CN116829995A - Liquid crystal composition, cured film, polarizing plate, and image display device - Google Patents
Liquid crystal composition, cured film, polarizing plate, and image display device Download PDFInfo
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- CN116829995A CN116829995A CN202280012542.3A CN202280012542A CN116829995A CN 116829995 A CN116829995 A CN 116829995A CN 202280012542 A CN202280012542 A CN 202280012542A CN 116829995 A CN116829995 A CN 116829995A
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- liquid crystal
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- carbon atoms
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 308
- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 150000001875 compounds Chemical class 0.000 claims abstract description 357
- 230000007704 transition Effects 0.000 claims abstract description 52
- 238000002844 melting Methods 0.000 claims abstract description 40
- 230000008018 melting Effects 0.000 claims abstract description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 97
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 68
- -1 acryloylamino group Chemical group 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 34
- 125000002947 alkylene group Chemical group 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 16
- 125000002252 acyl group Chemical group 0.000 claims description 15
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000005336 allyloxy group Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004378 air conditioning Methods 0.000 claims description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 138
- 239000000126 substance Substances 0.000 description 46
- 230000000694 effects Effects 0.000 description 39
- 239000000243 solution Substances 0.000 description 35
- 239000010410 layer Substances 0.000 description 33
- 239000007788 liquid Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 125000001931 aliphatic group Chemical group 0.000 description 18
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 16
- 239000001913 cellulose Substances 0.000 description 16
- 229920002678 cellulose Polymers 0.000 description 16
- 239000012788 optical film Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 229940125782 compound 2 Drugs 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 11
- 229940126214 compound 3 Drugs 0.000 description 10
- 230000007547 defect Effects 0.000 description 10
- 125000000623 heterocyclic group Chemical group 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 229940125904 compound 1 Drugs 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012069 chiral reagent Substances 0.000 description 6
- 125000006574 non-aromatic ring group Chemical group 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 5
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 125000005647 linker group Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000005268 rod-like liquid crystal Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- HJUFTIJOISQSKQ-UHFFFAOYSA-N fenoxycarb Chemical compound C1=CC(OCCNC(=O)OCC)=CC=C1OC1=CC=CC=C1 HJUFTIJOISQSKQ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000511976 Hoya Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000004419 alkynylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920006265 cellulose acetate-butyrate film Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011254 layer-forming composition Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- IZXDTJXEUISVAJ-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH+](C)CCCCCCCCCCCCCCCCCC IZXDTJXEUISVAJ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007767 slide coating Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- BSUNTQCMCCQSQH-UHFFFAOYSA-N triazine Chemical group C1=CN=NN=C1.C1=CN=NN=C1 BSUNTQCMCCQSQH-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
- C09K19/2021—Compounds containing at least one asymmetric carbon atom
- C09K19/2028—Compounds containing at least one asymmetric carbon atom containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -COO-CH*-CH3
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
- C09K2019/2078—Ph-COO-Ph-COO-Ph
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Abstract
The invention provides a liquid crystal composition, a cured film, a polarizing plate and an image display device, wherein the liquid crystal composition has a high phase transition temperature from a liquid crystal phase to an isotropic phase and can inhibit the generation of crystals in a solution obtained by mixing the liquid crystal composition with a solvent. The liquid crystal composition contains: a polymerizable liquid crystal compound (A) having 3 ring structures in the molecular long axis direction; a polymerizable liquid crystal compound (B) having 4 or more ring structures in the molecular long axis direction and having a phase transition temperature from the liquid crystal phase to the isotropic phase of 150 ℃ or higher; and a polymerizable compound (C) which has 3 ring structures in the molecular long axis direction and has a melting point of 65 to 120 ℃ unlike the polymerizable liquid crystal compound (A).
Description
Technical Field
The invention relates to a liquid crystal composition, a cured film, a polarizing plate and an image display device.
Background
The liquid crystal composition is used for forming various members such as an optically anisotropic film.
The liquid crystal composition is preferably operable to suppress precipitation of crystals and the like. For example, patent document 1 discloses a composition containing a predetermined compound as a liquid crystal composition having high crystallization inhibition performance.
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent application laid-open No. 2014-198814
Disclosure of Invention
Technical problem to be solved by the invention
The inventors of the present invention studied the crystal suppression property of the liquid crystal composition described in patent document 1, and as a result, found that although crystals generated after a solution obtained by mixing the liquid crystal composition and a solvent was applied to a substrate can be suppressed, the suppression of crystals generation in the solution before application was not necessarily sufficient, and further improvement was required.
In addition, in the liquid crystal composition containing a predetermined liquid crystal compound, the phase transition temperature from the liquid crystal phase to the isotropic phase is preferably high, in order to maintain the liquid crystallinity even when heated.
In view of the above-described circumstances, an object of the present invention is to provide a liquid crystal composition which has a high phase transition temperature from a liquid crystal phase to an isotropic phase and which suppresses the generation of crystals in a solution obtained by mixing the liquid crystal composition with a solvent.
The present invention also provides a cured film, a polarizing plate, and an image display device.
Means for solving the technical problems
As a result of intensive studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the following configuration.
(1) A liquid crystal composition comprising:
a polymerizable liquid crystal compound (A) having 3 ring structures in the molecular long axis direction;
a polymerizable liquid crystal compound (B) having 4 or more ring structures in the molecular long axis direction and having a phase transition temperature from the liquid crystal phase to the isotropic phase of 150 ℃ or higher; a kind of electronic device with high-pressure air-conditioning system
The polymerizable compound (C) has 3 ring structures in the molecular long axis direction and has a melting point of 65 to 120 ℃ unlike the polymerizable liquid crystal compound (A).
(2) The liquid crystal composition according to (1), wherein,
the melting enthalpy is less than 35 mJ/mg.
(3) The liquid crystal composition according to (1) or (2), wherein,
the polymerizable liquid crystal compound (A) is a compound represented by the following formula (1),
the polymerizable liquid crystal compound (B) has a phase transition temperature from the liquid crystal phase to the isotropic phase of 150 ℃ or higher and is represented by the following formula (2),
the polymerizable compound (C) has a melting point of 65 to 120 ℃ and is represented by the following formula (3).
(4) The liquid crystal composition according to (3), wherein,
in the formula (3), L 9 、L 10 、L 11 L and L 12 Independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 12 carbon atoms, L 9 、L 10 、L 11 L and L 12 At least 1 of them represents a group other than a hydrogen atom or a methyl group.
(5) The liquid crystal composition according to (3) or (4), wherein,
in the formula (3), L 9 、L 10 、L 11 L and L 12 Independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, L 9 、L 10 、L 11 L and L 12 At least 1 of them represents a group other than a hydrogen atom or a methyl group.
(6) The liquid crystal composition according to any one of (3) to (5), wherein,
the polymerizable liquid crystal compound (A) is a compound represented by the following formula (1-1).
(7) The liquid crystal composition according to (6), wherein,
in the formula (1-1), L 1 、L 2 、L 3 L and L 4 Each independently represents a hydrogen atom or a methyl group, L 1 、L 2 、L 3 L and L 4 At least 1 of which represents methyl.
(8) The liquid crystal composition according to any one of (3) to (7), wherein,
in the formula (2), Q 1 Q and Q 2 Each independently represents an aromatic ring which may have a substituent having 1 to 12 carbon atoms,
X 2 a group represented by the following formula (2B),
x and y each independently represent 0 or 1, and x+y is 1 or 2.
(9) The liquid crystal composition according to any one of (3) to (8), wherein,
the polymerizable liquid crystal compound (B) contains at least 1 compound selected from the group consisting of a compound represented by the following formula (2-1) and a compound represented by the following formula (2-2).
(10) The liquid crystal composition according to (9), wherein,
in the formula (2-1) and the formula (2-2), L 5 、L 6 、L 7 L and L 8 Each independently represents a hydrogen atom or a methyl group, L 5 、L 6 、L 7 L and L 8 At least 1 of which represents methyl.
(11) The liquid crystal composition according to any one of (3) to (10), wherein,
the total content of the compound represented by the formula (1) and the compound represented by the formula (2) is 50 to 95% by mass relative to the total amount of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3),
the content of the compound represented by the formula (3) is 5 to 50% by mass based on the total amount of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3).
(12) The liquid crystal composition according to any one of (3) to (11), wherein,
the total content of the compound represented by the formula (1) and the compound represented by the formula (2) is 60 to 90% by mass relative to the total amount of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3),
the content of the compound represented by the formula (3) is 10 to 40 mass% relative to the total amount of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3).
(13) The liquid crystal composition according to any one of (1) to (12), which further contains a polymerizable compound different from any one of the polymerizable liquid crystal compound (A), the polymerizable liquid crystal compound (B) and the polymerizable compound (C).
(14) The liquid crystal composition according to any one of (1) to (13), which further contains a polymerization initiator.
(15) A cured film obtained by curing the liquid crystal composition according to any one of (1) to (14).
(16) The cured film according to (15), which is an optically anisotropic film.
(17) The cured film according to (15), which is a film obtained by fixing a twisted orientation liquid crystal phase.
(18) A polarizing plate comprising the cured film of (15) and a polarizer.
(19) An image display device comprising (15) the cured film or (18) the polarizing plate.
Effects of the invention
According to the present invention, a liquid crystal composition having a high phase transition temperature from a liquid crystal phase to an isotropic phase and capable of suppressing the generation of crystals in a solution obtained by mixing the liquid crystal composition with a solvent can be provided.
Further, according to the present invention, a cured film, a polarizing plate, and an image display device can be provided.
Detailed Description
The present invention will be described in detail below.
The explanation of the constituent elements described below is sometimes completed according to the representative embodiment of the present invention, but the present invention is not limited to this embodiment.
In the present specification, a numerical range indicated by "to" refers to a range in which numerical values described before and after "to" are included as a lower limit value and an upper limit value.
In the present specification, 1 type of substance corresponding to each component may be used alone, or 2 or more types may be used in combination. In the case where 2 or more kinds of substances are used in combination for each component, the content of the component means the total content of the substances used in combination unless otherwise specified.
The bonding direction of the 2-valent group labeled in this specification is not limited unless otherwise specified. For example, in the case where M in the compound represented by the general formula "X-M-Y" is-COO- (-CO-O-) and the position bonded to the X side is 1 and the position bonded to the Y side is 2, M may be 1-CO-O-. Times.2 or 1-O-CO-. Times.2.
The liquid crystal composition of the present invention contains: a polymerizable liquid crystal compound (A) having 3 ring structures in the molecular long axis direction; a polymerizable liquid crystal compound (B) having 4 or more ring structures in the molecular long axis direction and having a phase transition temperature from the liquid crystal phase to the isotropic phase of 150 ℃ or higher; and a polymerizable compound (C) which has 3 ring structures in the molecular long axis direction and has a melting point of 65 to 120 ℃ unlike the polymerizable liquid crystal compound (A).
It was found that the desired effect can be obtained by combining the above specific compounds in the liquid crystal composition of the present invention.
The following describes each compound in detail.
< polymerizable liquid Crystal Compound (A) >)
The polymerizable liquid crystal compound (a) is a polymerizable liquid crystal compound having 3 ring structures in the molecular long axis direction. The polymerizable liquid crystal compound (a) may have 3 ring structures along the long axis direction of the molecule, and the ring structures may be bonded directly to each other or may be bonded via a 2-valent linking group.
The ring structure may be an aromatic ring or a non-aromatic ring, and an aromatic ring is preferable.
Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
The aromatic hydrocarbon ring may be a single ring or a condensed ring. The number of carbon atoms of the aromatic hydrocarbon ring is preferably 6 to 18, more preferably 6 to 10. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring. In this specification, a condensed ring formed of a plurality of rings may be regarded as a 1-ring structure.
The aromatic heterocycle may be a single ring or a condensed ring. The number of rings of the aromatic heterocycle is preferably 5 to 10. The hetero atom contained in the aromatic heterocyclic ring is not particularly limited, but examples thereof include a nitrogen atom, an oxygen atom and a sulfur atom. The aromatic heterocycle is not particularly limited, but examples thereof include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine (triazine) ring, a thiophene ring, a thiazole ring, and an imidazole ring.
Examples of the non-aromatic ring include aliphatic hydrocarbon rings and aliphatic heterocyclic rings.
The aliphatic hydrocarbon ring may be a single ring or a condensed ring. The number of carbon atoms of the aliphatic hydrocarbon ring is not particularly limited, but is preferably 3 to 20, more preferably 3 to 10. Examples of the aliphatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.
The aliphatic heterocyclic ring may be a single ring or a condensed ring. The number of the aliphatic heterocyclic ring is preferably 5 to 10. The hetero atom contained in the aliphatic heterocyclic ring is not particularly limited, but examples thereof include a nitrogen atom, an oxygen atom and a sulfur atom. The aliphatic heterocyclic ring is not particularly limited, but for example, pyrazoline ring, pyridine ring and morpholine ring can be mentioned.
The ring structure may have a substituent. The kind of the substituent is not particularly limited, and a known substituent may be mentioned. The substituent is not particularly limited, but examples thereof include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, an alkoxy group, an aryl group, a formyl group, a nitro group, a cyano group, an acyl group, an acyloxy group, a (meth) acryloyloxy group, a (meth) acryloylamino group, a dialkylamino group, a monoalkylamino group, an amino group, a maleimido group, an acetylamido group, an allyloxycarbamoyl group, an alkoxycarbamoyl group, an N- ((meth) acryloyloxyalkyl) carbamoyloxy group, an alkoxycarbonyl group, a carboxyl group, and a sulfonamide group, and combinations thereof.
The polymerizable liquid crystal compound (a) preferably has a structure represented by formula (XA).
(XA) - (L-Y) 3 -
L represents a single bond or a 2-valent linking group. The 2-valent linking group is not particularly limited, but examples thereof include a 2-valent aliphatic hydrocarbon group (which may be any of linear, branched and cyclic, and preferably has 1 to 10 carbon atoms, and examples thereof include alkylene, alkenylene and alkynylene), a 2-valent aromatic hydrocarbon group, a 2-valent heterocyclic group, -O-, -S-, -SO 2 -、-NR A -CO-, -n=n-, -ch=n-, and combinations of 2 or more of these. In addition, R A Represents a hydrogen atom or an alkyl group (preferably having 1 to 5 carbon atoms).
Y represents a 2-valent ring structure, and examples thereof include groups obtained by removing 2 hydrogen atoms from the above-mentioned ring structure. Specifically, a 2-valent aromatic ring group and a 2-valent non-aromatic ring group are exemplified. Examples of the aromatic ring constituting the 2-valent aromatic ring group include the above aromatic ring. Examples of the non-aromatic ring constituting the 2-valent non-aromatic ring group include the above-mentioned non-aromatic ring.
As the polymerizable liquid crystal compound (a), a compound represented by the formula (1) (hereinafter, also simply referred to as "compound 1") is preferable in terms of at least one effect from the viewpoint of obtaining a higher phase transition temperature from the liquid crystal phase to the isotropic phase and further suppressing the generation of crystals in a solution obtained by mixing the liquid crystal composition and the solvent (hereinafter, also simply referred to as "an effect of the present invention is more excellent").
[ chemical formula 1]
In the formula (1), R 1 Represents a hydrogen atom or a methyl group.
A 1 Representing carbon atomsAlkylene of 2 to 18, 1 CH in alkylene 2 Or not adjacent more than 2 CH 2 May be substituted with-O-.
In the aspect of the invention with more excellent effect, the method is represented by A 1 The number of carbon atoms of the alkylene group is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6.
Z 1 Z is as follows 2 Each independently represents-COO-, -O-or a single bond. Wherein Z is more excellent in the effect of the present invention 1 Z is as follows 2 Each independently is preferably-COO-or-O-, more preferably-O-.
X 1 The group represented by the formula (1A) is preferable in terms of curability of the liquid crystal composition, because it represents a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a vinyl group, a formyl group, a nitro group, a cyano group, an acetyl group, an acetoxy group, an N-acetylamide group, an acryloylamino group, an N, N-dimethylamino group, a maleimide group, a methacryloylamino group, an allyloxy carbamoyl group, an N-alkyloxycarbamoyl group having 1 to 4 carbon atoms of an alkyl group, an N- (2-methacryloxyethyl) carbamoyl group, an N- (2-acryloxyethyl) carbamoyl group, or a group represented by the formula (1A) described below.
Formula (1A) x-A 2 -P 1
In the formula (1A), A 2 Represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted with-O-.
In the aspect of the invention with more excellent effect, the method is represented by A 2 The number of carbon atoms of the alkylene group is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6.
P 1 The hydrogen atom, the acryloyloxy group or the methacryloyloxy group is preferably an acryloyloxy group or a methacryloyloxy group in view of the more excellent effect of the present invention.
* Indicating the bonding location.
L 1 、L 2 、L 3 L and L 4 Respectively independent earth's surfaceShows hydrogen atom, alkyl group with 1-4 carbon atoms, alkoxy group with 1-4 carbon atoms, alkoxycarbonyl group with 2-5 carbon atoms, acyl group with 2-4 carbon atoms or halogen atom, L 1 、L 2 、L 3 L and L 4 At least 1 of which represents a group other than a hydrogen atom.
Among them, L is preferable in terms of more excellent effect of the present invention 1 、L 2 、L 3 L and L 4 Independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or an acyl group having 2 to 4 carbon atoms, and L 1 、L 2 、L 3 L and L 4 At least 1 of them represents a group other than a hydrogen atom, more preferably L 1 、L 2 、L 3 L and L 4 Independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and L 1 、L 2 、L 3 L and L 4 At least 1 of which represents a group other than a hydrogen atom. Of these, L is further preferred 1 、L 2 、L 3 L and L 4 Each independently represents a hydrogen atom or a methyl group and L 1 、L 2 、L 3 L and L 4 At least 1 of (a) represents methyl, particularly preferably L 1 、L 2 L and L 3 Is a hydrogen atom and L 4 Is methyl.
Among them, in terms of the more excellent effect of the present invention, the polymerizable liquid crystal compound (a) is preferably a compound represented by the formula (1-1).
[ chemical formula 2]
R in the above formula (1-1) 1 、A 1 、Z 1 、Z 2 、L 1 、L 2 、L 3 L and L 4 Respectively with R in formula (1) 1 、A 1 、A 2 、Z 1 、Z 2 、L 1 、L 2 、L 3 L and L 4 Meaning of (a) is the same, preferred modeAs described above. A in the above formula (1-1) 2 Meaning of (A) and A in formula (1A) 2 The meaning of (2) is the same, and the preferred manner is as described above.
In the formula (1-1), L is 1 、L 2 、L 3 L and L 4 At least 1 of which represents a group other than a hydrogen atom.
R 4 Represents a hydrogen atom or a methyl group.
The phase transition temperature of the polymerizable liquid crystal compound (a) from the liquid crystal phase to the isotropic phase is not particularly limited, but is preferably more than 120 ℃ in view of the more excellent effect of the present invention. The upper limit of the phase transition temperature of the polymerizable liquid crystal compound (a) from the liquid crystal phase to the isotropic phase is not particularly limited, but is usually 250 ℃ or less, and more usually 200 ℃ or less.
The method for measuring the phase transition temperature of the polymerizable liquid crystal compound (a) from the liquid crystal phase to the isotropic phase (hereinafter, this method is also referred to as "specific method") is as follows.
Two pieces of polarizers of an optical microscope (NIKON co., ltd. ECLIPSE E600 POL) were arranged in a mutually orthogonal manner, and a sample stage was fixed between the two pieces of polarizers. Next, a small amount of the polymerizable liquid crystal compound (a) was placed on the slide glass, and the slide glass was fixed on a hot stage placed on the sample stage. While observing the state of the sample with a microscope, the temperature of the heat stage was raised at 5 ℃/min, and the temperature at which the liquid crystal phase was converted into the isotropic phase was recorded.
< polymerizable liquid Crystal Compound (B) >)
The polymerizable liquid crystal compound (B) has 4 or more ring structures in the molecular long axis direction, and has a phase transition temperature from the liquid crystal phase to the isotropic phase of 150 ℃ or higher.
The polymerizable liquid crystal compound (B) may have 4 or more ring structures along the long axis direction of the molecule, and the ring structures may be bonded directly to each other or may be bonded via a 2-valent linking group. The ring structure of the polymerizable liquid crystal compound (B) includes the ring structure of the polymerizable liquid crystal compound (a). The number of ring structures of the polymerizable liquid crystal compound (B) is 4 or more, preferably 4 to 6, more preferably 4 or 5.
The phase transition temperature of the polymerizable liquid crystal compound (B) from the liquid crystal phase to the isotropic phase is 150 ℃ or higher, and in terms of the more excellent effect of the present invention, it is preferably 150 to 400 ℃, more preferably 150 to 300 ℃.
The method for measuring the phase transition temperature of the polymerizable liquid crystal compound (B) from the liquid crystal phase to the isotropic phase is the same as the method for measuring the phase transition temperature of the polymerizable liquid crystal compound from the liquid crystal phase to the isotropic phase.
The polymerizable liquid crystal compound (B) preferably has a structure represented by the formula (XB).
(XB) - (L-Y) n -
The meanings of L and Y in the formula (XB) are the same as those of L and Y in the formula (XA), respectively.
n represents an integer of 4 or more, preferably an integer of 4 to 6.
As the polymerizable liquid crystal compound (B), a compound having a phase transition temperature from the liquid crystal phase to the isotropic phase of 150 ℃ or higher and represented by formula (2) (hereinafter, also simply referred to as "compound 2") is preferable in terms of further excellent effects of the present invention. That is, the compound 2 is a compound represented by the formula (2) and having a phase transition temperature from the liquid crystal phase to the isotropic phase of 150 ℃.
The phase transition temperature range of the compound 2 from the liquid crystal phase to the isotropic phase is preferably the same as that of the polymerizable liquid crystal compound (B) described above.
[ chemical formula 3]
In the formula (2), R 2 Represents a hydrogen atom or a methyl group.
A 3 Represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted with-O-.
In the aspect of the invention with more excellent effect, the method is represented by A 3 The number of carbon atoms of the alkylene group represented is preferably 2 to 10, more preferably 2 to 8.
Z 3 、Z 4 、Z 5 Z is as follows 6 Each independently represents-COO-, -O-or a single bond. Wherein Z is more excellent in the effect of the present invention 3 、Z 4 、Z 5 Z is as follows 6 Each independently is preferably-COO-or-O-.
Q 1 Q and Q 2 Each independently represents an aromatic ring group or an alicyclic group which may have a substituent having 1 to 12 carbon atoms.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Examples of the aromatic hydrocarbon ring constituting the aromatic heterocyclic group include aromatic hydrocarbon rings which can be used as the above-mentioned ring structure. Examples of the aromatic heterocycle constituting the aromatic heterocyclic group include rings exemplified as aromatic heterocycles which can be used as the above-mentioned ring structures.
Examples of the alicyclic group include an aliphatic hydrocarbon ring group and an aliphatic heterocyclic group. Examples of the aliphatic hydrocarbon ring constituting the aliphatic hydrocarbon ring group include those exemplified as the aliphatic hydrocarbon ring which can be used as the above-mentioned ring structure. Examples of the aliphatic heterocyclic ring constituting the aliphatic heterocyclic group include rings exemplified as aliphatic heterocyclic rings which can be used as the above-mentioned ring structures.
The number of carbon atoms of the substituent which the aromatic ring group and the alicyclic group may have is 1 to 12, preferably 1 to 10, more preferably 1 to 8, and still more preferably 2 to 6. Examples of the substituent include an alkyl group, an alkoxy group, and an alkoxycarbonyl group.
Among them, in terms of the more excellent effect of the present invention, an aromatic ring group which may have a substituent having 1 to 12 carbon atoms is preferable, and a phenylene group which may have a substituent having 1 to 12 carbon atoms is more preferable.
X 2 Represents a hydrogen atom, a halogen atom, a C1-4 linear alkyl group, a methoxy group, an ethoxy group, an optionally substituted aromatic ring group, a cyclohexyl group, a vinyl group, a formyl group, a nitro groupIn terms of the more excellent effect of the present invention, the group represented by the formula (2A) is preferable, and the group represented by the formula (2B) is more preferable.
Formula (2A) x-A 4 -P 2
In the formula (2A), A 4 Represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted with-O-.
In the aspect of the invention with more excellent effect, the method is represented by A 4 The number of carbon atoms of the alkylene group is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6.
P 2 The hydrogen atom, the acryloyloxy group or the methacryloyloxy group is preferably an acryloyloxy group or a methacryloyloxy group in view of the more excellent effect of the present invention.
* Indicating the bonding location.
[ chemical formula 4]
In the formula (2B), R 5 Represents a hydrogen atom or a methyl group.
A in formula (2B) 4 Meaning of (A) and A in the formula (2A) 4 Meaning the same.
* Indicating the bonding location.
L 5 、L 6 、L 7 L and L 8 Independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a halogen atom, L 5 、L 6 、L 7 L and L 8 At least 1 of which represents a group other than a hydrogen atom.
Among them, L is preferable in terms of more excellent effect of the present invention 5 、L 6 、L 7 L and L 8 Independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or an acyl group having 2 to 4 carbon atoms, and L 5 、L 6 、L 7 L and L 8 At least 1 of them represents a group other than a hydrogen atom, more preferably L 5 、L 6 、L 7 L and L 8 Each independently represents a hydrogen atom or a methyl group and L 5 、L 6 、L 7 L and L 8 At least 1 of which represents methyl. Of these, L is further preferred 5 、L 6 L and L 7 Is a hydrogen atom and L 8 Is methyl.
x and y each independently represent 0, 1 or 2, and at least one of x and y represents 1 or 2. Among them, in terms of the more excellent effect of the present invention, it is preferable that x and y each independently represent 0 or 1 and x+y is 1 or 2.
Among them, in terms of the more excellent effect of the present invention, it is preferable that the polymerizable liquid crystal compound (B) contains at least 1 compound selected from the group consisting of the compound represented by the formula (2-1) and the compound represented by the formula (2-2).
[ chemical formula 5]
R in formula (2-1) and formula (2-2) 2 、A 3 、Z 4 、L 5 、L 6 、L 7 L and L 8 Meaning of (C) and R in formula (2) 2 、A 3 、Z 4 、L 5 、L 6 、L 7 L and L 8 The meaning of (2) is the same, and the preferred manner is as described above. A in the above formula (2-1) and formula (2-2) 4 Meaning of (A) and A in the formula (2A) 4 The meaning of (2) is the same, and the preferred manner is as described above. R in the above formula (2-1) and formula (2-2) 5 Meaning of (C) and R in formula (2B) 5 The meaning of (2) is the same, and the preferred manner is as described above.
In the above formula (2-1) and formula (2-2), L 5 、L 6 、L 7 L and L 8 At least 1 of which represents a group other than a hydrogen atom.
< polymerizable Compound (C) >)
The polymerizable compound (C) is a compound different from the polymerizable liquid crystal compound (A), has 3 ring structures in the molecular long axis direction, and has a melting point of 65 to 120 ℃. In addition, the melting point refers to the phase transition temperature from the solid state to the liquid state when the polymerizable compound (C) does not exhibit liquid crystallinity, and the melting point refers to the phase transition temperature from the liquid crystal phase to the isotropic phase when the polymerizable compound (C) exhibits liquid crystallinity.
The polymerizable compound (C) may have 3 ring structures along the long axis direction of the molecule, and the ring structures may be bonded directly to each other or may be bonded via a 2-valent linking group. The ring structure of the polymerizable liquid crystal compound (C) includes the ring structure of the polymerizable liquid crystal compound (a).
The melting point of the polymerizable compound (C) is 65 to 120℃and, in view of the more excellent effect of the present invention, it is preferably 70 to 110℃and more preferably 80 to 110 ℃.
When the polymerizable compound (C) exhibits liquid crystallinity, the method for measuring the melting point of the polymerizable compound (C) is the same as the method for measuring the phase transition temperature of the polymerizable liquid crystal compound (a) from the liquid crystal phase to the isotropic phase. In the case where the polymerizable compound (C) does not exhibit liquid crystallinity, the same procedure as the method for measuring the phase transition temperature of the polymerizable liquid crystal compound (a) from the liquid crystal phase to the isotropic phase is carried out, and the temperature at which the polymerizable compound (C) changes from the solid state to the liquid state is used as the melting point.
The polymerizable compound (C) may be a compound exhibiting liquid crystallinity, or may be a compound not exhibiting liquid crystallinity, and is preferably a compound exhibiting liquid crystallinity.
The polymerizable compound (C) preferably has a structure represented by the formula (XC).
(XC) - (L-Y) 3 -
The meanings of L and Y in the formula (XC) are the same as those of L and Y in the formula (XA), respectively.
As the polymerizable compound (C), a compound having a melting point of 65 to 120 ℃ and represented by the formula (3) (hereinafter, also simply referred to as "compound 3") is preferable in terms of more excellent effects of the present invention. Namely, the compound 3 is a compound represented by the formula (3) and having a melting point of 65 to 120 ℃.
The melting point range of the compound 3 is preferably the same as that of the polymerizable liquid crystal compound (C), as described above.
[ chemical formula 6]
In the formula (3), R 3 R is R 6 Represents a hydrogen atom or a methyl group.
A 5 A is a 6 Each independently represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted with-O-.
In the aspect of the invention with more excellent effect, the method is represented by A 5 A is a 6 The number of carbon atoms of the alkylene group is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6.
Z 7 Z is as follows 8 Each independently represents-COO-, -O-or a single bond. Wherein Z is more excellent in the effect of the present invention 7 Z is as follows 8 Each independently is preferably-COO-or-O-, more preferably-O-.
L 9 、L 10 、L 11 L and L 12 Independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, a formyl group, a cyano group, a nitro group, an N-alkylamido group having 1 to 12 carbon atoms in the alkyl group, or a carbon atom in the alkyl groupN, N-dialkylamino, maleimido, acryloylamino, methacryloylamino, allyloxy, allyloxycarbamoyl, N-alkyloxycarbamoyl, N- (2-methacryloyloxyethyl) carbamoyloxy, N- (2-acryloyloxyethyl) carbamoyloxy or halogen atom having 1 to 12 carbon atoms in the alkyl group, L 9 、L 10 、L 11 L and L 12 At least 1 of them represents a group other than a hydrogen atom or a methyl group.
Among them, L is preferable in terms of more excellent effect of the present invention 9 、L 10 、L 11 L and L 12 Independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms or an acyl group having 2 to 12 carbon atoms, and L 9 、L 10 、L 11 L and L 12 At least 1 of them represents a hydrogen atom or a group other than methyl, more preferably L 9 、L 10 、L 11 L and L 12 Independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms and L 9 、L 10 、L 11 L and L 12 At least 1 of them represents a group other than a hydrogen atom or a methyl group. Of these, L is further preferred 9 、L 10 L and L 11 Is a hydrogen atom and L 12 Is an alkyl group having 2 to 12 carbon atoms.
In addition, in terms of the more excellent effect of the present invention, the carbon number of the alkyl group is preferably 2 to 10, more preferably 2 to 7, and even more preferably 3 to 4.
In terms of the more excellent effect of the present invention, the carbon number of the alkoxy group is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 to 2.
In terms of the more excellent effect of the present invention, the carbon number of the alkoxycarbonyl group is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 to 2.
In terms of the more excellent effect of the present invention, the number of carbon atoms of the acyl group is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 to 2.
The liquid crystal composition of the present invention may contain a compound other than the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C).
The other compound may contain, for example, a polymerizable compound different from any of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C). The polymerizable compound may be a polymerizable liquid crystal compound.
Further, as the other compound, a polymerization initiator is exemplified. The polymerization initiator to be used may be selected according to the form of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
Examples of the other compounds include chiral agents, surfactants, adhesion improvers, vertical alignment agents, horizontal alignment agents, and crosslinking agents.
The liquid crystal composition of the present invention is preferably substantially free of solvent. Substantially free of solvent means that the content of the solvent is 1 mass% or less relative to the total mass of the liquid crystal composition. The lower limit is not particularly limited, and may be 0 mass%.
In the liquid crystal composition of the present invention, the content of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C) is not particularly limited, but in terms of the effect of the present invention, the total content of the polymerizable liquid crystal compound (a) and the polymerizable liquid crystal compound (B) is 60 to 90 mass% with respect to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C), preferably the total content of the polymerizable compound (C) is 5 to 50 mass% with respect to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C), more preferably the total content of the polymerizable liquid crystal compound (a) and the polymerizable liquid crystal compound (B) is 60 to 90 mass% with respect to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C) and the total amount of the polymerizable compound (C) is 10 to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C) is 10 to the total amount of the polymerizable compound (C).
In the case where the liquid crystal composition of the present invention contains compound 1, compound 2 and compound 3, the total content of compound 1 and compound 2 is 50 to 95% by mass relative to the total amount of compound 1, compound 2 and compound 3, preferably the total content of compound 3 is 5 to 50% by mass relative to the total amount of compound 1, compound 2 and compound 3, more preferably the total content of compound 1 and compound 2 is 60 to 90% by mass relative to the total amount of compound 1, compound 2 and compound 3 and the total content of compound 3 is 10 to 40% by mass relative to the total amount of compound 1, compound 2 and compound 3.
Further, if the total content of the polymerizable compounds (C) is 5 to 50% by mass relative to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C), the viscosity in the liquid crystal composition of the present invention can be increased as compared with the liquid crystal composition containing the polymerizable liquid crystal compound (a) alone, and particularly, the dishing defect which is likely to occur when the cured film after curing the liquid crystal composition of the present invention is a layer having a fixed twist alignment liquid crystal phase can be suppressed.
In addition, the dent defect means a defective portion generated in the cured film as a result of the liquid crystal composition being repelled from a local area on the object to be coated to generate an area where the liquid crystal composition is not coated when the liquid crystal composition is coated on the object to be coated.
The mixing ratio of the polymerizable liquid crystal compound (a) and the polymerizable liquid crystal compound (B) in the liquid crystal composition of the present invention is not particularly limited, and the content of the polymerizable liquid crystal compound (a) is preferably 50 to 97% by mass, more preferably 70 to 95% by mass, relative to the total content of the polymerizable liquid crystal compound (a) and the polymerizable liquid crystal compound (B).
In terms of the more excellent effect of the present invention, the total content of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C) is preferably 60 mass% or more, more preferably 70 mass% or more, relative to the total mass of the liquid crystal composition of the present invention. The upper limit is not particularly limited, and is 100% by mass, but is at most 99% by mass.
In the case where the liquid crystal composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, relative to the total mass of the liquid crystal composition.
The polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C) may be contained in the liquid crystal composition singly or in combination of 1 kind or 2 or more kinds.
In addition, in the case where 2 or more kinds of compounds corresponding to both the polymerizable liquid crystal compound (a) and the polymerizable compound (C) are contained in the liquid crystal composition, at least 1 is the polymerizable liquid crystal compound (a) and at least 1 is the polymerizable compound (C).
The melting enthalpy of the liquid crystal composition is not particularly limited, but in terms of the effect of the present invention being more excellent, it is preferably 35mJ/mg or less, more preferably 30mJ/mg or less. The lower limit of the melting enthalpy is not particularly limited, but is at most 20mJ/mg or more.
The melting enthalpy of the liquid crystal composition was measured as follows.
First, a polymerizable liquid crystal compound (a), a polymerizable liquid crystal compound (B), a polymerizable compound (C), a polymerization inhibitor (Irganox 1010, manufactured by BASF JAPAN ltd.) and a solvent (for example, acetone) contained in a liquid crystal composition are mixed to prepare a solution. The content ratio of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B), and the polymerizable compound (C) in the solution is the same as the content ratio of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B), and the polymerizable compound (C) in the liquid crystal composition. The content of the polymerization inhibitor in the solution was 1 mass% relative to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B), the polymerizable compound (C), and the polymerization inhibitor. The content of the solvent in the solution was 88 mass% based on the total mass of the solution.
The obtained solution was dried under reduced pressure at 30℃for 2 hours, the solvent in the solution was removed, and using the obtained solid sample, heating was performed at 5℃per minute from 25℃to 140℃by a differential scanning calorimeter (X-DSC 7000, manufactured by Hitachi High-Tech Science Corporatio n), and measurement was performed, to calculate the melting enthalpy.
The method for producing the liquid crystal composition is not particularly limited, and a known method can be used.
< cured film >)
The cured film of the present invention is a film obtained by curing the above-mentioned liquid crystal composition.
The method for forming the cured film is not particularly limited, and the following methods are exemplified: the liquid crystal composition is applied to form a coating film, the coating film is subjected to an alignment treatment to align the polymerizable liquid crystal compound, and a curing treatment is performed.
The object to be coated with the liquid crystal composition is not particularly limited, and examples thereof include a support described later and a polarizer described later.
In the case where the cured film is an optically anisotropic film, the object to which the liquid crystal composition is applied may be subjected to rubbing treatment so that the in-plane slow axis direction of the optically anisotropic film is set to a predetermined direction. For example, a support subjected to a rubbing treatment may be used.
Examples of the method for applying the liquid crystal composition include curtain coating, dip coating, spin coating, print coating, spray coating, slit coating, roll coating, slide coating, doctor blade coating, gravure coating, and bar coating.
Then, the formed coating film is subjected to an alignment treatment to align the polymerizable liquid crystal compound in the coating film. The polymerizable liquid crystal compound in the coating film includes at least a polymerizable liquid crystal compound (a) and a polymerizable liquid crystal compound (B). When the polymerizable compound (C) is a compound having liquid crystal properties, the polymerizable compound (C) corresponds to the polymerizable liquid crystal compound.
The orientation treatment can be performed by drying the coating film at room temperature or heating the coating film. The liquid crystal phase formed by the alignment treatment can generally be changed according to a change in temperature or pressure.
The conditions for heating the coating film are not particularly limited, but the heating temperature is preferably 50 to 250 ℃, more preferably 50 to 150 ℃, and the heating time is preferably 10 seconds to 10 minutes.
After the coating film is heated, the coating film may be cooled as needed before a curing treatment (light irradiation treatment) described later. The cooling temperature is preferably 20 to 200℃and more preferably 30 to 150 ℃.
The type of the liquid crystal phase formed in the alignment treatment is not particularly limited, and can be appropriately adjusted according to the components contained in the liquid crystal composition. Examples of the liquid crystal phase include nematic phase, smectic phase, and twist-aligned liquid crystal.
The twist-alignment liquid crystal phase refers to a phase of twist-aligning a liquid crystal compound along a helical axis extending in the thickness direction. The twist angle is not particularly limited, and for example, the twist angle may be a twist oriented liquid crystal phase exceeding 0 ° and 360 ° or less. In addition, as one of the twisted alignment liquid crystal phases, a cholesteric liquid crystal phase is exemplified. In this specification, a cholesteric liquid crystal phase refers to a mode in which the twist angle exceeds 360 °.
Then, the coating film having the polymerizable liquid crystal compound aligned is subjected to a curing treatment.
The method of curing the coating film to which the polymerizable liquid crystal compound is oriented is not particularly limited, and examples thereof include a light irradiation treatment and a heat treatment. Among them, the light irradiation treatment is preferable, and the ultraviolet irradiation treatment is more preferable in view of the manufacturing applicability.
The irradiation condition of the light irradiation treatment is not particularly limited, and is preferably 50 to 1000mJ/cm 2 Is used for the irradiation amount of the light source.
The atmosphere in the light irradiation treatment is not particularly limited, but a nitrogen atmosphere is preferable.
The cured film obtained by the above method is a film in which a predetermined liquid crystal phase is fixed.
The cured film may be, for example, a film in which a nematic phase is fixed, or a film in which a twisted alignment liquid crystal phase is fixed. The cured film may have a plurality of regions in which the alignment states of the liquid crystal compounds different from each other are fixed in the thickness direction. For example, the cured film may have a region in which a uniformly aligned liquid crystal compound is fixed and a region in which a twisted aligned liquid crystal compound is fixed in the thickness direction.
And, the cured film may be an optically anisotropic film. The optically anisotropic film is a film having a predetermined in-plane retardation and/or retardation in the thickness direction.
The optically anisotropic film may be a so-called λ/4 plate or λ/2 plate in terms of being applicable to various uses.
The "λ/4 plate" is a plate having a function of converting linearly polarized light of a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light). More specifically, the in-plane retardation Re at a predetermined wavelength λnm is represented by λ/4 (or an odd multiple thereof).
The retardation in plane (Re (550)) of the lambda/4 plate at a wavelength of 550nm may have an error of about 25nm around an ideal value (137.5 nm), and is preferably 110 to 160nm, more preferably 120 to 150nm.
Also, the λ/2 plate refers to an optically anisotropic film whose in-plane retardation Re (λ) at a specific wavelength λnm satisfies Re (λ) ≡λ/2. This expression is only required to be realized at a wavelength (for example, 550 nm) in any of the visible ray regions. Among them, the in-plane retardation Re (550) at a wavelength of 550nm preferably satisfies the following relationship.
210nm≤Re(550)≤300nm
The thickness of the cured film is not particularly limited, and the optimum thickness is appropriately selected depending on the application used, but is preferably 0.05 to 10. Mu.m, more preferably 0.1 to 8.0. Mu.m, from the viewpoint of handleability.
< optical film >)
The optical film of the present invention comprises a support and a cured film disposed on the support.
The manner of curing the film is as described above.
As the support, a transparent support is preferable. The transparent support means a support having a transmittance of 60% or more of visible light, and the transmittance thereof is preferably 80% or more, more preferably 90% or more.
The support may be a long-strip support (long-strip support). The length of the long support in the longitudinal direction is not particularly limited, and a support of 10m or more is preferable, and from the viewpoint of productivity, 100m or more is preferable. The length in the longitudinal direction is not particularly limited, and is usually 10000m or less.
The width of the long support is not particularly limited, but is usually 150 to 3000mm, preferably 300 to 2000mm.
As a material for forming the support, a polymer excellent in optical transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable.
Examples of the polymer film that can be used as the support include cellulose acylate films (for example, cellulose triacetate films, cellulose diacetate films, cellulose acetate butyrate films, cellulose acetate propionate films), polyolefin films such as polyethylene and polypropylene, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyacrylic acid films such as polymethyl methacrylate, polyether sulfone films, polyurethane films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyether ketone films, (meth) acrylonitrile films, and films of polymers having alicyclic structures (norbornene resins (trade names, manufactured by JSR Corporation, amorphous polyolefin (ZEONEX: trade names, manufactured by ZEOn Corporation)).
Among them, triacetyl cellulose, polyethylene terephthalate, or a polymer having an alicyclic structure is preferable as a material of the polymer film.
The support may contain various additives (for example, an optical anisotropy adjuster, a wavelength dispersion adjuster, microparticles, a plasticizer, an ultraviolet ray inhibitor, a degradation inhibitor, and a peeling agent).
The retardation value (Rth (550)) of the support in the thickness direction at a wavelength of 550nm is not particularly limited, and is preferably-110 to 110nm, more preferably-80 to 80nm.
The in-plane retardation (Re (550)) of the support at a wavelength of 550nm is not particularly limited, but is preferably 0 to 50nm, more preferably 0 to 30nm, and still more preferably 0 to 10nm.
The thickness of the support is not particularly limited, but is preferably 10 to 200. Mu.m, more preferably 10 to 100. Mu.m, and still more preferably 20 to 90. Mu.m.
The support may be formed by stacking a plurality of pieces.
In order to improve adhesion of the support and the layer provided thereon, a surface treatment (for example, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, and flame treatment) may be performed on the surface of the support.
An adhesive layer (primer layer) may be provided on the support.
The support may be a so-called pseudo support or a peelable support.
Further, the surface of the support may be directly subjected to a rubbing treatment. That is, a support subjected to friction treatment may be used. The direction of the rubbing treatment is not particularly limited, and the optimum direction is appropriately selected according to the direction in which the liquid crystal compound is desired to be aligned.
The rubbing treatment can be applied to a treatment method widely used as a liquid crystal alignment treatment process for an LCD (liquid crystal display ). That is, a method of obtaining orientation by wiping the surface of the support in a predetermined direction using paper, gauze, felt, rubber, nylon fiber, polyester fiber, or the like can be used.
The optical film may contain a support and other members than the cured film.
For example, the optical film may have an orientation film between the support and the cured film.
The alignment film can be formed by a rubbing treatment of an organic compound (preferably a polymer), oblique evaporation of an inorganic compound, formation of a layer having micro grooves, or a method of accumulating an organic compound (for example, ω -ditridecanoic acid, dioctadecyl methyl ammonium chloride, methyl stearate) based on langmuir-blodgett method (LB film).
Further, an alignment film that generates an alignment function by applying an electric field, a magnetic field, or light irradiation (preferably polarized light) is also known.
Also, the optical film may have an adhesive layer or an adhesive layer.
As the adhesive constituting the adhesive layer, a known adhesive can be used. The adhesive constituting the adhesive layer may be a known adhesive.
< usage >
The cured film and the optical film of the present invention can be suitably used for various applications.
For example, the cured film or optical film of the present invention can be combined with a polarizer to produce a polarizer. As the polarizing plate, a circular polarizing plate is preferable.
Also, the cured film, optical film or polarizing plate of the present invention may be included in a display device. For example, the cured film and the optical film of the present invention can be used for more specific applications, for example, as an optical compensation film for optically compensating a liquid crystal cell, and the polarizing plate of the present invention can be used for more specific applications, for example, as an antireflection film for use in a display device such as an organic electroluminescence display device.
Among them, a circularly polarizing plate including a cured film as an optically anisotropic film and a polarizer is preferable. The circularly polarizing plate can be preferably used as the antireflection film. That is, in a display device having a display element (for example, an organic electroluminescence display element) and a circularly polarizing plate disposed on the display element, the reflection color tone can be further suppressed.
The polarizer may be a member (linear polarizer) having a function of converting light into specific linearly polarized light, and an absorption type polarizer can be mainly used.
Examples of the absorption type polarizer include iodine type polarizers, dye type polarizers using dichroic dyes, and polyene type polarizers. Among the iodine-based polarizer and the dye-based polarizer, both of a coating-type polarizer and a stretching-type polarizer can be used, but a polarizer produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching the same is preferable.
The relationship between the absorption axis of the polarizer and the slow axis of the cured film as the optically anisotropic film is not particularly limited, but in the case where the optically anisotropic film (cured film) is a λ/4 plate and the optical film is used as a circular polarizing film, the angle formed by the absorption axis of the polarizer and the slow axis of the optically anisotropic film (cured film) is preferably 45 ° ± 10 °.
In addition, the cured film can be used as an optical laminate in combination with other optically anisotropic films. An optical laminate containing the cured film of the present invention may be used as a circular polarizing film in combination with a polarizer, in which case the slow axis of each layer in the optical laminate and the absorption axis of the polarizer are appropriately selected to have an optimal angular relationship.
As described above, when the cured film has regions in which alignment states of liquid crystal compounds different from each other are fixed in the thickness direction, such cured film and the polarizer may be combined to be used as a circular polarizing film, and in this case, the optimum angular relationship between the slow axis of each region in the cured film and the absorption axis of the polarizer is appropriately selected.
The cured film of the present invention is preferably used for an optical compensation film for a liquid crystal display device such as an IPS (In Plane Switching) liquid crystal display device, for example, and can improve a change in color tone when viewed from an oblique direction and light leakage when displayed in black.
Examples
The features of the present invention will be described in more detail below with reference to examples and comparative examples. The materials, amounts used, ratios, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a limiting manner by the following specific examples.
Example 1 >
The following compounds were mixed to prepare a solution 1.
74 parts by mass of a polymerizable liquid crystal compound (1-1)
11 parts by mass of a polymerizable liquid crystal compound (2-1)
15 parts by mass of the polymerizable compound (3-1)
117 parts by mass of methyl isobutyl ketone
39 parts by mass of ethyl propionate
Polymerizable liquid crystalline compound (1-1) (refer to the following chemical formula) (corresponding to the compound represented by formula (1): phase transition temperature from liquid crystal phase to isotropic phase: 123 ℃ C.)
[ chemical formula 7]
Polymerizable liquid crystalline compound (2-1) (refer to the following chemical formula) (corresponding to the compound represented by formula (2): phase transition temperature from liquid crystal phase to isotropic phase: 236 ℃ C.)
[ chemical formula 8]
Polymerizable compound (3-1) (refer to the following chemical formula) (corresponding to the compound represented by formula (3): melting point: 107 ℃ C.). In addition, me represents a methyl group. The polymerizable compound (3-1) does not exhibit liquid crystallinity, and the melting point refers to the phase transition temperature from the solid state to the liquid state.
[ chemical formula 9]
Examples 2 to 10 and comparative examples 1 to 4 >, respectively
Solutions 2 to 10 and solutions C1 to C4 were prepared in the same manner as in example 1, except that the compounds and the composition ratios shown in table 1 were changed.
In addition, each compound used in table 1 is as follows.
Polymerizable liquid crystalline compound (2-2) (refer to the following chemical formula) (corresponding to the compound represented by formula (2): phase transition temperature from liquid crystalline phase to isotropic phase: 300 ℃ C.)
[ chemical formula 10]
Polymerizable compound (3-2) (refer to the following chemical formula) (corresponding to the compound represented by formula (3): melting point: 91 ℃ C.). The polymerizable compound (3-2) exhibits liquid crystallinity, and the melting point refers to the phase transition temperature from the liquid crystal phase to the isotropic phase.
[ chemical formula 11]
The polymerizable compound (3-3) (refer to the following chemical formula) (corresponding to the compound represented by the formula (3): melting point: 87 ℃ C.) further, the polymerizable compound (3-3) exhibits liquid crystallinity, and the melting point refers to the phase transition temperature from the liquid crystal phase to the isotropic phase.
[ chemical formula 12]
Polymerizable compound (3-4) (refer to the following chemical formula) (corresponding to the compound represented by formula (3): melting point: 100 ℃ C.). The polymerizable compound (3-4) does not exhibit liquid crystallinity, and the melting point refers to the phase transition temperature from the solid state to the liquid state.
[ chemical formula 13]
Polymerizable compound (3-5) (refer to the following chemical formula) (corresponding to the compound represented by formula (3): melting point: 78 ℃ C.). The polymerizable compound (3-5) does not exhibit liquid crystallinity, and the melting point refers to the phase transition temperature from the solid state to the liquid state.
[ chemical formula 14]
Polymerizable compounds (3-6) (refer to the following chemical formula) (corresponding to the compound represented by formula (3): melting point: 66 ℃ C.). The polymerizable compounds (3-6) do not exhibit liquid crystallinity, and the melting point refers to the phase transition temperature from the solid state to the liquid state.
[ chemical formula 15]
Polymerizable compounds (3-7) (refer to the following chemical formula) (corresponding to the compound represented by formula (3): melting point: 107 ℃ C.). The polymerizable compounds (3-7) do not exhibit liquid crystallinity, and the melting point refers to the phase transition temperature from the solid state to the liquid state.
[ chemical formula 16]
The phase transition temperature of the polymerizable liquid crystal compound and the polymerizable compound used in the examples from the liquid crystal phase to the isotropic phase and the phase transition temperature from the solid state to the liquid state were determined by the specific methods described above.
< evaluation >
(phase transition temperature test)
The solutions prepared in examples and comparative examples were applied to the rubbed mucous membrane via a rod to volatilize the solvent, and observation samples containing a liquid crystal composition were prepared. Two pieces of polarizers of an optical microscope (Nikon co., ltd. ECLIPSE E600 POL) were arranged in a mutually orthogonal manner, and a sample stage was fixed between the two pieces of polarizers. The prepared observation sample was fixed to a hot stage placed on a sample stage. The phase transition temperature (Iso point) of the liquid crystal composition from the liquid crystal phase to the isotropic phase was measured by heating the sample at 20 ℃/min while observing the state of the sample by a microscope.
The phase transition temperatures obtained were evaluated according to the following criteria. The results are summarized in Table 1.
A: the phase transition temperature is above 110 DEG C
B: the phase transition temperature is more than 100 ℃ and less than 110 DEG C
C: the phase transition temperature is more than 95 ℃ and less than 100 DEG C
D: the phase transition temperature is less than 95 DEG C
(precipitation test)
The solutions prepared in each of examples and comparative examples were immersed in stainless steel plates (SUS 304, longitudinal 2 cm. Times.transverse 2 cm) for 30 seconds, taken out with pliers, and dried at room temperature for 5 minutes. The above procedure was repeated 5 times, and the weight increase of the stainless steel sheet before the test was taken as the precipitation amount (g). In a solution in which crystals are likely to be generated, crystals are likely to precipitate on the stainless steel sheet, and as a result, the weight increase is large as compared with the stainless steel sheet before the test.
The obtained precipitation amount was evaluated according to the following criteria. The results are summarized in Table 1.
A: the precipitation amount is below 0.012g
B: the amount of the precipitate exceeds 0.012g and is 0.020g or less
C: the precipitation amount exceeds 0.020g and is less than 0.025g
D: the precipitation amount is more than 0.025g
(measurement of melting enthalpy)
The polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B), the polymerizable compound (C), and a polymerization inhibitor (Irganox 1010, manufactured by BASF JAPAN ltd.) contained in the solutions prepared in the examples and comparative examples were mixed with acetone to prepare a solution for measuring sample preparation. The content ratio of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C) in the sample preparation solution was measured and was the same as the content ratio of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C) in the solutions of each example and comparative example. The content of the polymerization inhibitor in the sample preparation solution was measured and found to be 1% by mass based on the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B), the polymerizable compound (C) and the polymerization inhibitor. The content of the solvent in the sample preparation solution was measured and found to be 88 mass% based on the total mass of the solution.
The obtained solution for producing a measurement sample was dried under reduced pressure at 30℃for 2 hours, acetone in the solution for producing a measurement sample was removed, and using the obtained solid sample, the solid sample was heated at 5℃per minute from 25℃to 140℃by a differential scanning calorimeter (X-DSC 7000, manufactured by Hitachi High-Tech Science Corporation), and the measurement was performed, whereby the melting enthalpy was calculated. The results are summarized in Table 1.
In table 1, the column of "phase transition temperature (. Degree. C.) of the" polymerizable liquid crystal compound (B) "indicates the phase transition temperature (. Degree. C.) of the polymerizable liquid crystal compound (B) from the liquid crystal phase to the isotropic phase.
In Table 1, the column "melting point (. Degree. C.) of the" polymerizable compound (C) "indicates the melting point (. Degree. C.) of the polymerizable compound (C). However, the "melting point" represents the phase transition temperature (. Degree. C.) from the liquid crystal phase to the isotropic phase when the polymerizable compound (C) exhibits liquid crystallinity, and represents the phase transition temperature (. Degree. C.) from the solid state to the liquid state when the polymerizable compound (C) does not exhibit liquid crystallinity.
In Table 1, the column "functional group type" in the column "polymerizable compound (C)" represents L in the formula (3) 9 、L 10 、L 11 L and L 12 The kind of functional group other than the hydrogen atom corresponding to any one of them.
In Table 1, the column "number of functional groups" in the column "polymerizable compound (C)" represents L in the formula (3) 9 、L 10 、L 11 L and L 12 The number of functional groups other than the hydrogen atom corresponding to any one of the above groups.
In table 1, the numerical value of a in the column of "mass ratio (a/B/C)" represents the ratio (mass%) of the content of the polymerizable liquid crystal compound (a) to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C), the numerical value of B represents the ratio (mass%) of the content of the polymerizable liquid crystal compound (B) to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C), and the numerical value of C represents the ratio (mass%) of the content of the polymerizable compound (C) to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C).
However, in comparative example 2, the content of the polymerizable liquid crystal compound (2-1) was 14.7 mass% with respect to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C), and the content of the polymerizable liquid crystal compound (2-2) was 2.0 mass% with respect to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C).
In example 10, the content of the polymerizable liquid crystal compound (2-1) was 11.9 mass% relative to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C), and the content of the polymerizable liquid crystal compound (2-2) was 1.7 mass% relative to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C).
In table 1, the column "phase transition temperature test" indicates the results of the above phase transition temperature test, and the values in brackets indicate the phase transition temperature (. Degree. C.) of the liquid crystal composition from the liquid crystal phase to the isotropic phase.
In table 1, the column "precipitation test" indicates the results of the above-mentioned precipitation test, and the numerical values in brackets indicate the precipitation amount (g).
TABLE 1
As shown in table 1 above, it was confirmed that the liquid crystal composition according to the present invention can obtain the desired effect. The method of comparative example 2 corresponds to the method specifically disclosed in patent document 1 (example 84).
As is confirmed from the comparison of examples 1 to 4, L in the formula (3) 9 、L 10 、L 11 L and L 12 When the functional group other than the hydrogen atom corresponding to any one of the above is an alkyl group, a more excellent effect can be obtained.
From comparison of examples 4 and 5, it was confirmed that L in formula (3) 9 、L 10 、L 11 L and L 12 When the number of carbons of the alkyl group other than the hydrogen atom corresponding to any one of the above is 7 or less, a more excellent effect can be obtained.
From comparison of examples 6 and 7 with other examples, it was confirmed that more excellent effects were obtained in the case where the number of substituents was 1.
From the comparison of examples 4, 8 and 9, it was confirmed that more excellent effects were obtained when the total content of the polymerizable liquid crystal compound (a) and the polymerizable liquid crystal compound (B) was 50 to 90 mass% with respect to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C) and the content of the polymerizable compound (C) was 10 to 50 mass% with respect to the total amount of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C).
The same evaluation (phase transition temperature test, precipitation test) as in example 1 was further carried out by mixing the following exemplified compounds (ethylene oxide modified trimethylolpropane triacrylate, photopolymerization initiator, levorotatory chiral reagent (L), dextrorotatory chiral reagent (R), polymer (a), polymer (B)) with the solution 1 obtained in example 1, and as a result, the same results were obtained.
Further, even when the compounds exemplified below were further mixed with the solutions 2 to 10 obtained in examples 2 to 10, the same results as those obtained in the respective examples were obtained.
The solution obtained by further mixing the compound exemplified below with the solution 10 obtained in example 10 was referred to as a solution 10A.
4 parts by mass of ethylene oxide modified trimethylolpropane triacrylate (V#360, OSAKA ORGANIC CHEMICAL INDUSTRY LTD.)
3 parts by mass of a photopolymerization initiator (Irgacure 819, manufactured by BASF corporation)
0.45 part by mass of a L-chiral reagent (L)
0.40 part by mass of dextrorotatory chiral reagent (R)
0.08 part by mass of Polymer (A)
0.50 part by mass of polymer (B)
L-chiral reagent (L) (refer to the following chemical formula)
[ chemical formula 17]
Dextrorotatory chiral reagent (R) (refer to the following chemical formula)
[ chemical formula 18]
Polymer A (refer to the following chemical formula)
[ chemical formula 19]
Polymer B (refer to the following chemical formula)
[ chemical formula 20]
Example 11 >
The ingredients described below (cellulose acylate dope) were put into a mixing tank, stirred, and heated at 90℃for 10 minutes. Then, the obtained composition was filtered through a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm to prepare a dope. The solid content concentration of the dope was 23.5 mass%, the addition amount of the plasticizer was a ratio to the cellulose acylate, and the solvent of the dope was methylene chloride/methanol/butanol=81/18/1 (mass ratio).
(cellulose acylate dope) cellulose acylate dope 100 parts by mass of cellulose acylate (acetyl substitution degree 2.86, viscosity average polymerization degree 310)
6.0 parts by mass of sugar ester compound 1 (represented by the formula (S4))
Sugar ester Compound 2 (represented by the formula (S5)) 2.0 parts by mass
0.1 part by mass of a silica particle dispersion (AEROSIL R972, NIPPON AEROSIL CO., LTD.)
Solvent (dichloromethane/methanol/butanol)
[ chemical formula 21]
[ chemical formula 22]
The dope prepared in the above was cast using a roll laminator. The dope was cast from the die so as to be in contact on the metal support cooled to 0 ℃, and then the obtained web (film) was peeled off. In addition, the drum is made of SUS. After the web (film) obtained by casting was peeled off from the drum, at the time of film conveyance, the web was dried in the tenter device at 30 to 40 ℃ for 20 minutes using the tenter device conveyed with both ends of the web sandwiched by jigs. Subsequently, the sheet was fed by a roll and then dried by zone heating. After the obtained web was subjected to knurling treatment, winding was performed. The film thickness of the obtained cellulose acylate film was 40. Mu.m, the in-plane retardation Re (550) at a wavelength of 550nm was 1nm, and the retardation Rth (550) in the thickness direction at a wavelength of 550nm was 26nm.
The cellulose acylate film produced in the above was subjected to a rubbing treatment successively. At this time, the longitudinal direction of the long film was parallel to the conveying direction, and the angle between the film longitudinal direction (conveying direction) and the rotation axis of the rubbing roller was set to 80 °. When the film longitudinal direction (conveying direction) is set to 90 °, the rotation axis of the rubbing roller is set to 10 ° with respect to the film width direction (0 °) as viewed from the film side, and a positive value is indicated as clockwise. In other words, the position of the rotation shaft of the rubbing roller is a position rotated counterclockwise by 80 ° with respect to the film longitudinal direction. The solution 10A prepared in the above was applied to a substrate of the cellulose acylate film subjected to the rubbing treatment using a die coater, to form a composition layer. The resulting composition layer was then heated at 80℃for 60 seconds. Then, the composition layer was irradiated with ultraviolet light (irradiation amount: 35 mJ/cm) at 30℃in an oxygen-containing atmosphere (oxygen concentration: about 20% by volume) using a 365nm LED lamp (manufactured by AcroEdge Corporation) 2 ). Subsequently, the obtained composition layer was heated at 80 ℃ for 10 seconds. Then, nitrogen purging was performed to set the oxygen concentration to 100 ppm by volume, and ultraviolet rays (irradiation amount: 500 mJ/cm) were irradiated to the composition layer at 80℃using a metal halide lamp (EYE GRAPHICS Co., ltd.) 2 ) An optically anisotropic film is formed which fixes the alignment state of the liquid crystal compound. Thus, an optical film in which an optically anisotropic film was disposed on a cellulose acylate film as a support was produced.
The obtained optically anisotropic film had, from the support side, the 2 nd region where the uniformly aligned liquid crystal compound was fixed and the 1 st region where the twist-aligned liquid crystal compound was fixed.
A polyvinyl alcohol (PVA) film having a thickness of 80 μm was immersed in an aqueous iodine solution having an iodine concentration of 0.05 mass% at 30℃for 60 seconds, and dyed. Subsequently, the obtained film was immersed in an aqueous boric acid solution having a boric acid concentration of 4 mass% for 60 seconds, and after stretching in the machine direction at 5 times the original length, it was dried at 50℃for 4 minutes, whereby a polarizer having a thickness of 20 μm was obtained.
A commercially available cellulose acylate-based film was prepared, FUJITAC TG40UL (manufactured by FUJIFILM Corporation), immersed in a 1.5 mol/L aqueous solution of sodium hydroxide at 55℃and then washed thoroughly with water. Then, the obtained film was immersed in a dilute sulfuric acid aqueous solution at 35℃for 1 minute at 0.005 mol/liter, and then immersed in water to sufficiently clean the dilute sulfuric acid aqueous solution. Finally, the obtained film was sufficiently dried at 120℃to prepare a polarizer protective film having a saponification-treated surface.
The optical film produced in the above was subjected to saponification treatment in the same manner as in the production of the polarizer protective film, and the polarizer protective film were continuously bonded to the surface of a support contained in the optical film using a polyvinyl alcohol-based adhesive, thereby producing a long circular polarizing plate. That is, the circularly polarizing plate has a polarizer protective film, a polarizer, a support, and an optically anisotropic film in this order. The absorption axis of the polarizer was aligned with the longitudinal direction of the circularly polarizing plate, and the rotation angle of the in-plane slow axis of the 2 nd region was 10 ° with respect to the absorption axis of the polarizer, and the rotation angle of the in-plane slow axis of the surface of the 1 st region opposite to the 2 nd region side was 85 ° with respect to the absorption axis of the polarizer.
Example 12 >
(production of cellulose acylate film (substrate))
A cellulose acylate film was prepared in the same manner as in example 11.
(formation of a laminate of optically Anisotropic layer (C) and optically Anisotropic layer (B))
(formation of optically Anisotropic layer (1 c))
An optically anisotropic layer coating liquid (1 c) containing a rod-like liquid crystal compound having the following composition was applied onto the cellulose acylate film produced as described above using a die coater, to form a composition layer. Then, both ends of the film were held, a cooling plate (9 ℃) was provided on the side of the film on which the coating film was formed so that the distance from the film became 5mm, and a heating element (75 ℃) was provided on the side of the film opposite to the side on which the coating film was formed so that the distance from the film became 5mm, and the film was dried for 2 minutes.
Next, the mixture was heated with warm air at 60℃for 1 minute, and irradiated with UV-LEDs at 365nm at an irradiation dose of 100mJ/cm while nitrogen purging was performed so as to obtain an ambient gas having an oxygen concentration of 100 ppm by volume or less 2 Is a ultraviolet ray of (a). Then, annealing was performed at 120℃for 1 minute with warm air, thereby forming an optically anisotropic layer (1 c).
The optically anisotropic layer (1 c) thus obtained was irradiated with 7.9mJ/cm at room temperature 2 (wavelength: 313 nm) UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) passing through the wire grid polarizer, thereby forming an optically anisotropic layer (1 c) having orientation control ability on the surface.
The film thickness of the optically anisotropic layer (1 c) thus formed was 0.5. Mu.m. The in-plane retardation Re at a wavelength of 550nm was 0nm, and the retardation Rth in the thickness direction at a wavelength of 550nm was-68 nm. The long axis direction of the rod-like liquid crystal compound was 90 ° relative to the average tilt angle of the film surface, and it was confirmed that the rod-like liquid crystal compound was oriented perpendicularly to the film surface.
Polymerization initiator S-1
[ chemical formula 23]
Photoacid generator D-1
[ chemical formula 24]
Polymer M-1
[ chemical formula 25]
Vertical alignment agent S01
[ chemical formula 26]
Photo-alignment polymer A-1 (the numerical value described in each repeating unit represents the content (mass%) of each repeating unit relative to the total repeating units, and the repeating units on the left side were 43 mass%, 27 mass%, 30 mass%. And the weight average molecular weight was 69800.)
The following polymer A-1 was synthesized by changing the composition ratio by the method described in example 1 of Japanese patent application No. 2020-128049.
[ chemical formula 27]
(formation of optically Anisotropic layer (1 b))
Subsequently, an optically anisotropic layer coating liquid (1 b) containing a rod-like liquid crystal compound having the following composition was applied onto the optically anisotropic layer (1 c) prepared as described above using a die coater, and heated with warm air at 80℃for 60 seconds. Subsequently, the obtained composition layer was subjected to UV irradiation (500 mJ/cm 2 ) The alignment of the liquid crystal compound is immobilized, and an optically anisotropic layer (1 b) is formed.
The optically anisotropic layer (1 b) had a thickness of 1.5 μm, a Δnd at a wavelength of 550nm of 164nm, and a twist angle of the liquid crystal compound of-81 °. When the width direction of the film is 0 ° (90 ° in the longitudinal direction), the alignment axis angle of the liquid crystal compound is-14 ° on the air side and-95 ° on the side contacting the optically anisotropic layer (1 c) when viewed from the optically anisotropic layer (1 b) side.
The alignment axis angle of the liquid crystal compound contained in the optically anisotropic layer was set to 0 ° with respect to the width direction of the substrate, and the substrate was observed from the surface side of the optically anisotropic layer, and the substrate was represented as negative in the clockwise direction (right turn) and positive in the counterclockwise direction (left turn).
The twist angle of the liquid crystal compound is a negative value when the alignment axis direction of the liquid crystal compound on the substrate side (back side) is clockwise (right turn) and a positive value when counterclockwise (left turn) is counterclockwise, based on the alignment axis direction of the liquid crystal compound on the front side (right front side) when the substrate is viewed from the front side of the optically anisotropic layer.
Fluorine-containing compound D (numerical values in each repeating unit represent content (mass%) of total repeating units, content of repeating units on the left side is 76 mass%, content of repeating units on the right side is 24 mass%)
[ chemical formula 28]
By the above steps, a laminate (1 c-1 b) was produced in which the optically anisotropic layer (1 c) and the optically anisotropic layer (1 b) were directly laminated on the long cellulose acylate film.
Example 13 >
As shown in Table 2, a laminate (1 c-2 b) was produced in the same manner as in example 12, except that the composition ratios of the polymerizable liquid crystal compound (1-1), the polymerizable liquid crystal compound (2-2) and the polymerizable compound (3-4) in the optically anisotropic layer-forming composition (1 b) were changed.
< evaluation >
(dent defect)
The above-mentioned laminates (1 c-1 b) and (1 c-2 b) were cut into a size of 20 cm. Times.20 cm, placed in an observation window provided with a polarizing plate in crossed nicols, and the dent defects of the optically anisotropic layers (1 b) and (2 b) placed on the side opposite to the cellulose acylate film side were counted visually. In addition, a failure that appears to fall off in a circle or an ellipse is regarded as a dent defect. The evaluation of the dent defect is C if 5 or more dent defects, B if 1 to 4 dent defects, and a if no dent defects. The results are summarized in Table 2.
In Table 2, "(1-1) + (2-1) + (2-2)" indicates the ratio (mass%) of the total amount of the polymerizable liquid crystal compound (1-1), the polymerizable liquid crystal compound (2-1), and the polymerizable liquid crystal compound (2-2) to the total amount of the polymerizable liquid crystal compound (1-1), the polymerizable liquid crystal compound (2-2), and the polymerizable compound (3-4), and "(3-4)" indicates the ratio (mass%) of the total amount of the polymerizable compound (3-4) to the polymerizable liquid crystal compound (1-1), the polymerizable liquid crystal compound (2-2), and the polymerizable compound (3-4).
In examples 12 and 13, the composition ratio of the polymerizable liquid crystal compound (1-1), the polymerizable liquid crystal compound (2-1) and the polymerizable liquid crystal compound (2-2) was 84/14/2.
TABLE 2
From the results of table 2, it was confirmed that, when the total content of the polymerizable compounds (C) was 5 to 50 mass% with respect to the total amount of the polymerizable liquid crystal compounds (a), the polymerizable liquid crystal compounds (B) and the polymerizable compounds (C), the dishing defect was further suppressed.
Claims (19)
1. A liquid crystal composition comprising:
a polymerizable liquid crystal compound (A) having 3 ring structures in the molecular long axis direction;
a polymerizable liquid crystal compound (B) having 4 or more ring structures in the molecular long axis direction and having a phase transition temperature from the liquid crystal phase to the isotropic phase of 150 ℃ or higher; a kind of electronic device with high-pressure air-conditioning system
The polymerizable compound (C) is a compound different from the polymerizable liquid crystal compound (A), has 3 ring structures in the molecular long axis direction, and has a melting point of 65 to 120 ℃.
2. The liquid crystal composition according to claim 1, wherein,
the melting enthalpy is less than 35 mJ/mg.
3. The liquid crystal composition according to claim 1 or 2, wherein,
the polymerizable liquid crystal compound (A) is a compound represented by the formula (1),
the polymerizable liquid crystal compound (B) has a phase transition temperature from a liquid crystal phase to an isotropic phase of 150 ℃ or higher and is represented by the formula (2),
the polymerizable compound (C) has a melting point of 65-120 ℃ and is represented by the formula (3),
in the formula (1), R 1 Represents a hydrogen atom or a methyl group,
A 1 represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted by-O-and,
Z 1 z is as follows 2 Each independently represents-COO-, -O-or a single bond,
X 1 a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a vinyl group, a formyl group, a nitro group, a cyano group, an acetyl group, an acetoxy group, an N-acetylamido group, an acryloylamino group, an N, N-dimethylamino group, a maleimide group, a methacryloylamino group, an allyloxy group, an allyloxycarbamoyl group, an N-alkyloxycarbamoyl group having 1 to 4 carbon atoms in the alkyl group, an N- (2-methacryloxyethyl) carbamoyl group, an N- (2-acryloxyethyl) carbamoyl group, or a group represented by the formula (1A),
L 1 、L 2 、L 3 L and L 4 Independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a halogen atom, L 1 、L 2 、L 3 L and L 4 At least 1 of which represents a group other than a hydrogen atom,
formula (1A) x-A 2 -P 1
In the formula (1A), A 2 Represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted by-O-and,
P 1 represents a hydrogen atom, an acryloyloxy group or a methacryloyloxy group,
* The bonding position is indicated by the number of the bonding sites,
in the formula (2), R 2 Represents a hydrogen atom or a methyl group,
A 3 represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted by-O-and,
Z 3 、Z 4 、Z 5 z is as follows 6 Each independently represents-COO-, -O-or a single bond,
Q 1 q and Q 2 Each independently represents an aromatic ring group or an alicyclic group which may have a substituent having 1 to 12 carbon atoms,
X 2 a linear alkyl group having 1 to 4 carbon atoms, a halogen atom, a methoxy group, an ethoxy group, an aromatic ring group which may have a substituent, a cyclohexyl group, a vinyl group, a formyl group, a nitro group, a cyano group, an acetyl group, an acetoxy group, an N-acetylamide group, an acryloylamino group, an N, N-dimethylamino group, a maleimido group, a methacryloylamino group, an allyloxy group, an allyloxycarbamoyl group, an N-alkyloxycarbamoyl group having 1 to 4 carbon atoms of an alkyl group, an N- (2-methacryloyloxyethyl) carbamoyl group, an N- (2-acryloyloxyethyl) carbamoyl group, or a group represented by the following formula (2A),
L 5 、L 6 、L 7 L and L 8 Independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a halogen atom, L 5 、L 6 、L 7 L and L 8 At least 1 of which represents a group other than a hydrogen atom,
x and y each independently represent 0, 1 or 2, at least one of x and y represents 1 or 2,
formula (2A) x-A 4 -P 2
In the formula (2A), A 4 Represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted by-O-and,
P 2 represents a hydrogen atom, an acryloyloxy group or a methacryloyloxy group,
* The bonding position is indicated by the number of the bonding sites,
in the formula (3), R 3 R is R 6 Represents a hydrogen atom or a methyl group,
A 5 a is a 6 Each independently represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted by-O-and,
Z 7 z is as follows 8 Each independently represents-COO-, -O-or a single bond,
L 9 、L 10 、L 11 l and L 12 Independently of one another, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, a formyl group, a cyano group, a nitro group, an N-alkylamido group having 1 to 12 carbon atoms, an N, N-dialkylamino group having 1 to 12 carbon atoms, a maleimido group, an acryloylamino group, a methacryloylamino group, an allyloxy group, an allyloxycarbamoyl group, an N-alkyloxycarbamoyl group having 1 to 12 carbon atoms, an N- (2-methacryloyloxyethyl) carbamoyl group, an N- (2-acryloyloxyethyl) carbamoyl group, or a halogen atom, L 9 、L 10 、L 11 L and L 12 At least 1 of them represents a group other than a hydrogen atom or a methyl group.
4. The liquid crystal composition according to claim 3, wherein,
in the formula (3), L 9 、L 10 、L 11 L and L 12 Independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 12 carbon atoms, L 9 、L 10 、L 11 L and L 12 At least 1 of them represents a group other than a hydrogen atom or a methyl group.
5. The liquid crystal composition according to claim 3 or 4, wherein,
in the formula (3), L 9 、L 10 、L 11 L and L 12 Independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, L 9 、L 10 、L 11 L and L 12 At least 1 of them represents a group other than a hydrogen atom or a methyl group.
6. The liquid crystal composition according to any one of claims 3 to 5, wherein,
the polymerizable liquid crystal compound (A) is a compound represented by the formula (1-1),
in the formula (1-1), R 1 R is R 4 Represents a hydrogen atom or a methyl group,
A 1 a is a 2 Each independently represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted by-O-and,
Z 1 z is as follows 2 Each independently represents-COO-, -O-or a single bond,
L 1 、L 2 、L 3 l and L 4 Independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a halogen atom, L 1 、L 2 、L 3 L and L 4 At least 1 of which represents a group other than a hydrogen atom.
7. The liquid crystal composition according to claim 6, wherein,
in the formula (1-1), L 1 、L 2 、L 3 L and L 4 Each independently represents a hydrogen atom or a methyl group, L 1 、L 2 、L 3 L and L 4 At least 1 of which represents methyl.
8. The liquid crystal composition according to any one of claims 3 to 7, wherein,
in the formula (2), Q 1 Q and Q 2 Each independently represents an aromatic ring which may have a substituent having 1 to 12 carbon atoms,
X 2 represents a group represented by the formula (2B),
x and y each independently represent 0 or 1, x+y is 1 or 2,
in the formula (2B), R 5 Represents a hydrogen atom or a methyl group,
A 4 represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 May be substituted by-O-and,
* Indicating the bonding location.
9. The liquid crystal composition according to any one of claims 3 to 8, wherein,
the polymerizable liquid crystal compound (B) contains at least 1 compound selected from the group consisting of a compound represented by the formula (2-1) and a compound represented by the formula (2-2),
in the formula (2-1) and the formula (2-2), R 2 R is R 5 Each independently represents a hydrogen atom or a methyl group,
A 3 a is a 4 Each independently represents an alkylene group having 2 to 18 carbon atoms, 1 CH in the alkylene group 2 Or not adjacent more than 2 CH 2 Can be substituted by-O-)，
Z 4 Z is as follows 5 Each independently represents-COO-, -O-or a single bond,
L 5 、L 6 、L 7 l and L 8 Independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a halogen atom, L 5 、L 6 、L 7 L and L 8 At least 1 of which represents a group other than a hydrogen atom.
10. The liquid crystal composition according to claim 9, wherein,
in the formula (2-1) and the formula (2-2), L 5 、L 6 、L 7 L and L 8 Each independently represents a hydrogen atom or a methyl group, L 5 、L 6 、L 7 L and L 8 At least 1 of which represents methyl.
11. The liquid crystal composition according to any one of claims 3 to 10, wherein,
the total content of the compound represented by the formula (1) and the compound represented by the formula (2) is 50 to 95% by mass based on the total amount of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3),
the content of the compound represented by the formula (3) is 5 to 50% by mass based on the total amount of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3).
12. The liquid crystal composition according to any one of claims 3 to 11, wherein,
The total content of the compound represented by the formula (1) and the compound represented by the formula (2) is 60 to 90% by mass relative to the total amount of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3),
the content of the compound represented by the formula (3) is 10 to 40% by mass based on the total amount of the compound represented by the formula (1), the compound represented by the formula (2) and the compound represented by the formula (3).
13. The liquid crystal composition according to any one of claims 1 to 12, further comprising a polymerizable compound different from any one of the polymerizable liquid crystal compound (a), the polymerizable liquid crystal compound (B) and the polymerizable compound (C).
14. The liquid crystal composition according to any one of claims 1 to 13, further comprising a polymerization initiator.
15. A cured film obtained by curing the liquid crystal composition according to any one of claims 1 to 14.
16. The cured film of claim 15, wherein the cured film is an optically anisotropic film.
17. The cured film according to claim 15, wherein the cured film is a film obtained by fixing a twisted orientation liquid crystal phase.
18. A polarizing plate comprising the cured film of claim 15, and a polarizer.
19. An image display device comprising the cured film of claim 15, or the polarizing plate of claim 18.
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| PCT/JP2022/003992 WO2022168851A1 (en) | 2021-02-05 | 2022-02-02 | Liquid crystal composition, cured film, polarizing plate, and image display device |
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| JP4708287B2 (en) * | 2006-08-25 | 2011-06-22 | 富士フイルム株式会社 | Manufacturing method of optical film, optical film, polarizing plate, transfer material, liquid crystal display device, and polarized ultraviolet exposure device |
| EP2129743B1 (en) * | 2007-03-30 | 2010-11-10 | Merck Patent GmbH | Birefringent polymer film with negative optical dispersion |
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| EP3246378B1 (en) * | 2016-05-17 | 2019-03-20 | Merck Patent GmbH | Polymerisable liquid crystal material and polymerised liquid crystal film |
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