CN113620805B - Polymerizable compound, composition, and optically anisotropic body - Google Patents
Polymerizable compound, composition, and optically anisotropic body Download PDFInfo
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- CN113620805B CN113620805B CN202110836384.0A CN202110836384A CN113620805B CN 113620805 B CN113620805 B CN 113620805B CN 202110836384 A CN202110836384 A CN 202110836384A CN 113620805 B CN113620805 B CN 113620805B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 64
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- 230000003287 optical effect Effects 0.000 abstract description 16
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 238000004383 yellowing Methods 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 142
- -1 homography Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 125000003545 alkoxy group Chemical group 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 14
- 125000002947 alkylene group Chemical group 0.000 description 14
- 125000004438 haloalkoxy group Chemical group 0.000 description 14
- 125000001188 haloalkyl group Chemical group 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 125000004093 cyano group Chemical group *C#N 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 12
- 150000002367 halogens Chemical group 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 8
- 230000009977 dual effect Effects 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 125000003302 alkenyloxy group Chemical group 0.000 description 6
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- 125000004448 alkyl carbonyl group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 125000000262 haloalkenyl group Chemical group 0.000 description 6
- 125000005291 haloalkenyloxy group Chemical group 0.000 description 6
- 125000004993 haloalkoxycarbonyl group Chemical group 0.000 description 6
- 125000004692 haloalkylcarbonyl group Chemical group 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
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- 239000000463 material Substances 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HSFWJUIIFWCPBM-UHFFFAOYSA-N 4-carbonochloridoyloxybutyl prop-2-enoate Chemical compound ClC(=O)OCCCCOC(=O)C=C HSFWJUIIFWCPBM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 101000767534 Arabidopsis thaliana Chorismate mutase 2 Proteins 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 101000986989 Naja kaouthia Acidic phospholipase A2 CM-II Proteins 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
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- 230000001070 adhesive effect Effects 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000005755 decalin-2,6-ylene group Chemical group [H]C1([H])C([H])([H])C2([H])C([H])([H])C([H])([*:2])C([H])([H])C([H])([H])C2([H])C([H])([H])C1([H])[*:1] 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001543 furan-2,5-diyl group Chemical group O1C(=CC=C1*)* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- RNPZEWACDMXHOX-UHFFFAOYSA-N ClCCCCCCC(C(=C)C)=O Chemical compound ClCCCCCCC(C(=C)C)=O RNPZEWACDMXHOX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004890 Hydrophobing Agent Substances 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229940008309 acetone / ethanol Drugs 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
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- 235000005513 chalcones Nutrition 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/94—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
-
- 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
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polarising Elements (AREA)
Abstract
Disclosed is a polymerizable compound selected from the group consisting of compounds of the general formula (1). Further, a polymerizable composition and an optically anisotropic body formed from the polymerizable compound are also disclosed. The polymerizable compound is capable of exhibiting one or more of favorable substrate high adhesion, high transparency to Vis-light, reduced random yellowing, and good high temperature stability in RM optical retardation films.
Description
Technical Field
The present invention relates to a polymerizable compound and a method for producing the same, a polymerizable composition and a method for producing the same, and applications of the polymerizable compound and the polymerizable composition in various optically anisotropic bodies.
Background
Polymerizable (mesogenic) compounds (RM) are receiving increasing attention as starting materials for the preparation of various optically anisotropic bodies. The prior art generally applies a solution of a polymerizable compound onto a substrate, aligns it, and cures it by heating or irradiating an activating energy ray, thereby forming an optically anisotropic polymer film having a uniform orientation, also called optically anisotropic body. The orientation of the film may be planar (liquid crystal molecules oriented substantially parallel to the layer), homeotropic (rectangular or perpendicular to the layer) or tilted, or cholesteric.
Depending on the application field, the optically anisotropic body includes, but is not limited to, an optical retardation film (phase difference film), an optical compensation film, a vision-expanding film, a reflection film, a selective reflection film, an antireflection film, a brightness enhancement film, a liquid crystal alignment film, a polarizing element, a circular polarizing element, an elliptical polarizing element, and other various optical elements.
The polymerizable compounds, although stable at room temperature, degrade at elevated temperatures. For example, after heating for a period of time, the dispersed or delayed optical properties decrease, resulting in a decrease in the properties of the optically anisotropic body over time. This can be attributed to the low degree of polymerization, correspondingly high residual radical content of the polymer, shrinkage or thermooxidative degradation of the polymer, etc., as reported by various studies.
The optically anisotropic body is required to have various characteristics satisfying required optical characteristics, polymerization rate, solubility, melting point or glass transition temperature, transparency, mechanical strength, surface hardness, heat resistance, light resistance, and the like. In many cases, it is desirable to use polymerizable compositions containing two or more polymerizable compounds. Thus, the properties of the optically anisotropic body depend not only on the kind of polymerizable compound used but also on the proportion of the polymerizable compound.
In one example, the desired characteristics of the optical retardation film (e.g., homography, film structure, film adhesion, temperature stability, and optical properties) all depend on the particular composition of the polymerizable composition. For this purpose, one possible way of adjusting the alignment distribution in the direction perpendicular to the film plane is to rationally select the ratio of mono-reactive mesogenic compounds and di-reactive mesogenic compounds. Furthermore, RM optical retardation films with low diacrylate content are very suitable for applications where good adhesion of the RM optical retardation film to the substrate is important. However, in RM optical retardation films with low diacrylate content, the optical retardation generally drops significantly, especially due to polymer shrinkage.
Therefore, there is a demand for development of a polymerizable compound or a polymerizable composition, the use of which can solve the above-mentioned technical problems.
Disclosure of Invention
It is an object of the present invention to provide a polymerizable compound capable of exhibiting one or more of favorable substrate high adhesion in RM optical retardation films, high transparency to Vis-light, reduced random yellowing, and good high temperature stability. Further, the compound can exhibit not only favorable substrate high adhesion in the RM optical retardation film but also good high temperature stability.
It is a second object of the present invention to further provide a polymerizable composition and a polymerizable composition solution comprising the polymerizable compound as described above and below.
It is a further object of the present invention to provide the use of the polymerizable compounds and polymerizable compositions described above and below.
In order to achieve the above object, in one aspect, the present invention provides a polymerizable compound selected from compounds of the general formula (1),
In the method, in the process of the invention,
P 1 and P 2 each independently represent a polymerizable group;
Each L 1-L4 independently represents a single bond 、-O-、-S-、-NH-、-CO-、-OCO-、-COO-、-SCO-、-COS-、-OCOO-、-NHCO-、-CONH-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-OCF2-、-CF2O-、-SCF2-、-CF2S-、-CH＝CHOCO-、-CH＝CHCOO-、-OCOCH＝CH-、-COOCH＝CH-、-CH2CH2OCO-、-CH2CH2COO-、-OCOCH2CH2-、-COOCH2CH2-、-CH2OCO-、-CH2COO-、-OCOCH2-、-COOCH2-、-CH＝CH-、-N＝CH-、-CH＝N-、-N＝N-、-CH＝CF-、-CF＝CH-、-N＝CF-、-CF＝N-、-C≡C- or an alkylene group having 1 to 30 carbon atoms; one or more of the alkylene groups-CH 2 -may be substituted with-O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-; when there are a plurality of L 1-L4, they may be the same or different;
C 1 and C 2 each independently represent -O-、-S-、-NH-、-CO-、-OCO-、-COO-、-SCO-、-COS-、-OCOO-、-NHCO-、-CONH-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-OCF2-、-CF2O-、-SCF2-、-CF2S-、-CH＝CHOCO-、-CH＝CHCOO-、-OCOCH＝CH-、-COOCH＝CH-、-CH2CH2OCO-、-CH2CH2COO-、-OCOCH2CH2-、-COOCH2CH2-、-CH2OCO-、-CH2COO-、-OCOCH2-、-COOCH2-、-CH＝CH-、-N＝CH-、-CH＝N-、-N＝N-、-CH＝CF-、-CF＝CH-、-N＝CF-、-CF＝N-、-C≡C- or a single bond;
Ring a represents a group selected from:
(a) 1, 4-cyclohexylene; wherein 1-CH 2 -or non-adjacent more than 2-CH 2 -present therein may be substituted with-O-, -S-, -NH-;
(b) 1, 4-phenylene; wherein 1-ch=or non-adjacent 2 or more-ch=present may be substituted with-n=;
(c) 1, 4-cyclohexenylene, 2, 4-cyclopentadiene-2, 5-diyl, thiophene-2, 5-diyl, furan-2, 5-diyl, piperidine-2, 5-diyl, naphthalene-2, 6-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, decalin-2, 6-diyl;
The above-mentioned group (a), group (b) or group (c) may each independently be substituted with halogen, cyano, alkyl of 1 to 30 carbon atoms, haloalkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, haloalkoxy of 1 to 30 carbon atoms, alkenyl of 2 to 30 carbon atoms, haloalkenyl of 2 to 30 carbon atoms, alkenyloxy of 2 to 30 carbon atoms, haloalkenyloxy of 2 to 30 carbon atoms, alkoxycarbonyl of 1 to 30 carbon atoms, haloalkoxycarbonyl of 1 to 30 carbon atoms, alkylcarbonyl of 1 to 30 carbon atoms, haloalkylcarbonyl of 1 to 30 carbon atoms, alkanoyloxy of 1 to 30 carbon atoms or haloalkoyloxy of 1 to 30 carbon atoms;
R 1 and R 2 each independently represents an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a haloalkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a haloalkenyl group having 2 to 30 carbon atoms, an alkenyloxy group having 2 to 30 carbon atoms, a haloalkenyloxy group having 2 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, a haloalkoxycarbonyl group having 1 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, a haloalkylcarbonyl group having 1 to 30 carbon atoms, an alkylacyloxy group having 1 to 30 carbon atoms or a haloalkylacyloxy group having 1 to 30 carbon atoms; m and n each independently represent an integer of 0 to 8.
As the compound of the general formula (1), wherein the polymerizable group is selected from the following groups:
Wherein R 3 each independently represents a hydrogen atom, halogen, cyano, alkyl group having 1 to 30 carbon atoms, haloalkyl group having 1 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, haloalkoxy group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, haloalkenyl group having 2 to 30 carbon atoms, alkenyloxy group having 2 to 30 carbon atoms, haloalkenyloxy group having 2 to 30 carbon atoms, alkoxycarbonyl group having 1 to 30 carbon atoms, haloalkoxycarbonyl group having 1 to 30 carbon atoms, alkylcarbonyl group having 1 to 30 carbon atoms, haloalkylcarbonyl group having 1 to 30 carbon atoms, alkylacyloxy group having 1 to 30 carbon atoms or haloalkylacyloxy group having 1 to 30 carbon atoms.
As the compound of the general formula (1), P 1 and P 2 each independently represent a group of (P-1) and (P-2).
As a compound of the general formula (1), wherein ring A represents 1, 4-phenylene; wherein 1-ch=or non-adjacent 2 or more-ch=present may be substituted with-n=; and/or ring A may be substituted with halogen, cyano, alkyl of 1 to 30 carbon atoms, haloalkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, haloalkoxy of 1 to 30 carbon atoms, alkylacyloxy of 1 to 30 carbon atoms, and haloalkylacyloxy of 1 to 30 carbon atoms.
Preferably, ring A may be substituted with halogen, cyano, alkyl of 1 to 20 carbon atoms, haloalkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, haloalkoxy of 1 to 20 carbon atoms, alkylacyloxy of 1 to 20 carbon atoms and haloalkylacyloxy of 1 to 20 carbon atoms.
Further preferably, ring A may be substituted with halogen, cyano, alkyl of 1 to 10 carbon atoms, haloalkyl of 1 to 10 carbon atoms, alkoxy of 1 to 10 carbon atoms, haloalkoxy of 1 to 10 carbon atoms, alkylacyloxy of 1 to 10 carbon atoms and haloalkylacyloxy of 1 to 10 carbon atoms.
More preferably, ring A may be substituted with halogen, cyano, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylacyloxy of 1 to 6 carbon atoms and haloalkylacyloxy of 1 to 6 carbon atoms.
As the compound of the general formula (1), wherein each L 1-L2 independently represents an alkylene group having 1 to 30 carbon atoms; one or more of the alkylene groups-CH 2 -may be substituted with-O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-; and/or L 3-L4 each independently represents a single bond 、-O-、-S-、-NH-、-CO-、-OCO-、-COO-、-SCO-、-COS-、-OCOO-、-NHCO-、-CONH-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-OCF2-、-CF2O-、-SCF2-、-CF2S-.
Preferably, each L 1-L2 independently represents an alkylene group of 1 to 30 carbon atoms; and/or the number of the groups of groups, L 3-L4 each independently represents-OCO-, -COO-, -SCO-, COS-, -OCOO-, -NHCO-, -CONH-.
Further preferably, each L 1-L2 independently represents an alkylene group having 2 to 20 carbon atoms; and/or the number of the groups of groups, L 3-L4 each independently represents-OCO-, -COO-, SCO-, -COS-, -OCOO-.
More preferably, each L 1-L2 independently represents an alkylene group of 2 to 15 carbon atoms; and/or, L 3-L4 each independently represents-OCO-, -COO-.
As the compound of the general formula (1), wherein, C 1 and C 2 each independently represent-OCO-, -COO-, -SCO-, -COS-, -OCOO-.
Preferably, the method comprises the steps of, C 1 and C 2 each independently represent-OCO-, -COO-, -OCOO-.
In another aspect, the present invention also provides a polymerizable composition comprising a single reactive mesogenic compound and a dual reactive mesogenic compound, characterized in that the dual reactive mesogenic compound comprises a compound of formula (1) as described above and below.
As context of the polymerizable composition, wherein the dual reactive mesogenic compound further comprises a compound of general formula (2),
In the method, in the process of the invention,
P 1 'and P 2' each independently represent a polymerizable group;
L 1'-L4' each independently represents a single bond 、-O-、-S-、-NH-、-CO-、-OCO-、-COO-、-SCO-、-COS-、-OCOO-、-NHCO-、-CONH-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-OCF2-、-CF2O-、-SCF2-、-CF2S-、-CH＝CHOCO-、-CH＝CHCOO-、-OCOCH＝CH-、-COOCH＝CH-、-CH2CH2OCO-、-CH2CH2COO-、-OCOCH2CH2-、-COOCH2CH2-、-CH2OCO-、-CH2COO-、-OCOCH2-、-COOCH2-、-CH＝CH-、-N＝CH-、-CH＝N-、-N＝N-、-CH＝CF-、-CF＝CH-、-N＝CF-、-CF＝N-、-C≡C- or an alkylene group having 1 to 30 carbon atoms; one or more of the alkylene groups-CH 2 -may be substituted with-O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-; when there are a plurality of L 1'-L4', they may be the same or different;
C 1 'and C 2' each independently represent -O-、-S-、-NH-、-CO-、-OCO-、-COO-、-SCO-、-COS-、-OCOO-、-NHCO-、-CONH-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-OCF2-、-CF2O-、-SCF2-、-CF2S-、-CH＝CHOCO-、-CH＝CHCOO-、-OCOCH＝CH-、-COOCH＝CH-、-CH2CH2OCO-、-CH2CH2COO-、-OCOCH2CH2-、-COOCH2CH2-、-CH2OCO-、-CH2COO-、-OCOCH2-、-COOCH2-、-CH＝CH-、-N＝CH-、-CH＝N-、-N＝N-、-CH＝CF-、-CF＝CH-、-N＝CF-、-CF＝N-、-C≡C- or a single bond;
Ring a' represents a group selected from:
(a) 1, 4-cyclohexylene; wherein 1-CH 2 -or non-adjacent more than 2-CH 2 -present therein may be substituted with-O-, -S-, -NH-;
(b) 1, 4-phenylene; wherein 1-ch=or non-adjacent 2 or more-ch=present may be substituted with-n=;
(c) 1, 4-cyclohexenylene, 2, 4-cyclopentadiene-2, 5-diyl, thiophene-2, 5-diyl, furan-2, 5-diyl, piperidine-2, 5-diyl, naphthalene-2, 6-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, decalin-2, 6-diyl;
The above-mentioned group (a), group (b) or group (c) may each independently be substituted with halogen, cyano, alkyl of 1 to 30 carbon atoms, haloalkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, haloalkoxy of 1 to 30 carbon atoms, alkenyl of 2 to 30 carbon atoms, haloalkenyl of 2 to 30 carbon atoms, alkenyloxy of 2 to 30 carbon atoms, haloalkenyloxy of 2 to 30 carbon atoms, alkoxycarbonyl of 1 to 30 carbon atoms, haloalkoxycarbonyl of 1 to 30 carbon atoms, alkylcarbonyl of 1 to 30 carbon atoms, haloalkylcarbonyl of 1 to 30 carbon atoms, alkanoyloxy of 1 to 30 carbon atoms or haloalkoyloxy of 1 to 30 carbon atoms;
R 1 'and R 2' each independently represent an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a haloalkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a haloalkenyl group having 2 to 30 carbon atoms, an alkenyloxy group having 2 to 30 carbon atoms, a haloalkenyloxy group having 2 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, a haloalkoxycarbonyl group having 1 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, a haloalkylcarbonyl group having 1 to 30 carbon atoms, an alkylacyloxy group having 1 to 30 carbon atoms or a haloalkylacyloxy group having 1 to 30 carbon atoms; m and n each independently represent an integer of 0 to 4.
As the compound of the general formula (2), wherein the polymerizable group is selected from the following groups:
Wherein R 3 each independently represents a hydrogen atom, halogen, cyano, alkyl group having 1 to 30 carbon atoms, haloalkyl group having 1 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, haloalkoxy group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, haloalkenyl group having 2 to 30 carbon atoms, alkenyloxy group having 2 to 30 carbon atoms, haloalkenyloxy group having 2 to 30 carbon atoms, alkoxycarbonyl group having 1 to 30 carbon atoms, haloalkoxycarbonyl group having 1 to 30 carbon atoms, alkylcarbonyl group having 1 to 30 carbon atoms, haloalkylcarbonyl group having 1 to 30 carbon atoms, alkylacyloxy group having 1 to 30 carbon atoms or haloalkylacyloxy group having 1 to 30 carbon atoms.
As the compound of the general formula (2), wherein P 1 'and P 2' each independently represent a group of (P-1) and (P-2).
As the compound of the general formula (2), wherein the ring a' represents a1, 4-phenylene group; wherein 1-ch=or non-adjacent 2 or more-ch=present may be substituted with-n=; and/or ring A' may be substituted with halogen, cyano, alkyl of 1 to 30 carbon atoms, haloalkyl of 1 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, haloalkoxy of 1 to 30 carbon atoms, alkylacyloxy of 1 to 30 carbon atoms, and haloalkylacyloxy of 1 to 30 carbon atoms.
Preferably, ring A' may be substituted with halogen, cyano, alkyl of 1 to 20 carbon atoms, haloalkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, haloalkoxy of 1 to 20 carbon atoms, alkylacyloxy of 1 to 20 carbon atoms and haloalkylacyloxy of 1 to 20 carbon atoms.
Further preferably, ring A' may be substituted with halogen, cyano, alkyl of 1 to 10 carbon atoms, haloalkyl of 1 to 10 carbon atoms, alkoxy of 1 to 10 carbon atoms, haloalkoxy of 1 to 10 carbon atoms, alkylacyloxy of 1 to 10 carbon atoms and haloalkylacyloxy of 1 to 10 carbon atoms.
More preferably, ring A' may be substituted with halogen, cyano, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkylacyloxy of 1 to 6 carbon atoms and haloalkylacyloxy of 1 to 6 carbon atoms.
As the compound of the general formula (2), wherein each L 1'-L2' independently represents an alkylene group having 1 to 30 carbon atoms; one or more of the alkylene groups-CH 2 -may be substituted with-O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-; and/or L 3'-L4' each independently represents a single bond 、-O-、-S-、-NH-、-CO-、-OCO-、-COO-、-SCO-、-COS-、-OCOO-、-NHCO-、-CONH-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-OCF2-、-CF2O-、-SCF2-、-CF2S-.
Preferably, L 1'-L2' each independently represents an alkylene group of 1 to 30 carbon atoms; and/or the number of the groups of groups, L 3-L4 each independently represents-OCO-, -COO-, -SCO-, COS-, -OCOO-, -NHCO-, -CONH-.
Further preferably, each L 1'-L2' independently represents an alkylene group having 2 to 20 carbon atoms; and/or the number of the groups of groups, L 3'-L4' each independently represents-OCO-, -COO-, -SCO-, -COS-, -OCOO-.
More preferably, each L 1'-L2' independently represents an alkylene group of 2 to 15 carbon atoms; and/or, L 3'-L4' each independently represents-OCO-, -COO-.
As the compound of the general formula (2), wherein, C 1 'and C 2' each independently represent-O-; -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-, -OCOO-.
Preferably, the method comprises the steps of, C 1 'and C 2' each independently represent-O-, -S-, -NH-, -CO-, -OCO-, -COO-, -OCOO-.
As context requires, the polymerizable composition wherein the content of the dual reactive mesogenic compound is 80-99 wt. -%, based on the total weight of the polymerizable composition.
Preferably, the content of the dual reactive mesogenic compound is 85-98wt%, based on the total weight of the polymerizable composition; more preferably, the content of the dual reactive mesogenic compound is 90-97wt%, based on the total weight of the polymerizable composition; and, most preferably, the content of the dual reactive mesogenic compound is 92-96.5wt%, based on the total weight of the polymerizable composition.
As the context of the polymerizable composition, wherein the content of the compound of the general formula (1) as described in the context is 6 to 18wt% based on the total weight of the polymerizable composition.
Preferably, the compound of formula (1) is present in an amount of 8 to 15wt%, based on the total weight of the polymerizable composition; more preferably, the compound of formula (1) is present in an amount of 9 to 14wt%, based on the total weight of the polymerizable composition; and, most preferably, the compound of formula (1) is present in an amount of 10 to 12wt% based on the total weight of the polymerizable composition.
In one embodiment, the dual reactive mesogenic compound consists of a compound of formula (1) and a compound of formula (2).
As context requires, the polymerizable composition wherein the content of the mono-reactive mesogenic compound is 0.5-10 wt. -%, based on the total weight of the polymerizable composition.
Preferably, the content of the single reactive mesogenic compound is from 1 to 8wt%, based on the total weight of the polymerizable composition; more preferably, the content of the single reactive mesogenic compound is from 1.5 to 6wt%, based on the total weight of the polymerizable composition; and, most preferably, the content of the single reactive mesogenic compound is from 2 to 5wt%, based on the total weight of the polymerizable composition.
As a polymerizable composition, as described above and below, further comprises an additive.
As the additive, there are included, but not limited to, polymerization initiator, sensitizer, stabilizer, leveling agent, surfactant, polymerization inhibitor, antioxidant, colorant, dispersant, lubricant, hydrophobing agent, adhesive, flow improver, defoamer, deaerator, diluent, thixotropic agent, gelling agent, catalyst, metal complex, luminescent material, and the like.
Advantageously, the content of additives is from 0.01 to 10% by weight, preferably from 0.02 to 8% by weight, more preferably from 0.05 to 5% by weight, and most preferably from 0.1 to 2% by weight, based on the total weight of the polymerizable composition.
In yet another aspect, the present invention also provides a polymerizable composition solution comprising a polymerizable composition as described above and below and an organic solvent.
As the organic solvent, it is preferable that the solubility to the polymerizable composition is good, and that it can be removed by drying at 100 ℃ or less. Organic solvents, including, but not limited to,
The organic solvent in which the polymerizable liquid crystal compound exhibits good solubility is not particularly limited, but is preferably an aromatic solvent such as toluene, xylene, cumene, mesitylene, or the like; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and the like; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; ether solvents such as tetrahydrofuran, 1, 2-dimethoxyethane, anisole, and amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, gamma-butyrolactone, chlorobenzene, and the like.
The organic solvents described above and below may be used alone or in combination of two or more.
From the viewpoint of solution stability, it is preferable to use one or more of a ketone solvent, an ether solvent, an ester solvent, and an aromatic solvent.
As the polymerizable composition solution, wherein the organic solvent content is 30 to 95wt%, preferably 40 to 90wt%, more preferably 50 to 85wt%, and most preferably 60 to 80wt%, based on the total weight of the polymerizable composition solution.
In preparing the polymerizable composition solution, heating and/or stirring is advantageously performed in order to promote dissolution of the polymerizable composition.
In yet another aspect, the present invention also provides an optically anisotropic body comprising a substrate and a polymeric film formed by solution curing of the polymerizable composition described above and below, and, if desired, an oriented film.
In one embodiment, a base material, an alignment film, if necessary, and a polymer film formed by curing a polymerizable composition solution are sequentially laminated to form an optically anisotropic body.
In another embodiment, the substrate, the orientation film if necessary, and the polymer film formed by curing the polymerizable composition solution are sequentially laminated, and then a second orientation film if necessary, and a second polymer film formed by curing the polymerizable composition solution described above and below or a polymerizable composition solution different therefrom are sequentially laminated thereon.
Substrates for optically anisotropic bodies include, but are not limited to, glass substrates, metal substrates, ceramic substrates, and polymeric substrates. Further, as the polymer substrate, for example, there may be mentioned: cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyethersulfones, polyamides, polyimides, polyphenylene sulfides, polyphenylene oxides or polystyrenes, and the like.
The process applicability based on optically anisotropic bodies, in particular, polyester, polystyrene, polyolefin, cellulose derivatives, polyarylates, polycarbonates are preferred from the viewpoint of heat resistance and chemical stability.
As the alignment film material of the optically anisotropic body, polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene oxide, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, acrylic resin, epoxy acrylic resin, coumarin, chalcone, cinnamate, anthraquinone, azo compound, aryl vinyl compound, and the like are included, but not limited thereto.
The orientation treatment may be a stretching treatment, a rubbing treatment, polarized ultraviolet-visible light irradiation, an ion beam treatment, or the like. Preferably the orientation treatment is preferably a rubbing treatment or polarized uv-vis irradiation.
As a coating method for obtaining the optically anisotropic body of the present invention, methods known in the art such as an applicator method, a bar coating method, a spin coating method, a gravure printing method, a flexographic printing method, an inkjet method, a die coating method, a CAP coating method, and dipping can be used. After the polymerizable composition solution is applied, it is dried.
In the case of polymerizing the solution of the polymerizable composition of the present invention, it is desirable to rapidly polymerize the composition, and therefore, it is preferable to polymerize the composition by irradiation with active energy rays such as ultraviolet-visible light or electron rays. In the case of using ultraviolet-visible light, a polarized light source may be used, or an unpolarized light source may be used.
The optically anisotropic body of the present invention is advantageously a retardation film. The retardation film of the present invention is produced in the same manner as the optically anisotropic body of the present invention.
When the polymerizable compound in the polymerizable composition solution is polymerized in a planar orientation state, a retardation film having in-plane birefringence with respect to the substrate can be obtained.
When the polymerizable compound and the polymerizable chiral compound in the polymerizable composition solution are polymerized in a planar orientation state, a retardation film having birefringence out of plane with respect to the substrate can be obtained.
When the polymerizable compound and the polymerizable discotic compound in the polymerizable composition solution are polymerized in a planar orientation state, a retardation film having birefringence with respect to the substrate both in-plane and out-of-plane can be obtained.
When the base material has a similar retardation, the retardation film of the present invention is superimposed on the birefringence of the base material to obtain a birefringent retardation film. The birefringence of the two may be the same or different in the plane of the substrate.
Detailed Description
In the present invention, technical terms are further explained and defined in detail.
The term "liquid crystal" or "mesogenic compound" refers to a compound that forms a mesogenic or liquid crystal phase under certain conditions.
The term "polymerizable mesogenic" or "polymerizable compound" is abbreviated as RM and denotes polymerizable liquid crystal or mesogenic compounds, in particular monomeric compounds.
The term "single reactive" or "double reactive" means that the polymerizable mesogenic or polymerizable compound has one or two polymerizable groups.
The term "polymerizable group" means a group that is polymerized by means of light, heat, or a catalyst to form a higher molecular weight polymer.
The term "film" means a rigid or flexible coating or layer having mechanical stability; optionally, the film may be present alone; on top of the support substrate; or sandwiched between two substrates.
The term "R" or "Re" denotes an optical retardation amount, particularly, a phase retardation amount between ordinary rays and extraordinary rays.
The term "R λ" or "Re λ" represents the amount of phase retardation at normal incidence to the film plane at wavelength λnm.
The term "R in" or "Re in" represents the amount of phase delay at the initial time.
The present invention is further described below with reference to synthesis examples and examples, which are not intended to limit the scope of the invention. Unless otherwise indicated, the percentages in the examples are by mass.
Synthesis example 1: synthesis of Compound A
Synthesis of intermediate A-1:
10g of 6-hydroxy-2-anthranilic acid is added into a 500ml reaction bottle, 8.4g of diisopropylethylamine and 200ml of dichloromethane are added, then 4-acryloyloxy butyl chloroformate is dropwise added at the temperature of 0-5 ℃, the temperature is kept for 2 hours after the dropwise addition, the organic layer is subjected to aftertreatment, 6N hydrochloric acid is used for washing, drying and concentration are carried out, a viscous solid is obtained, ethanol is added for pulping, suction filtration is carried out, the solid is crystallized by a mixed solvent of dichloromethane and petroleum ether again, and the solid is obtained, the liquid phase content is 96.7%, and the yield is 74%.
Synthesis of compound a:
10g of compound A-1 is put into a reaction bottle, 200ml of dichloromethane and 2 drops of DMF are added, then oxalyl chloride is dripped at the temperature of 20-25 ℃, the temperature is kept for 4 hours at the temperature of 25 ℃ after the dripping is finished, solvent and redundant oxalyl chloride are removed by rotary evaporation, new dichloromethane 200ml,1, 4-dihydroxyl-2-methyl benzoate 2g are added again, diisopropylethylamine 4.8g is dripped at the temperature of 0-5 ℃ and the temperature is kept for 2 hours after the dripping is finished, 6N hydrochloric acid is added for washing, drying and concentration are carried out, ethanol is pulped to obtain solid, and the solid is crystallized by using a mixture solvent of acetone/toluene/ethanol to obtain the compound A8.1g with the yield of 69 percent and the liquid phase content of 94.2 percent.
The structure of compound A is characterized by ：1H NMR(400MHz,DMSO-d6)：δ8.79(s,2H),8.72(s,2H),8.44(s,2H),8.05(d,J＝8Hz,2H),8.02(d,J＝9Hz,2H),7.88(dd,J＝8Hz,2Hz,2H),7.41(d,J＝2Hz,2H),7.22(dd,J＝9Hz,2Hz,2H),7.10(m,1H),6.95(d,J＝8.8Hz,2H),6.32(dd,J＝17.4,1.4Hz,2H),6.17(dd,J＝17.4,10.5Hz,2H),5.84(dd,J＝10.3Hz,1.6Hz,2H),4.20(t,J＝5.9Hz,4H),4.10(t,J＝5.9Hz,4H),3.94(s,3H),1.63-1.79(m,8H).
Synthesis example 2: synthesis of Compound B
Synthesis of intermediate B-1:
10g of 6-hydroxy-2-anthranilic acid, 2.6g of o-methyl hydroquinone, 0.5g of potassium hydrogen sulfate, 100ml of trimethylbenzene, heating, refluxing and water diversion for 30h, cooling to room temperature, filtering, washing a filter cake twice with methanol slurry, and drying to obtain 19.7g, wherein the filter cake is directly used for the next reaction without purification.
Synthesis of compound B:
10g of intermediate B-1,4.5g of triethylamine and 100ml of dichloromethane are added into a 250ml three-neck flask, 8.1g of chloroformate 4-acryloxybutyl ester is dropwise added under stirring at the temperature of 0-5 ℃, the reaction is carried out for 1 hour after the dropwise addition is finished, then the temperature is raised to 30 ℃ for reaction for 4 hours, 50ml of 10% hydrochloric acid is added for washing, 2% sodium bicarbonate aqueous solution is used for washing to neutrality, 50ml of dichloromethane is concentrated, 200ml of ethanol is added, solid precipitation is carried out, suction filtration is carried out, crude products are obtained, and 10.35g of white products with the content of 95.4% and the yield of 64.5% are obtained after drying toluene column chromatography and ethanol slurry washing.
The structure of compound B is characterized by ：1H NMR(400MHz,DMSO-d6)：δ8.72(s,2H),8.70(s,2H),8.44(s,2H),8.05(d,J＝8Hz,2H),8.02(d,J＝9Hz,2H),7.88(dd,J＝8Hz,2Hz,2H),7.41(d,J＝2Hz,2H),7.22(dd,J＝9Hz,2Hz,2H),7.13(m,1H),6.95(d,J＝8.8Hz,2H),6.32(dd,J＝17.4,1.4Hz,2H),6.17(dd,J＝17.4,10.5Hz,2H),5.94(dd,J＝10.3,1.6Hz,2H),4.25(t,J＝5.9Hz,4H),4.15(t,J＝5.9Hz,4H),2.16(s,3H),1.68-1.79(m,8H).
Synthesis example 3: synthesis of Compound C
10G of intermediate B-1, 100g of DMF, 5.4g of potassium carbonate, heating to 80 ℃, adding 5.6g of 6-chloro-1-methacryloyl hexane, preserving heat for 12 hours to the end of the reaction after the dripping, cooling, adding water into the system, separating out the product, filtering, collecting a filter cake, crystallizing the filter cake by using a mixed solvent of dichloromethane/acetone/ethanol to obtain 9.4g, wherein the content is 92.7%, and the yield is 60%.
The structure of compound C is characterized by ：1H NMR(400MHz,DMSO-d6)：δ(8.01-8.84(t,12H),7.31-7.54(m,3H),6.94-7.17(q,4H)6.42(d,2H),6.38(d,2H),4.17(t,4H),4.04(t,4H),2.23(s,3H),2.01(s,3H),1.84(m,4H),1.72(m,4H),1.66-1.36(m,8H).
Example 1:
Durability test
The retardation rate (R in) of each cured film was measured using a Axoscan ellipsometer. The R in was analyzed using a light source with a wavelength of 550 nm. To determine the retardation dispersion R in-450/Rin-550, the retardation of the material was measured at wavelengths of 450nm and 550nm, and if not otherwise stated, each film was then placed in an oven at 85 ℃ for a total time of 100 hours, and if not otherwise stated after 100 hours the film was removed from the oven and cooled to room temperature, and the retardation curve was again recorded, and the durability was quantified by the difference between R in and R in-450/Rin-550 before and after oven testing.
Adhesion test
The adhesion of the film to the substrate was tested using the Nichiban 305 tape test. The adhesive tape was thus applied 305 to a polymer film, which was then peeled off sharply, and if the film was not removed, the adhesion was considered to pass. The adhesive composition is characterized by comprising X, delta and o, wherein X and delta are respectively completely separated from the substrate and a certain adhesion property.
The mixture used:
Mixture CM-1
Mixture CM-2
Mixture CM-3
Experiment 1.1 mixture CM-1 was dissolved in toluene/cyclopentanone (7:3) at 33.3% solids, and the solution was coated with Meyer rod #05 onto a TAC substrate coated with an alignment layer. The film was annealed at 65 ℃ for 120 seconds and cured under a nitrogen atmosphere using a fused H bulb lamp (75% power, 10 m/min). The film was laminated onto a pressure sensitive adhesive and covered with blank glass, so the total film was TAC/polymer film/pressure sensitive adhesive/glass, and durability experiments were performed on the film.
Experiment 1.2 mixture CM-2 was dissolved in toluene/cyclopentanone (7:3) at 33.3% solids, and the solution was coated with Meyer rod #05 onto a TAC substrate coated with an alignment layer. The film was annealed at 65 ℃ for 120 seconds and cured under a nitrogen atmosphere using a fusion H bulb lamp (75% power, 10 m/min), laminated onto a pressure sensitive adhesive and covered with blank glass, so the total film was laminated as TAC/polymer film/pressure sensitive adhesive/glass, and durability experiments were performed on the film.
Experiment 1.3 mixture CM-3 was dissolved in toluene/cyclopentanone (7:3) at 33.3% solids, and the solution was coated with Meyer rod #05 onto a TAC substrate coated with an alignment layer. The film was annealed at 65 ℃ for 120 seconds and cured under a nitrogen atmosphere using a fused H bulb lamp (75% power, 10 m/min). The film was laminated onto a pressure sensitive adhesive and covered with blank glass, so the total film was TAC/polymer film/pressure sensitive adhesive/glass, and durability experiments were performed on the film.
The results are shown in Table 1.
As can be seen from table 1, the polymerizable compound, composition and optically anisotropic body of the present invention are capable of exhibiting not only favorable high adhesion of the substrate in the RM optical retardation film but also good high temperature stability.
It should be understood that the description of the specific embodiments is merely illustrative of the principles and spirit of the invention, and not in limitation thereof. Further, it should be understood that various changes, substitutions, omissions, modifications, or adaptations to the present invention may be made by those skilled in the art after having read the present disclosure, and such equivalent embodiments are within the scope of the present invention as defined in the appended claims.
Claims (3)
1. A solution of a polymerizable composition selected from the group consisting of mixture CM-1, having the composition:
the content of the compound is% -W/W BYK-388.5%;
2. an optically anisotropic body comprising a substrate and a polymer film formed by solution curing the polymerizable composition of claim 1.
3. The optically anisotropic body according to claim 2, wherein the optically anisotropic body is selected from a phase difference film.
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