any one of claims 1 to 7, wherein the homeotropic liquid crystal cured film comprises a nonionic silane compound as a homeotropic alignment accelerator.
9. The laminate according to any one of claims 1 to 8, wherein the homeotropic alignment liquid crystal cured film comprises a nonionic silane compound as a homeotropic alignment accelerator, the nonionic silane compound being a silane coupling agent.
10. The laminate according to any one of claims 1 to 9, wherein the vertically aligned liquid crystal cured film contains an ionic compound formed of a nonmetallic atom as a vertical alignment accelerator.
11. The laminate according to any one of claims 1 to 10, wherein the vertical alignment liquid crystal cured film contains an ionic compound formed of a nonmetallic atom as a vertical alignment accelerator, and the molecular weight of the ionic compound is 100 or more and 10,000 or less.
12. The laminate according to any one of claims 1 to 11, wherein the vertical alignment liquid crystal cured film contains a nonionic silane compound and an ionic compound formed of a nonmetallic atom as a vertical alignment accelerator.
13. The laminate according to any one of claims 1 to 12, wherein the horizontally oriented liquid crystal cured film is a liquid crystal cured film in which a polymerizable liquid crystal compound having at least one radical polymerizable group is cured in a state of being oriented horizontally with respect to an in-plane direction of the liquid crystal cured film, and the vertically oriented liquid crystal cured film is a liquid crystal cured film in which a polymerizable liquid crystal compound having at least one radical polymerizable group is cured in a state of being oriented vertically with respect to an in-plane direction of the liquid crystal cured film.
14. The laminate according to any one of claims 1 to 13, wherein the vertically oriented liquid crystal cured film has at least one maximum absorption between 300 and 400nm in wavelength.
15. The laminate according to any one of claims 1 to 14, wherein the vertically aligned liquid crystal cured film satisfies the following formula (2):
RthC(450)/RthC(550)≤1 (2)
in the formula (2), rthC (450) represents a phase difference in the thickness direction at a wavelength of 450nm of the vertical alignment liquid crystal cured film, and RthC (550) represents a phase difference in the thickness direction at a wavelength of 550nm of the vertical alignment liquid crystal cured film.
16. An elliptical polarizing plate comprising the laminate of any one of claims 1 to 15 and a polarizing film.
17. An elliptical polarizing plate comprising a laminate obtained by removing the base material from the laminate according to any one of claims 1 to 15, and a polarizing film.
18. The elliptical polarizing plate of claim 16 or 17, wherein an angle between a slow axis of the horizontally oriented liquid crystal cured film constituting the laminate and an absorption axis of the polarizing film is 45.+ -. 5 °.
19. An organic EL display device comprising the elliptical polarizing plate according to any one of claims 16 to 18.
20. The method for producing a laminate according to any one of claims 1 to 15, comprising the following steps in order:
A step of forming a coating film of a polymerizable liquid crystal composition for forming a cured film of a homeotropic liquid crystal, the coating film containing a polymerizable liquid crystal compound;
forming a coating film of the composition for forming a horizontal alignment film, and forming a horizontal alignment film from the coating film; the method comprises the steps of,
and a step of forming a coating film of the polymerizable liquid crystal composition for forming a cured film of a horizontally oriented liquid crystal containing the polymerizable liquid crystal compound, and forming a cured film of a horizontally oriented liquid crystal from the coating film.
21. The method according to claim 20, wherein the step of forming a vertically oriented liquid crystal cured film, the step of forming a horizontally oriented film, and the step of forming a horizontally oriented liquid crystal cured film are sequentially performed.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
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| JP2018-024566 | 2018-02-14 | ||
| JP2018024566 | 2018-02-14 | ||
| JP2019007263A JP7329926B2 (en) | 2018-02-14 | 2019-01-18 | Laminate and its manufacturing method |
| JP2019-007263 | 2019-01-18 | ||
| PCT/JP2019/004845 WO2019159888A1 (en) | 2018-02-14 | 2019-02-12 | Layered body and method for manufacturing same |
| CN201980011829.2A CN111684326B (en) | 2018-02-14 | 2019-02-12 | Laminate and method for producing same |
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| CN201980011829.2A Division CN111684326B (en) | 2018-02-14 | 2019-02-12 | Laminate and method for producing same |
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| CN116184553A true CN116184553A (en) | 2023-05-30 |
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| JP7461122B2 (en) * | 2019-09-17 | 2024-04-03 | 住友化学株式会社 | Laminate and elliptically polarizing plate including same |
| JP2022176121A (en) * | 2021-05-13 | 2022-11-25 | 住友化学株式会社 | Laminate and display |
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| JP2001100208A (en) * | 1995-11-17 | 2001-04-13 | Fuji Photo Film Co Ltd | Liquid crystal display device |
| JP4390540B2 (en) * | 2003-12-02 | 2009-12-24 | 大日本印刷株式会社 | OPTICAL ELEMENT AND ITS MANUFACTURING METHOD, AND LIQUID CRYSTAL ORIENTATION SUBSTRATE AND LIQUID CRYSTAL DISPLAY |
| JP2007241011A (en) * | 2006-03-10 | 2007-09-20 | Fujifilm Corp | Optical anisotropic film, retardation plate and liquid crystal display device |
| US7999893B2 (en) * | 2006-06-28 | 2011-08-16 | Sharp Kabushiki Kaisha | Complex birefringent medium, polarizing plate, and liquid crystal device |
| JP4911297B2 (en) * | 2006-10-16 | 2012-04-04 | 大日本印刷株式会社 | Optical element, liquid crystal display device, and method of manufacturing optical element |
| WO2013137464A1 (en) * | 2012-03-15 | 2013-09-19 | 富士フイルム株式会社 | Organic el display element comprising optical laminate |
| JP6216323B2 (en) * | 2012-10-04 | 2017-10-18 | 富士フイルム株式会社 | Circularly polarizing plate and manufacturing method thereof, optical laminate |
| JP2016004142A (en) * | 2014-06-17 | 2016-01-12 | 林テレンプ株式会社 | Optical film laminate and production method of the same, and liquid crystal display panel containing laminate |
| GB2542747A (en) * | 2014-07-15 | 2017-03-29 | Dainippon Ink & Chemicals | Liquid crystal display device |
| WO2017069252A1 (en) * | 2015-10-23 | 2017-04-27 | 富士フイルム株式会社 | Composition for photo-alignment films, photo-alignment film, optical laminate and image display device |
| JP6527076B2 (en) * | 2015-12-01 | 2019-06-05 | 富士フイルム株式会社 | Polarized film |
| JP7165491B2 (en) * | 2017-02-23 | 2022-11-04 | 住友化学株式会社 | Optical film and its manufacturing method |
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