CN112534022A - Polymerizable liquid crystal composition and liquid crystal display element - Google Patents
Polymerizable liquid crystal composition and liquid crystal display element Download PDFInfo
- Publication number
- CN112534022A CN112534022A CN201980051672.6A CN201980051672A CN112534022A CN 112534022 A CN112534022 A CN 112534022A CN 201980051672 A CN201980051672 A CN 201980051672A CN 112534022 A CN112534022 A CN 112534022A
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- liquid crystal
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- mass
- carbon atoms
- crystal composition
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 291
- 239000000203 mixture Substances 0.000 title claims abstract description 192
- 150000001875 compounds Chemical class 0.000 claims abstract description 359
- 125000004432 carbon atom Chemical group C* 0.000 claims description 154
- 125000000217 alkyl group Chemical group 0.000 claims description 105
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 64
- 238000001179 sorption measurement Methods 0.000 claims description 53
- 125000003545 alkoxy group Chemical group 0.000 claims description 45
- 239000000758 substrate Substances 0.000 claims description 45
- 125000002947 alkylene group Chemical group 0.000 claims description 34
- 125000005843 halogen group Chemical group 0.000 claims description 28
- 230000001939 inductive effect Effects 0.000 claims description 21
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 13
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 5
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 230000007547 defect Effects 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 68
- 125000004122 cyclic group Chemical group 0.000 description 47
- -1 acryloyloxy group Chemical group 0.000 description 26
- 239000010408 film Substances 0.000 description 24
- 125000004093 cyano group Chemical group *C#N 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 229910052731 fluorine Inorganic materials 0.000 description 17
- 125000001153 fluoro group Chemical group F* 0.000 description 17
- 230000008859 change Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 125000001309 chloro group Chemical group Cl* 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 125000000962 organic group Chemical group 0.000 description 8
- 125000006850 spacer group Chemical group 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 230000000274 adsorptive effect Effects 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 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 4
- 239000004642 Polyimide Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 210000002858 crystal cell Anatomy 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004988 Nematic liquid crystal Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000004375 physisorption Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 2
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 125000005725 cyclohexenylene group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical group 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- WYFCZWSWFGJODV-MIANJLSGSA-N 4-[[(1s)-2-[(e)-3-[3-chloro-2-fluoro-6-(tetrazol-1-yl)phenyl]prop-2-enoyl]-5-(4-methyl-2-oxopiperazin-1-yl)-3,4-dihydro-1h-isoquinoline-1-carbonyl]amino]benzoic acid Chemical compound O=C1CN(C)CCN1C1=CC=CC2=C1CCN(C(=O)\C=C\C=1C(=CC=C(Cl)C=1F)N1N=NN=C1)[C@@H]2C(=O)NC1=CC=C(C(O)=O)C=C1 WYFCZWSWFGJODV-MIANJLSGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125846 compound 25 Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000006238 prop-1-en-1-yl group Chemical group [H]\C(*)=C(/[H])C([H])([H])[H] 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- 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
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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- 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
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
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- 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
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/16—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon double bonds, e.g. stilbenes
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- 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
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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- 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
- C09K19/38—Polymers
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- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
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- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G—PHYSICS
- G02—OPTICS
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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Abstract
The present invention provides a liquid crystal composition containing a polymerizable compound, which does not inhibit orientation constraint force for vertically aligning liquid crystal molecules, does not or rarely cause display defects due to changes in pretilt angle, and has a high voltage holding ratio, and a liquid crystal display element using the liquid crystal composition. The liquid crystal composition of the present invention solves the above problems by providing a liquid crystal composition containing a specific polymerizable compound, and a liquid crystal display element using the liquid crystal composition.
Description
Technical Field
The present invention relates to a liquid crystal composition containing a polymerizable compound and a liquid crystal display element using the same.
Background
In general, liquid crystal display elements such as liquid crystal panels and liquid crystal displays change the alignment state of liquid crystal molecules by external stimuli such as electric fields, and use the change in optical properties associated with the change in alignment state for display. In general, such a liquid crystal display element is configured such that a gap between two transparent substrates is filled with liquid crystal molecules, and an alignment film for aligning the liquid crystal molecules in a specific direction in advance is formed on a surface of the substrate in contact with the liquid crystal molecules.
However, there are the following problems: the problem of the occurrence of alignment defects due to damage or dust occurring on the surface of an alignment film in the process of manufacturing a liquid crystal display element is that it is difficult to design and manage an alignment film for obtaining uniform alignment over the entire surface of a substrate for a long time as the substrate size increases.
In contrast, in recent years, liquid crystal display elements have been developed which do not require an alignment film by using a liquid crystal composition containing a spontaneous alignment material for controlling the alignment of liquid crystal molecules in a liquid crystal layer (patent documents 1 and 2).
The liquid crystal display element requiring no alignment film is manufactured in such a manner that: a liquid crystal composition containing a polymerizable compound and containing a liquid crystal compound, a spontaneous alignment material and a polymerizable compound is injected between substrates, and the spontaneous alignment material and the polymerizable compound are polymerized while liquid crystal molecules are aligned by applying a voltage, thereby fixing the alignment of the liquid crystal molecules. Factors of display defects (i.e., burn-in) of the liquid crystal display element include factors caused by impurities and changes in the alignment of liquid crystal molecules (changes in pretilt angle).
The burn-in caused by the change of the pretilt angle of the liquid crystal molecules is: when a liquid crystal display element is configured, the structure of the polymer changes when the same pattern is displayed for a long time, and as a result, the pretilt angle changes. Therefore, a polymerizable compound which forms a polymer having a rigid structure without changing the polymer structure is required.
Documents of the prior art
Patent document
Patent document 1: U.S. patent publication 2017-0123275
Patent document 2: japanese laid-open patent publication No. 2015-168826
Disclosure of Invention
Problems to be solved by the invention
The invention provides a liquid crystal composition containing a polymerizable compound, which does not hinder the orientation constraint force for vertically aligning liquid crystal molecules, inhibits the residual polymerizable compound when the liquid crystal display element is manufactured, and does not generate or generates very little display defects caused by the reduction of voltage holding ratio and the change of pretilt angle; and a liquid crystal display element using the liquid crystal composition.
Means for solving the problems
The present inventors have made extensive studies and as a result, have found that the above problems can be solved by a liquid crystal composition containing 1 or 2 or more polymerizable compounds represented by the general formula (i), and have completed the present invention.
[ solution 1]
(in the formula, Xi1、Xi2、Xi3、Xi4、Xi5、Xi6、Xi7、Xi8、Xi9、Xi10、Xi11And Xi12Each independently represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom,
is selected from Xi1～Xi12At least two of (a) each independently represent an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a halogen atom,
Pi1and Pi2Each independently represents any one of the following formulae (R-I) to (R-IX),
[ solution 2]
(in the formula, R21、R31、R41、R51And R61Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, W represents a single bond, -O-, or methylene, T represents a single bond or-COO-, p, T, and q each independently represents 0, 1, or 2),
Spi1and Spi2Each independently represents a single bond or an alkylene group having 1 to 15 carbon atoms, and 1 or 2 or more-CH in the alkylene group2Can be substituted by-O-, -OCO-or-COO-in such a way that the oxygen atoms are not directly adjacent,
ni1represents a number of 0, 1 or 2,
Li1and Li2Each independently represents a single bond, -OCH2-、-CH2O-、-C2H4-、-OC2H4O-、-COO-、-OCO-、-CH＝CRa-COO-、-CH＝CRa-OCO-、-COO-CRa＝CH-、-OCO-CRa＝CH-、-(CH2)z-COO-、-(CH2)z-OCO-、-OCO-(CH2)z-、-COO-(CH2)z-、-CH＝CH-、-CF2O-、-OCF2-or-C ≡ C- (wherein, R isaRepresents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, z represents an integer of 1 to 4),
when there are a plurality of Xi5、Xi6、Xi7、Xi8And/or Li2In the case of (3), they may be the same or different. )
Further, the present invention aims to provide a liquid crystal display element using the liquid crystal composition, a liquid crystal display element for driving an active matrix using the liquid crystal composition, a liquid crystal display element for PSA mode, PSVA mode, PS-IPS mode, or PS-FSS mode using the liquid crystal composition, and a liquid crystal display element using the liquid crystal composition and having no alignment film on at least one of a pair of substrates.
ADVANTAGEOUS EFFECTS OF INVENTION
By using the polymerizable liquid crystal composition of the present invention, a liquid crystal display element with little change in pretilt angle can be obtained. In addition, a liquid crystal display element produced using the polymerizable liquid crystal composition of the present invention has the following features: has a high Voltage Holding Ratio (VHR), and further, the amount of unpolymerized polymerizable compound in the device is extremely small.
Detailed Description
In the above general formula (i), Xi1、Xi2、Xi3、Xi4、Xi5、Xi6、Xi7、Xi8、Xi9、Xi10、Xi11And Xi12Each independently represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, and the alkyl group and the alkoxy group are preferably linear, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a fluorine atom or a chlorine atom, preferably a hydrogen atom, a methyl group, an ethyl groupA methoxy group or a fluorine atom, preferably a hydrogen atom, a methyl group, a methoxy group or a fluorine atom. Preferably 2 or more are groups other than hydrogen atoms, preferably 2 or 3 are groups other than hydrogen atoms, and preferably 2 are groups other than hydrogen atoms.
The alkyl group and the alkoxy group preferably have 10 to 18 carbon atoms when importance is placed on the orientation of the liquid crystal, and preferably have 1 to 4 carbon atoms when importance is placed on the solubility in the liquid crystal compound. In addition, when importance is attached to the tilt angle stability, an alkyl group is preferable. The alkyl group and the alkoxy group may be linear or branched, and are particularly preferably linear.
Preferably Xi1、Xi2、Xi3、Xi4、Xi5、Xi6、Xi7、Xi8、Xi9、Xi10、Xi11And Xi12Wherein 2 or more of the alkyl groups represent any of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom, and the alkyl group and the alkoxy group preferably have 10 to 18 carbon atoms when the orientation of the liquid crystal is important, and preferably have 1 to 4 carbon atoms when the solubility in the liquid crystal compound is important. In addition, when importance is attached to the tilt angle stability, an alkyl group is preferable. The alkyl group and the alkoxy group may be linear or branched, and are particularly preferably linear.
In addition, when importance is attached to the voltage holding ratio, X is preferablei5、Xi6、Xi7、Xi8、Xi9、Xi10、Xi11And Xi12At least one of them is an alkyl group having 1 to 18 carbon atoms. The preferred number of carbon atoms of the alkyl group is 10 to 18 when importance is placed on the orientation of the liquid crystal, and 1 to 4 when importance is placed on the solubility in the liquid crystal compound. In addition, when importance is attached to the tilt stability, the tilt stability is preferably 1 to 3. The alkyl group may be linear or branched, and is particularly preferably linear.
In the general formula (i), X is preferably used in order to reduce the amount of residual monomers after UV irradiationi11Or Xi121 or 2 of (a) are hydrogen atoms。
In the general formula (i), when importance is attached to solubility in the liquid crystal composition, X is preferably usedi5、Xi6、Xi7、Xi8、Xi9、Xi10、Xi11And Xi12At least 1 or more of (2) are halogen atoms, and fluorine is particularly preferable.
In the above general formula (i), n isi1When the value is 1, X is selected when the tilt angle stability is importanti5、Xi6、Xi7And Xi8The 2 of (3) are preferably an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom, and particularly preferably an alkyl group having 1 to 3 carbon atoms, or fluorine.
In the above general formula (i), Li1Preferably a single bond, -OCH2-、-CH2O-、-C2H4-、-COO-、-OCO-、-CH＝CH-COO-、-CH＝CH-OCO-、-COO-CH＝CH-、-OCO-CH＝CH-、-C2H4-COO-、-C2H4-OCO-、-OCO-C2H4-、-COO-C2H4-、-CH＝CH-、-CF2O-、-OCF2-or-C ≡ C-, more preferably a single bond, -OCH2-、-CH2O-、-C2H4-、-COO-、-OCO-、-C2H4-COO-、-C2H4-OCO-、-OCO-C2H4-、-COO-C2H4-、-CF2O-、-OCF2-or-C.ident.C-, particularly preferably a single bond.
In the above general formula (i), Li2Preferably a single bond, -OCH2-、-CH2O-、-C2H4-、-COO-、-OCO-、-CH＝CH-COO-、-CH＝CH-OCO-、-COO-CH＝CH-、-OCO-CH＝CH-、-C2H4-COO-、-C2H4-OCO-、-OCO-C2H4-、-COO-C2H4-、-CH＝CH-、-CF2O-、-OCF2-or-C ≡ C-, more preferably a single bond, -OCH2-、-CH2O-、-C2H4-、-COO-、-OCO-、-C2H4-COO-、-C2H4-OCO-、-OCO-C2H4-、-COO-C2H4-、-CH＝CH-、-CF2O-、-OCF2-or-C.ident.C-, particularly preferably a single bond.
In the above general formula (i), Li1And Li2May be the same as or different from each other, more preferably Li1And Li2The same is true.
In the general formula (i), Pi1And Pi2Each independently represents any one of the following formulae (R-I) to (R-IX).
[ solution 3]
(in the formula, R21、R31、R41、R51And R61Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, W represents a single bond, -O-, or methylene, T represents a single bond or-COO-, and p, T, and q each independently represents 0, 1, or 2. )
Among them, in the above general formula (i), Pi1And Pi2Each independently preferably represents formula (R-I), formula (R-II), formula (R-III), formula (R-IV), formula (R-V) or formula (R-VII), more preferably formula (R-I), formula (R-II), formula (R-III) or formula (R-IV), more preferably formula (R-I), and further preferably acryloyloxy group (R-I) wherein R is21A substituent of a hydrogen atom) or a methacryloxy group (R in (R-I)21A substituent of a methyl group), more preferably a methacryloyloxy group.
In the general formula (i), Spi1And Spi2Each of the groups is preferably a single bond or an alkylene group having 1 to 3 carbon atoms, and more preferably a single bond.
The polymerizable compound represented by the general formula (i) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The liquid crystal composition according to the present invention preferably contains 1 to 5 kinds of polymerizable compounds represented by the general formula (i), preferably 1 to 4 kinds of polymerizable compounds represented by the general formula (i), and preferably 1 to 3 kinds of polymerizable compounds represented by the general formula (i).
The lower limit of the content of the polymerizable compound represented by the general formula (i) in the liquid crystal composition of the present invention is preferably 0.05 mass%, preferably 0.08 mass%, preferably 0.1 mass%, preferably 0.15 mass%, preferably 0.17 mass%, preferably 0.2 mass%, preferably 0.22 mass%, preferably 0.25 mass%, preferably 0.27 mass%, preferably 0.3 mass%, preferably 0.32 mass%, preferably 0.35 mass%, preferably 0.37 mass%, preferably 0.4 mass%, preferably 0.42 mass%, preferably 0.45 mass%, preferably 0.48 mass%, preferably 0.5 mass%, preferably 0.53 mass%, preferably 0.55 mass%, preferably 0.58 mass%, preferably 0.60 mass%, preferably 0.63 mass%, preferably 0.65 mass%, preferably 0.68 mass%, preferably 0.70 mass%, preferably 0.73 mass%, preferably 0.75 mass%, preferably 0.78 mass%, preferably 0.8 mass%. The upper limit of the content of the polymerizable compound represented by the general formula (i) in the liquid crystal composition of the present invention is preferably 2.5% by mass, preferably 2.3% by mass, preferably 2.1% by mass, preferably 2% by mass, preferably 1.8% by mass, preferably 1.6% by mass, preferably 1.5% by mass, preferably 1% by mass, preferably 0.95% by mass, preferably 0.9% by mass, preferably 0.85% by mass, preferably 0.8% by mass, preferably 0.75% by mass, preferably 0.7% by mass, preferably 0.65% by mass, preferably 0.6% by mass, preferably 0.55% by mass, preferably 0.5% by mass, preferably 0.45% by mass, and preferably 0.4% by mass.
When the polymerizable compound represented by the general formula (i) is used alone, it is preferably used in a small amount from the viewpoint of storage stability at low temperature, and when a plurality of polymerizable compounds represented by the general formula (i) are used in combination, it is preferably used in a large amount in order to more exhibit the effects of the present invention.
In order to achieve both storage stability at low temperatures and a change in pretilt angle, the content of the polymerizable compound represented by the general formula (i) in the liquid crystal composition of the present invention is preferably 0.1 to 1%, preferably 0.2 to 0.8%, preferably 0.3 to 0.75%, preferably 0.35 to 0.7%, and preferably 0.4 to 0.7%. Suitable compounds of the polymerizable compound represented by the general formula (i) according to the present invention include the following formulae RM-1 to RM-33.
[ solution 4]
[ solution 5]
The above formulae RM-1 to RM-33 are preferable, RM-3 to RM-11 and RM-22 to RM-30 are more preferable, and RM-3, RM-11, RM-25 and RM-28 to RM-30 are still more preferable.
The liquid crystal composition according to the present invention contains the polymerizable compound represented by the general formula (i), but other polymerizable compounds may be used in combination. The other polymerizable compound is preferably a compound represented by the following general formula (P). It is preferable that 1 or 2 or more of the polymerizable monomers are contained.
[ solution 6]
(in the above general formula (P), Rp1Represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or-Spp2-Pp21 or non-adjacent 2 or more-CH groups in the alkyl group2-is independently substituted with-CH- ═ CH-, -C.ident.C-, -O-, -CO-, -COO-or-OCO-, respectively, 1 or 2 or more hydrogen atoms in the alkyl group may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively,
Pp1and Pp2Each independently represents a general formula (P)p1-1) to formula (P)p1-any one of the above-mentioned-9),
[ solution 7]
(in the formula, Rp11And Rp12Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, Wp11Represents a single bond, -O-, -COO-or methylene, tp11Represents 0, 1 or 2, and a plurality of R exist in the moleculep11、Rp12、Wp11And/or tp11They may be the same or different. )
Spp1And Spp2Each independently represents a single bond or a spacer,
Zp1and Zp2Each independently represents a single bond, -O-, -S-, -CH2-、-OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-OCOOCH2-、-CH2OCOO-、-OCH2CH2O-、-CO-NRZP1-、-NRZP1-CO-、-SCH2-、-CH2S-、-CH＝CRZP1-COO-、-CH＝CRZP1-OCO-、-COO-CRZP1＝CH-、-OCO-CRZP1＝CH-、-COO-CRZP1＝CH-COO-、-COO-CRZP1＝CH-OCO-、-OCO-CRZP1＝CH-COO-、-OCO-CRZP1＝CH-OCO-、-(CH2)2-COO-、-(CH2)2-OCO-、-OCO-(CH2)2-、-(C＝O)-O-(CH2)2-、-CH＝CH-、-CF＝CF-、-CF＝CH-、-CH＝CF-、-CF2-、-CF2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-or-C ≡ C- (wherein, R isZP1Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a plurality of R's are present in the moleculeZP1When they are the same or different),
Ap1、Ap2and Ap3Each independently represents a group selected from the group consisting of (a)p) Group (c)p) A group of the group consisting of,
(ap)1, 4-cyclohexylideneRadical (1-CH present in the radical)2-or non-contiguous 2 or more-CH2Optionally substituted by-O) -,
(bp)1, 4-phenylene (1-CH-present in the radical or nonadjacent 2 or more-CH-may be substituted by-N), and
(cp) Naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, phenanthrene-2, 7-diyl or anthracene-2, 6-diyl (1-CH ═ or nonadjacent 2 or more-CH ═ s present in these groups may be substituted by-N ═ s),
present in the above-mentioned group (a)p) Group (b)p) And a group (c)p) Wherein 1 or 2 or more hydrogen atoms are independently substituted by a halogen atom, a cyano group, an alkyl group having 1 to 8 carbon atoms or-Spp2-Pp2Substituted, 1 or non-adjacent 2 or more-CH in the alkyl group2-is independently substitutable with-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-,
mp1represents 0, 1,2 or 3, and a plurality of Z's are present in the moleculep1、Ap2、Spp2And/or Pp2When they are the same or different, in mp1Is 0 and Ap1When it is phenanthrene-2, 7-diyl or anthracene-2, 6-diyl Ap3Represents a single bond.
Except for the compound represented by the general formula (i). )
In the general formula (P) related to the invention, Rp1Is preferably-Spp2-Pp2。
Pp1And Pp2Are each independently preferably of the formula (P)p1-1) to formula (P)p1-3), preferably (P)p1-1)。
Rp11And Rp12Each independently preferably a hydrogen atom or a methyl group.
tp11Preferably 0 or 1.
Wp11Preferably a single bond, methylene or ethylene.
mp1Preferably 0, 1 or 2, preferably 0 or 1.
Zp1And Zp2Are respectively independentPreferably a single bond, -OCH2-、-CH2O-、-CO-、-C2H4-、-COO-、-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-C2H4COO-、-CH＝CH-、-CF2-、-CF2O-、-(CH2)2-COO-、-(CH2)2-OCO-、-OCO-(CH2)2-、-CH＝CH-COO-、-COO-CH＝CH-、-OCOCH＝CH-、-COO-(CH2)2-、-OCF2-or-C ≡ C-, preferably a single bond, -OCH2-、-CH2O-、-C2H4-、-COO-、-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-C2H4COO-、-CH＝CH-、-(CH2)2-COO-、-(CH2)2-OCO-、-OCO-(CH2)2-、-CH＝CH-COO-、-COO-CH＝CH-、-OCOCH＝CH-、-COO-(CH2)2-or-C.ident.C-, preferably only 1 present in the molecule is-OCH2-、-CH2O-、-C2H4-、-COO-、-OCO-、-COOC2H4-、-OCOC2H4-、-C2H4OCO-、-C2H4COO-、-CH＝CH-、-(CH2)2-COO-、-(CH2)2-OCO-、-OCO-(CH2)2-、-CH＝CH-COO-、-COO-CH＝CH-、-OCOCH＝CH-、-COO-(CH2)2-or-C.ident.C-and all others are single bonds, preferably only 1 present in the molecule is-OCH2-、-CH2O-、-C2H4-, -COO-or-OCO-and the others are all single bonds, preferably all single bonds.
In addition, Z present in the molecule is preferablep1And Zp2Only 1 of which is selected from the group consisting of-CH-COO-, -COO-CH-, - (CH)2)2-COO-、-(CH2)2-OCO-、-O-CO-(CH2)2-、-COO-(CH2)2-a linker group of the group and others are single bonds.
Spp1And Spp2Each independently represents a single bond or a spacer, the spacer is preferably an alkylene group having 1 to 30 carbon atoms, in which-CH is present2The alkylene group may be substituted with-O-, -CO-, -COO-, -OCO-, -CH-or-C.ident.C-in the case where oxygen atoms are not directly bonded to each other, and a hydrogen atom in the alkylene group may be substituted with a halogen atom, and is preferably a linear alkylene group having 1 to 10 carbon atoms or a single bond.
Is preferably Ap1、Ap2And Ap3Each independently is 1, 4-phenylene or 1, 4-cyclohexylene, preferably 1, 4-phenylene. In order to improve the compatibility with the liquid crystal compound, the 1, 4-phenylene group is preferably substituted with 1 fluorine atom, 1 methyl group or 1 methoxy group.
The total content of the compounds represented by the general formula (P) is preferably 0.05 to 10%, preferably 0.1 to 8%, preferably 0.1 to 5%, preferably 0.1 to 3%, preferably 0.2 to 2%, preferably 0.2 to 1.3%, preferably 0.2 to 1%, preferably 0.2 to 0.56% of the composition containing the compounds represented by the general formula (P) of the present application.
The lower limit of the total content of the compounds represented by the general formula (P) is preferably 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3% of the composition containing the compounds represented by the general formula (P) in the present application.
The preferable upper limit of the total content of the compounds represented by the general formula (P) is 10%, 8%, 5%, 3%, 1.5%, 1.2%, 1%, 0.8%, 0.5% with respect to the composition containing the compounds represented by the general formula (P) of the present application.
If the content is small, the effect of adding the compound represented by the general formula (P) is hardly exhibited, and the liquid crystal composition has problems such as weak orientation-restraining force and weakening with time, and if it is too large, the amount remaining after curing increases, the curing time is long, and the reliability of the liquid crystal decreases. Therefore, their balance is considered to set the content.
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulae (P-1-1) to (P-1-46).
[ solution 8]
[ solution 9]
[ solution 11]
[ solution 12]
(in the formula, Pp11、Pp12、Spp11And Spp12Represents P in the general formula (P-1)p11、Pp12、Spp11And Spp12The same meaning is used. )
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulae (P-2-1) to (P-2-12).
[ solution 13]
(in the formula, Pp21、Pp22、Spp21And Spp22Represents P in the general formula (P-2)p21、Pp22、Spp21And Spp22The same meaning is used. )
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulae (P-3-1) to (P-3-15).
[ solution 14]
[ solution 15]
(in the formula, Pp31、Pp32、Spp31And Spp32Represents P in the general formula (P-3)p31、Pp32、Spp31And Spp32The same meaning is used. )
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulae (P-4-1) to (P-4-21).
[ solution 16]
[ solution 17]
[ solution 18]
[ solution 19]
(in the formula, Pp41、Pp42、Spp41And Spp42Represents P in the general formula (P-4)p41、Pp42、Spp41And Spp42The same meaning is used. )
The liquid crystal composition of the present invention may contain 1 to 3 kinds of polymerizable compounds represented by the general formula (i) and 1 to 3 kinds of polymerizable compounds represented by the general formula (P) having a structure different from that of the general formula (i).
The lower limit of the total content of the compound represented by the general formula (i) and the polymerizable compound represented by the general formula (P) is preferably 0.01% by mass, preferably 0.03% by mass, preferably 0.05% by mass, preferably 0.08% by mass, preferably 0.10% by mass, preferably 0.12% by mass, preferably 0.15% by mass, preferably 0.17% by mass, preferably 0.2% by mass, preferably 0.22% by mass, preferably 0.25% by mass, preferably 0.27% by mass, preferably 0.3% by mass, preferably 0.32% by mass, preferably 0.35% by mass, preferably 0.37% by mass, preferably 0.4% by mass.
The upper limit of the total content of the polymerizable compound represented by the general formula (i) and the polymerizable compound represented by the general formula (P) in the liquid crystal composition of the present invention is preferably 2.0% by mass, preferably 1.8% by mass, preferably 1.5% by mass, preferably 1.0% by mass, preferably 0.8% by mass, preferably 0.5% by mass, preferably 0.47% by mass, preferably 0.0% by mass, preferably 0.45% by mass, preferably 0.43% by mass, preferably 0.40% by mass, preferably 0.37% by mass, preferably 0.35% by mass, preferably 0.32% by mass, preferably 0.30% by mass, preferably 0.27% by mass, preferably 0.25% by mass, preferably 0.23% by mass, and preferably 0.20% by mass.
The liquid crystal composition may further contain liquid crystal molecules and an alignment assistant having a function of spontaneously aligning the liquid crystal molecules and having an adsorption group (polar group).
(orientation aid)
The alignment aid (self-aligning compound) has the following functions: and a member (an electrode (e.g., ITO), a substrate (e.g., a glass substrate, an acrylic substrate, a transparent substrate, a flexible substrate, etc.), a resin layer (e.g., a color filter, an alignment film, an overcoat layer, etc.), an insulating film (e.g., an inorganic material film, SiNx, etc.)) directly contacting the liquid crystal layer containing the liquid crystal composition, and induces vertical alignment or planar alignment of liquid crystal molecules contained in the liquid crystal layer.
The alignment auxiliary preferably contains a polymerizable group for polymerization, a mesogen group (mesogen group) similar to the liquid crystal molecules, an adsorbing group (polar group) capable of interacting with a member directly contacting the liquid crystal layer, and an alignment-inducing group for inducing alignment of the liquid crystal molecules.
The adsorbing group and the orientation-inducing group are linked to the mesogen, and the polymerizable group is preferably substituted on the mesogen, the adsorbing group and the orientation-inducing group directly or via a spacer as necessary. It is particularly preferable that the polymerizable group is substituted on the mesogen in a state of being taken into the adsorbing group.
In the chemical formula, the left-hand symbol and the right-hand symbol represent a bond.
"orientation inducing group"
The orientation-inducing group has a function of inducing the orientation of liquid crystal molecules, and is preferably a group represented by the following general formula (AK).
[ solution 20]
RAK1-* (AK)
In the formula, RAK1Represents a linear or branched alkyl group having 1 to 20 carbon atoms. Wherein 1 or 2 or more-CH in the alkyl group2-may be independently substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-, respectively, in the case where the oxygen atoms are not directly linked, 1 or 2 or more hydrogen atoms in the alkyl group may be independently substituted by a halogen group, respectively.
RAK1Preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably represents a linear alkyl group having 1 to 20 carbon atoms, and still more preferably represents a linear alkyl group having 1 to 8 carbon atoms.
Further, 1 or 2 or more-CH not adjacent to each other in the alkyl group2-may be independently substituted with-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-.
Further, the hydrogen atom in the alkyl group may be substituted with a fluorine atom or a chlorine atom, and may be substituted with a fluorine atom.
The alignment-inducing group is preferably linked to the mesogen group from the viewpoint of imparting what is called amphiphilicity to the liquid crystal layer to the alignment auxiliary.
"polymerizable group"
The polymerizable group is preferably PAP1-SpAP1-represents.
PAP1Preferably selected from the group represented by the following general formulae (AP-1) to (AP-9).
[ solution 21]
In the formula, RAP1And RAP2Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. Wherein 1 or 2 or more-CH in the alkyl group2-may be substituted by-O-or-CO-, and 1 or more than 2 hydrogen atoms in the alkyl group may be independently substituted by a halogen atom or a hydroxyl group, respectively.
WAP1Represents a single bond, -O-, -COO-or-CH2-。
tAP1Represents 0, 1 or 2.
PAP1The group represented by the following general formula (AP-1) to general formula (AP-7) is preferable, the group represented by the following general formula (AP-1) or general formula (AP-2) is more preferable, and the group represented by the general formula (AP-1) is even more preferable.
SpAP1Preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms, and still more preferably a single bond or a linear alkylene group having 2 to 10 carbon atoms.
In addition, SpAP1In (2) or more-CH not adjacent to 1 or more of alkylene2-may be independently substituted with-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-.
In the orientation assistant, a polymerizable group (P)AP1-SpAP1-) is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, further preferably 2 or more and 4 or less, particularly preferably 2 or 3, and most preferably 2.
PAP1-SpAP1The hydrogen atom in (E-O-C) may be substituted with a polymerizable group, an adsorptive group and/or an orientation-inducing group.
A polymerizable group (P)AP1-SpAP1-) may be linked to a polymerizable group, a mesogen group, an adsorbing group and/or an orientation-inducing group.
In addition, a polymerizable group (P)AP1-SpAP1-) is preferably linked to a mesogen, an adsorbing group or an orientation-inducing group, more preferably to a mesogen or an adsorbing group.
Wherein a plurality of P's are present in the moleculeAP1And/or SpAP1When they are the same or different from each other.
"liquid Crystal primordium"
The term "mesogen" means a group having a rigid portion, for example, a group having one or more cyclic groups, preferably a group having 2 to 4 cyclic groups, and more preferably a group having 3 to 4 cyclic groups. Wherein the cyclic groups may be connected by a linker, as required. The mesogen preferably has a similar skeleton to the liquid crystal molecules (liquid crystal compounds) used in the liquid crystal layer.
In the present specification, the term "cyclic group" means an atomic group in which atoms are bonded to form a ring, and includes a carbon ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a monocyclic ring, a 2-cyclic structure, a polycyclic structure, aromatic groups, nonaromatic groups, and the like.
The cyclic group may contain at least 1 hetero atom, and may be substituted with at least 1 substituent (a halogen group, a polymerizable group, an organic group (an alkyl group, an alkoxy group, an aryl group, or the like)). When the cyclic group is a monocyclic ring, the mesogen group preferably contains 2 or more monocyclic rings.
The above-mentioned mesogen is preferably represented by, for example, general formula (AL).
[ solution 22]
In the formula, ZAL1Represents a single bond, -CH-, -CF-, -C.ident.C-, -COO-, -OCO-, -OCOO-, -CF2O-、-OCF2-、-CH＝CHCOO-、-OCOCH＝CH-、-CH2-CH2COO-、-OCOCH2-CH2-、-CH＝C(CH3)COO-、-OCOC(CH3)＝CH-、-CH2-CH(CH3)COO-、-OCOCH(CH3)-CH2-、-OCH2CH2O-or an alkylene group having 1 to 20 carbon atoms. Wherein 1 or 2 or more-CH not adjacent in the alkylene group2-may be substituted by-O-, -COO-or-OCO-.
AAL1And AAL2Each independently represents a 2-valent cyclic group.
ZAL1、AAL1And AAL2Wherein 1 or 2 or more hydrogen atoms are independently substituted with a halogen group, an adsorbing group, or PAP1-SpAP1-or 1-valent organic group.
Wherein a plurality of Z's are present in the moleculeAL1And AAL1They may be the same or different from each other.
mAL1Represents an integer of 1 to 5.
In the general formula (AL), ZAL1Preferably a single bond or an alkylene group having 2 to 20 carbon atoms, more preferably a single bond or an alkylene group having 2 to 10 carbon atoms, and still more preferably a single bond, - (CH)2)2-or- (CH)2)4-. 1 or 2 or more-CH not adjacent to each other in alkylene group2-may be substituted by-O-, -COO-or-OCO-.
Further, when the object is to improve the linearity of the rod-like molecule, ZAL1The number of atoms directly connecting the ring to the ring is preferably an even number, that is, a single bond. For example-CH2-CH2In the case of COO-, the number of atoms directly linking the ring to the ring is 4.
In the general formula (AL), AAL1And AAL2Each independently represents a 2-valent cyclic group. The 2-valent cyclic group is preferably selected from the group consisting of 1, 4-phenylene, 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, tetrahydrothiopyran-2, 5-diyl, thiophene-2, 5-diyl, 1, 4-bicyclo (2,2,2) octylene, decahydronaphthalene-2, 6-diyl, and pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, pyrazine-2, 5-diyl, thiophene-2, 5-diyl-, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, 2, 6-naphthylene, phenanthrene-2, 7-diyl, 9, 10-dihydrophenanthrene-2, 7-diyl, 1,2,3,4,4a,9,10 a-octahydrophenanthrene-2, 7-diyl, 1, 4-naphthylene, benzo [1, 2-b: 4, 5-b']Dithiophene-2, 6-diyl, benzo [1, 2-b: 4, 5-b']Diselenophene-2, 6-diyl, [ 1]]Benzothieno [3,2-b ]]Thiophene-2, 7-diyl ([ 1]]benzothieno[3,2-b]thiophene-2,7-diyl)、[1]Benzoselenopheno [3,2-b ] s]Selenophene-2, 7-diyl and fluorene-2, 7-diyl, more preferably 1, 4-phenylene, 1, 4-cyclohexylene, 2, 6-naphthylene or phenanthrene-2, 7-diyl, and still more preferably 1, 4-phenylene or 1, 4-cyclohexylene.
These groups may be unsubstituted or substituted by substituents, among others. The substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms. Further, the alkyl group may be substituted with a fluorine atom or a hydroxyl group.
Further, 1 or 2 or more hydrogen atoms in the cyclic group may be substituted with a halogen group, an adsorbing group, or PAP1-SpAP1-or 1-valent organic group.
In the general formula (AL), the 1-valent organic group is a group having a chemical structure such that the organic compound forms a 1-valent group, and means a group obtained by removing 1 hydrogen atom from the organic compound.
Examples of the 1-valent organic group include an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, an alkenyloxy group having 2 to 15 carbon atoms, and the like, preferably an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, and most preferably an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 carbon atom.
Further, 1 or 2 or more-CH not adjacent to each other among the above alkyl group, alkenyl group, alkoxy group and alkenyloxy group2-may be substituted by-O-, -COO-or-OCO-. Further, the above-mentioned 1-valent organic group may have a function as an orientation-inducing group described laterThe application is as follows.
In the above general formula (AL), mAL1Preferably 1 ~ 4 integer, more preferably 1 ~ 3 integer, more preferably 2 or 3.
Preferred examples of the above-mentioned mesogen include the following formulas (me-1) to (me-44).
[ solution 23]
[ solution 24]
[ solution 25]
[ solution 26]
The general formula (AL) is a structure in which 2 hydrogen atoms are detached from these compounds.
In the formulae (me-1) to (me-44), 1 or 2 or more hydrogen atoms in the cyclohexane ring, benzene ring or naphthalene ring may be independently substituted with a halogen group or PAP1-SpAP1A 1-valent organic group (e.g., an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms), an adsorbing group, or an orientation-inducing group.
Among the above-mentioned liquid crystal primordia, preferred embodiments are those of the formulae (me-8) to (me-44), more preferred embodiments are those of the formulae (me-8) to (me-10), those of the formulae (me-12) to (me-18), those of the formulae (me-22) to (me-24), those of the formulae (me-26) to (me-27), and those of the formulae (me-29) to (me-44), and still more preferred embodiments are those of the formulae (me-12), (me-15) to (me-16), (me-22) to (me-24), (me-29), (me-34), (me-36) to (me-37), and those of the formulae (me-42) to (me-.
Among the above-mentioned mesogens, the following general formula (AL-1) or (AL-2) is particularly preferable, and the following general formula (AL-1) is most preferable.
[ solution 27]
In the formula, XAL101～XAL118、XAL201～XAL214Each independently represents a hydrogen atom, a halogen group, PAPl-SpAPl-, an adsorption group or an orientation-inducing group.
Ring AAL11Ring AAL12And ring AAL21Each independently represents a cyclohexane ring or a benzene ring.
XAL101～XAL118、XAL201～XAL214Any 1 or more than 2 of them may be substituted by an adsorption group.
XAL101～XAL118、XAL201～XAL214Any 1 or more than 2 of them may be substituted with an orientation-inducing group.
The adsorption group and orientation-inducing group may be substituted with PAP1-SpAP1-substitution.
With respect to the general formula (AL-1) or the general formula (AL-2), 1 or 2 or more kinds of P are contained in the moleculeAP1-SpAPl-。
In the general formula (AL-1), XAL101Orientation inducing groups are preferred.
In the general formula (AL-1), X is preferredAL109、XAL110And XAL111At least 1 of them is an adsorption group, more preferably XAL109And XAL110Are all an adsorption group or XAL110For the adsorption group, X is further preferredAL110Is an adsorption group.
In the general formula (AL-1), X is preferredAL109、XAL110And XAL111At least 1 of which is PAP1-SpAP1Or an adsorptive group having a polymerizable site within the structure, more preferably XAL109And XAL111Either or both of (A) and (B) is PAP1-SpAP1-。
In the general formula (AL-1), XAL104～XAL108、XAL112～XAL1161 or 2 or more of them are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen group, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. XAL105、XAL106Or XAL107Each independently particularly preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom.
In the general formula (AL-2), XAL201Orientation inducing groups are preferred.
In the general formula (AL-2), X is preferredAL207、XAL208And XAL209At least 1 of them is an adsorption group, more preferably XAL207And XAL208Are all an adsorption group or XAL208For the adsorption group, X is further preferredAL208Is an adsorption group.
In the general formula (AL-2), X is preferredAL207、XAL208And XAL209At least 1 of which is PAP1-SpAP1Or an adsorptive group having a polymerizable site within the structure, more preferably XAL207And XAL209Either or both of (A) and (B) is PAP1-SpAP1-。
In the general formula (AL-2), XAL202～XAL206、XAL210～XAL2141 or 2 or more of them are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen group, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. XAL204、XAL205Or XAL206Each independently particularly preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom.
"adsorption group"
The adsorption group is a group having an action of adsorbing an adsorption medium, which is a layer in contact with the liquid crystal composition, such as a substrate, a film, or an electrode.
The adsorption is generally classified into chemisorption in which adsorption is performed between an adsorption medium and an adsorbent by forming a chemical bond (a covalent bond, an ionic bond, or a metal bond), and physisorption other than chemisorption. In the present specification, the adsorption may be either chemisorption or physisorption, and preferably physisorption. Therefore, the adsorption group is preferably a group capable of physical adsorption to the adsorption medium, and more preferably a group capable of bonding to the adsorption medium by intermolecular force.
Examples of the mode of bonding to the adsorption medium by intermolecular force include a mode utilizing interaction such as permanent dipole, permanent quadrupole, dispersion force, charge transfer force, or hydrogen bond.
As a preferred embodiment of the adsorption group, a method capable of binding to the adsorption medium by hydrogen bonding is cited. In this case, the adsorption group may function as either a donor or an acceptor of a proton having a hydrogen bond, or may function as both of them.
The adsorption group is preferably a group containing a polar element having an atomic group in which a carbon atom is bonded to a hetero atom (hereinafter, the "adsorption group" is also referred to as a "polar group"). In the present specification, the polar element means an atomic group in which a carbon atom and a hetero atom are directly bonded to each other.
The heteroatom is preferably at least 1 selected from the group consisting of N, O, S, P, B and Si, more preferably at least 1 selected from the group consisting of N, O and S, even more preferably at least 1 selected from the group consisting of N and O, and particularly preferably O.
In addition, in the orientation assistant, the number of the polar elements is not particularly limited, and the number of the polar elements in the adsorption group is not particularly limited, as long as the number of the polar elements is 1,2,3, or the like.
The orientation aid preferably has 1 to 8 adsorption groups in one molecule, more preferably 1 to 4 adsorption groups, and further preferably 1 to 3 adsorption groups.
Wherein the polymerizable group and the orientation-inducing group are excluded from the adsorbing group, but the hydrogen atom in the adsorbing group is substituted by PAP1-SpAP1-substituted structure and PAP1-SpAP1The structure in which the hydrogen atom in-is substituted with-OH is contained in the adsorption group.
The adsorption group contains 1 or 2 or more polar elements and is roughly classified into a cyclic base type and a chain base type.
The cyclic base type is a type including a cyclic base having a cyclic structure including a polar element in the structure thereof, and the chain type is a type not including a cyclic base having a cyclic structure including a polar element in the structure thereof.
The chain-type group may have a polar element in a linear or branched chain-type group, and a part of the chain-type group may have a cyclic structure containing no polar element.
The cyclic group-type adsorption group means a structure having at least 1 polar element in a cyclic atomic arrangement.
In the present specification, the cyclic group is as described above. Therefore, the cyclic group-type adsorption group may contain a cyclic group including a polar element, and the adsorption group may be branched or linear.
On the other hand, the chain-type adsorption group means a mode having a structure in which a cyclic atomic arrangement including no polar element is not included in a molecule and at least 1 polar element is included in a linear atomic arrangement (branching possibility).
In the present specification, a chain group means an atomic group in which atoms are linearly (branched) connected without including a cyclic atomic arrangement in a structural formula, and is referred to as a non-cyclic group. In other words, the chain group means a linear or branched aliphatic group and may contain either a saturated bond or an unsaturated bond.
Thus, the chain group includes, for example, an alkyl group, an alkenyl group, an alkoxy group, an ester, an ether, a ketone, or the like. Among them, the hydrogen atom in these groups may be substituted with at least 1 substituent (reactive functional group (vinyl group, acryloyl group, methacryloyl group, etc.), chain organic group (alkyl group, cyano group, etc.)). The chain group may be either linear or branched.
The cyclic-type adsorption group is preferably a heteroaromatic group having 3 to 20 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 20 carbon atoms (including a condensed ring), more preferably a heteroaromatic group having 3 to 12 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 12 carbon atoms (including a condensed ring), and still more preferably a heteroaromatic group having 5-membered ring, a heteroalicyclic group having 5-membered ring, a heteroaromatic group having 6-membered ring or a heteroalicyclic group having 6-membered ring. Wherein the hydrogen atoms in these ring structures may be substituted with a halogen group, a linear or branched alkyl group having 1 to 5 carbon atoms, or an alkoxy group.
As the chain type adsorption group, preferably the hydrogen atom, -CH in the structure2A linear or branched alkyl group having 1 to 20 carbon atoms substituted with a polar element. Wherein 1 or 2 or more-CH not adjacent to each other in the alkyl group2-may be substituted by-CH ═ CH-, -C.ident.C-, -O-, -CO-, -COO-, -OCO-, or-OCO-COO-. The chain-type adsorption group preferably contains 1 or 2 or more polar elements at its end.
The hydrogen atom in the adsorption group may be substituted with a polymerizable group.
Specific examples of the polar element include an oxygen atom-containing polar element (hereinafter referred to as an oxygen-containing polar element), a nitrogen atom-containing polar element (hereinafter referred to as a nitrogen-containing polar element), a phosphorus atom-containing polar element (hereinafter referred to as a phosphorus-containing polar element), a boron atom-containing polar element (hereinafter referred to as a boron-containing polar element), a silicon atom-containing polar element (hereinafter referred to as a silicon-containing polar element), and a sulfur atom-containing polar element (hereinafter referred to as a sulfur-containing polar element). From the viewpoint of adsorption capacity, the polar element is preferably a nitrogen-containing polar element, or an oxygen-containing polar element, and more preferably an oxygen-containing polar element.
The oxygen-containing polar element is preferably at least 1 group selected from the group consisting of a hydroxyl group, an alkanol group, an alkoxy group, a formyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group and an ester group, or a group in which the group is bonded to a carbon atom.
The nitrogen-containing polar element is preferably at least 1 group selected from the group consisting of a cyano group, a primary amino group, a secondary amino group, a tertiary amino group, a pyridyl group, a carbamoyl group and a ureido group, or a group in which the group is bonded to a carbon atom.
The phosphorus-containing polar element is preferably at least 1 group selected from the group consisting of a phosphinyl group (phosphinyl group) and a phosphoric group, or a group in which the group is bonded to a carbon atom.
Therefore, the adsorption group is preferably 1 or 2 or more groups selected from the group consisting of a cyclic group having an oxygen-containing polar element (hereinafter referred to as an oxygen-containing cyclic group), a cyclic group having a nitrogen-containing polar element (hereinafter referred to as a nitrogen-containing cyclic group), a cyclic group having a sulfur-containing polar element (hereinafter referred to as a sulfur-containing cyclic group), a chain group having an oxygen-containing polar element (hereinafter referred to as an oxygen-containing chain group), and a chain group having a nitrogen-containing polar element (hereinafter referred to as a nitrogen-containing chain group), and the adsorption group itself or contains the group, and more preferably contains 1 or 2 or more groups selected from the group consisting of an oxygen-containing cyclic group, a sulfur-containing cyclic group, an oxygen-containing chain group, and a nitrogen-containing chain group, from.
The oxygen-containing cyclic group preferably contains any of the following groups having an oxygen atom as an ether group in the ring structure.
[ solution 28]
The oxygen-containing cyclic group preferably contains any of the following groups having an oxygen atom in the form of a carbonyl group, a carbonate group, and an ester group in the ring structure.
[ solution 29]
The nitrogen-containing cyclic group preferably contains any of the following groups.
[ solution 30]
The oxygen-containing chain group preferably contains any of the following groups.
[ solution 31]
In the formula, Rat1Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Zat1Represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms. wherein-CH in alkylene or alkenylene2-can be substituted by-O-, -COO-, -C (═ O) -, -OCO-in such a way that the oxygen atoms are not directly adjacent.
Xat1Represents an alkyl group having 1 to 15 carbon atoms. wherein-CH in the alkyl group2-can be substituted by-O-, -COO-, -C (═ O) -, -OCO-in such a way that the oxygen atoms are not directly adjacent.
The nitrogen-containing chain group preferably contains any of the following groups.
[ solution 32]
In the formula, Rat、Rbt、RctAnd RdtEach independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The adsorption group is preferably a group represented by the following general formula (AT).
[ solution 33]
*-SpAT1-WAT1-ZAT1 (AT)
In the formula, SpAT1Represents a single bond, or a straight-chain or branched alkylene group having 1 to 25 carbon atoms. Wherein the hydrogen atoms in the alkylene group may be replaced by-OH, -CN, -WAT1-ZAT1Or PAP1-SpAP1-substituted, -CH in alkylene2-can be substituted by cyclic groups, -O-, -COO-, -C (═ O) -, -OCO-, -CH ═ CH-, or-OCO-COO-in such a way that the oxygen atoms are not directly linked.
WAT1Represents a single bond or a general formula (WAT1) or (WAT 2).
ZAT1The representation comprisesA 1-valent group of a polar element. Wherein Z isAT1The hydrogen atom in (A) may be replaced by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substitution.
[ chemical 34]
(wherein SpWAT1And SpWAT2Each independently represents a single bond, a straight-chain or branched alkylene group having 1 to 25 carbon atoms, and a hydrogen atom in the alkylene group may be replaced by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substituted, -CH in alkylene2-can be substituted by cyclic groups, -O-, -COO-, -C (═ O) -, -OCO-or-CH ═ CH-without direct connection of oxygen atoms. )
SpAT1、SpWAT1And SpWAT2Each independently preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms, and still more preferably a single bond or a linear alkylene group having 2 to 10 carbon atoms.
In addition, SpAT1、SpWAT1And SpWAT2In (2) or more-CH not adjacent to 1 or more of alkylene2-may each be independently substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-or-OCO-in such a way that the oxygen atoms are not directly attached.
In addition, SpAT1And SpWAT1The hydrogen atoms in (A) may each independently be replaced by-SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substitution.
ZAT1The 1-valent group containing a polar element is preferably a group represented by the following general formula (ZAT1-1) or (ZAT 1-2).
[ solution 35]
*-SpZAT11-ZZAT11-RZAT11 (ZAT1-1
In the formula, SpZAT11And SpZAT12Each independently represents a linear or branched alkylene group having 1 to 25 carbon atoms. Wherein the hydrogen atoms in the alkylene group may be replaced by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substituted, -CH in alkylene2-can be substituted by cyclic groups, -O-, -COO-, -C (═ O) -, -OCO-or-CH ═ CH-, in such a way that the oxygen atoms are not directly adjacent.
ZZAT11Represents a polar element-containing group.
Z is contained in the general formula (ZAT1-2)ZAT12The structure represented by the ring (b) represents a 5-to 7-membered ring.
ZZAT11And ZZAT12The hydrogen atom in (A) may be replaced by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substitution.
RZAT11And RZAT12Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms. Wherein the hydrogen atom in the alkyl group may be replaced by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substituted, -CH in alkyl2-can be substituted by cyclic groups, -O-, -COO-, -C (═ O) -, -OCO-or-CH ═ CH-without direct connection of oxygen atoms.
The group represented by the general formula (ZAT1-1) is preferably a group represented by the following general formulae (ZAT1-1-1) to (ZAT 1-1-30).
[ solution 36]
[ solution 37]
In the formula (II) with carbonThe atomically bound hydrogen atoms may be replaced by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substitution.
SpZAT11Represents a linear or branched alkylene group having 1 to 25 carbon atoms. Wherein the hydrogen atoms in the alkylene group may be replaced by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substituted, -CH in alkylene2-can be substituted by cyclic groups, -O-, -COO-, -C (═ O) -, -OCO-or-CH ═ CH-, in such a way that the oxygen atoms are not directly adjacent.
RZAT11Represents a linear or branched alkyl group having 1 to 8 carbon atoms. Wherein the hydrogen atom in the alkyl group may be replaced by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substituted, -CH in alkyl2-can be substituted by cyclic groups, -O-, -COO-, -C (═ O) -, -OCO-or-CH ═ CH-without direct connection of oxygen atoms.
The group represented by the general formula (ZAT1-2) is preferably a group represented by the following general formulae (ZAT1-2-1) to (ZAT 1-2-9).
[ solution 38]
Wherein the hydrogen atom bound to a carbon atom may be replaced by a halogen atom, -OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substitution.
SpZAT11Represents a linear or branched alkylene group having 1 to 25 carbon atoms. Wherein the hydrogen atoms in the alkylene group may be replaced by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substituted, -CH in alkylene2-can be substituted by cyclic groups, -O-, -COO-, -C (═ O) -, -OCO-or-CH ═ CH-, in such a way that the oxygen atoms are not directly adjacent.
Examples of the group represented by the general formula (ZAT1-1) include the following groups.
[ solution 39]
[ solution 40]
[ solution 41]
[ solution 42]
[ solution 43]
In the formula, RtcRepresents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or PAP1-SpAP1-. Wherein hydro-atoms in alkyl groups may be substituted by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substituted, -CH in alkyl2-can be substituted by cyclic groups, -O-, -COO-, -C (═ O) -, -OCO-or-CH ═ CH-, in such a way that the oxygen atoms are not directly adjacent.
Hydrogen atoms in the molecule may be replaced by PAP1-SpAP1-substitution.
It represents a connecting bond.
The orientation assistant is preferably a form in which a polar element contained in the adsorptive group or a polar element contained in the polymerizable group is locally present. The adsorption group is an important structure for vertically aligning liquid crystal molecules, and by making the adsorption group adjacent to the polymerizable group, more favorable alignment properties can be obtained, and favorable solubility in the liquid crystal composition is exhibited.
Specifically, the alignment aid is preferably a system having a polymerizable group and an adsorptive group on the same ring of the mesogen group. In this mode, the method includes: a mode in which 1 or more polymerizable groups and 1 or more adsorbing groups are connected to the same ring; at least one of 1 or more polymerizable groups or at least one of 1 or more adsorbing groups is bonded to another one, and the polymerizable group and the adsorbing group are provided on the same ring.
In this case, the hydrogen atom in the spacer group of the polymerizable group may be substituted with the adsorptive group, and the hydrogen atom in the adsorptive group may be substituted with the polymerizable group through the spacer group.
As the alignment aid, a compound represented by the following general formula (SAL) is preferable.
[ solution 44]
Wherein the hydrogen atom bonded to the carbon atom may be substituted by a linear or branched alkyl group having 1 to 25 carbon atoms, -OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substitution. Wherein the hydrogen atom in the alkyl group may be replaced by-OH, -CN, -SpAT1-WAT1-ZAT1Or PAP1-SpAP1-substituted, -CH in alkyl2-can be substituted by cyclic groups, -O-, -COO-, -C (═ O) -, -OCO-or-CH ═ CH-without direct connection of oxygen atoms.
RAK1Represents R in the general formula (AK)AK1The same meaning is used.
AAL1And AAL2Each independently represents a group represented by the general formula (AL)AL1And AAL2The same meaning is used.
ZAL1Is represented by the formula (AL) and ZAL1The same meaning is used.
mAL1Represents a group represented by the formula (AL) and mAL1The same meaning is used.
SpAT1Represents Sp in the general formula (AT)AT1The same meaning is used.
WAT1W in the general formula (AT)AT1The same meaning is used.
ZAT1Z in the general formula (AT)AT1The same meaning is used.
The compound represented by the general formula (SAL) is preferably a compound represented by the following formulae (SAL-1.1) to (SAL-2.9).
[ solution 45]
[ solution 46]
[ solution 47]
[ solution 48]
[ solution 49]
[ solution 50]
[ solution 51]
[ solution 52]
[ Hua 53]
[ solution 54]
[ solution 55]
[ solution 56]
[ solution 57]
The amount of the alignment aid contained in the liquid crystal composition is preferably about 0.01 to 50 mass%. From the viewpoint of more suitably aligning the liquid crystal molecules, the lower limit thereof is more preferably 0.05 mass% or 0.1 mass%. On the other hand, from the viewpoint of improving the response characteristics, more preferable upper limit values thereof are 30 mass%, 10 mass%, 7 mass%, 5 mass%, 4 mass%, and 3 mass%.
A compound represented by the general formula (i) or a compound represented by the general formula (SAL) (i.e., as containing an adsorption group Z)AT1The compound of (4), and the total content of the compound represented by the general formula (P) based on the liquid crystal compositionPreferably 0.05 to 10% by mass, preferably 0.1 to 8% by mass, preferably 0.1 to 5% by mass, preferably 0.1 to 3% by mass, preferably 0.2 to 2% by mass, preferably 0.2 to 1.3% by mass, preferably 0.2 to 1% by mass, preferably 0.2 to 0.56% by mass.
The polymerizable liquid crystal composition of the present invention contains a compound represented by the general formula (i) as a polymerizable compound, and preferably further contains a compound represented by the general formula (SAL) (i.e., as a polymerizable compound containing an adsorbate group Z)AT1The compound of (4) and a compound represented by the general formula (P).
Here, the compound represented by the general formula (SAL) as the alignment assistant has a function of aligning the liquid crystal compound in the liquid crystal composition substantially perpendicularly to the substrate, and the compound represented by the general formula (i) and the compound represented by the general formula (P) are used for stabilizing the alignment in which the liquid crystal compound is inclined in a certain direction with respect to the substrate in a state where no voltage is applied ". Although stabilization of the tilt of the liquid crystal compound with respect to the substrate can be achieved to some extent even when only the compound represented by the general formula (P) is used, the problem to be solved by the present application can be achieved by using the compound represented by the general formula (i).
A compound represented by the general formula (i) or a compound represented by the general formula (SAL) (i.e., as containing an adsorption group Z)AT1The lower limit of the total content of the compound (b) and the compound represented by the general formula (P) is preferably 0.01 mass%, 0.03 mass%, 0.05 mass%, 0.08 mass%, 0.1 mass%, 0.15 mass%, 0.2 mass%, 0.25 mass%, 0.3 mass% of the liquid crystal composition.
The preferable upper limit of the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is 10 mass%, 8 mass%, 5 mass%, 3 mass%, 1.5 mass%, 1.2 mass%, 1 mass%, 0.8 mass%, 0.5 mass% with respect to the liquid crystal composition.
If the compound represented by the general formula (i) or the compound represented by the general formula (SAL) (i.e., as containing an adsorption group Z)AT1An alignment assistant for the compound of (4), and a compound represented by the general formula (P)When the content is small, the effect of adding these compounds to the liquid crystal composition is difficult to be exhibited, and depending on the kind of liquid crystal molecules, for example, the alignment binding force of the liquid crystal molecules may be weak or may become weak with time. On the other hand, if the total content of the compound represented by general formula (SAL) and the compound represented by general formula (P) is too large, the following problem may occur depending on, for example, the illuminance of the active energy ray: the amount of the compound remaining after curing is large, the curing takes time, the reliability of the liquid crystal composition is lowered, and the like. Therefore, it is preferable to set the content thereof in consideration of their balance.
The liquid crystal composition of the present invention preferably contains one or more compounds selected from the group of compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05). These compounds correspond to compounds having negative dielectric anisotropy. The "compound having negative dielectric anisotropy" means a compound having a negative sign of Δ ∈ and an absolute value of Δ ∈ larger than 2. Wherein Δ ∈ of the compound is the following value: extrapolated values from measurements of dielectric anisotropy of a composition prepared by adding the compound to a composition having a dielectric property that is substantially neutral at 25 ℃.
The liquid crystal composition of the present invention preferably contains one or more compounds selected from the group of compounds represented by the general formulae (N-01), (N-02), (N-03) and (N-04).
[ solution 58]
In the formula, R21And R22Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, 1 or 2 or more-CH groups not adjacent to each other2-may also be independently substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-, Z1Each independently represents a single bond, -CH2CH2-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH ═ CH-, -CF ═ CF-or-C ≡ C-, and m independently represents 1 or 2, respectively.
R21The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. Wherein, in Z1R is other than a single bond21Preferably an alkyl group having 1 to 3 carbon atoms.
R22Preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and still more preferably an alkoxy group having 1 to 4 carbon atoms.
R21And R22In the case of an alkenyl group, it is preferably a group represented by any one selected from the group consisting of the formula (R1) to the formula (R5) (black dots in each formula represent carbon atoms in the ring structure),
[ chemical 59]
Further preferred is the formula (R1) or the formula (R2). But R is21And R22The content of the compound which is an alkenyl group is preferably as small as possible, and is preferably not contained.
Z1Each independently represents a single bond, -CH2CH2-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH-, -CF-or-C.ident.C-, preferably a single bond, -CH ≡ C-2CH2-、-OCH2-、-CH2O-, more preferably a single bond or-CH2O-。
When m is 1, Z1Preferably a single bond.
When m is 2, Z1Is preferably-CH2CH2-or-CH2O-。
The fluorine atom of the compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) may be substituted by a chlorine atom which is also a halogen group. Among them, the content of the compound substituted with a chlorine atom is preferably as small as possible, and is preferably not contained.
The hydrogen atoms present in the ring of the compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) may be replaced by fluorine atoms or chlorine atoms, but chlorine atoms are not preferred.
The compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) are preferably compounds having negative Δ ε and larger absolute values than 3. In particular, R22Preferably represents an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms.
In the liquid crystal composition of the present invention, the compound represented by the general formula (N-01) preferably contains one or more compounds selected from the group consisting of compounds represented by the general formula (N-01-1), the general formula (N-01-2), the general formula (N-01-3) and the general formula (N-01-4).
[ solution 60]
(in the formula, R21Represents the same meaning as described above, R23Each independently represents an alkoxy group having 1 to 4 carbon atoms. )
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and one or more compounds selected from the group of compounds represented by general formulae (N-01-1) to (N-01-4).
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-01-1), and a compound represented by the general formula (N-01-4).
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-01-3), and a compound represented by the general formula (N-01-4).
In the liquid crystal composition of the present invention, the compound represented by the general formula (N-02) preferably contains one or more compounds selected from the group consisting of compounds represented by the general formula (N-02-1), the general formula (N-02-2) and the general formula (N-02-3).
[ solution 61]
(in the formula, R21Represents the same meaning as described above, R23Each independently represents an alkoxy group having 1 to 4 carbon atoms. )
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and a compound represented by the general formula (N-02-1).
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-02-1), and a compound represented by the general formula (N-02-3).
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-02-1), and a compound represented by the general formula (N-01-4).
In the liquid crystal composition of the present invention, the compound represented by the general formula (N-03) preferably contains one or more compounds represented by the general formula (N-03-1).
[ solution 62]
(in the formula, R21Represents the same meaning as described above, R23Represents an alkoxy group having 1 to 4 carbon atoms. )
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and a compound represented by the general formula (N-03-1).
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-03-1), and a compound represented by the general formula (N-01-4).
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-03-1), and a compound represented by the general formula (N-02-1).
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-03-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-02-1).
In the liquid crystal composition of the present invention, the compound represented by the general formula (N-04) preferably contains one or more compounds represented by the general formula (N-04-1).
[ solution 63]
(in the formula, R21Represents the same meaning as described above, R23Represents an alkoxy group having 1 to 4 carbon atoms. )
The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and a compound represented by the general formula (N-04-1) at the same time.
The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-04-1), and a compound represented by the general formula (N-01-4) at the same time.
The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-02-1) at the same time.
The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-03-1) at the same time.
The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-02-1), and a compound represented by the general formula (N-03-1) at the same time.
The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4), a compound represented by the general formula (N-02-1), and a compound represented by the general formula (N-03-1) at the same time.
The liquid crystal composition of the present invention may contain a compound selected from the group consisting of compounds represented by the formulae (N-05-1) to (N-05-3) as the compound represented by the general formula (N-05).
[ solution 64]
The lower limit of the preferable content of the compound represented by the general formula (N-01) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.
The lower limit of the preferable content of the compound represented by the general formula (N-02) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.
The lower limit of the preferable content of the compound represented by the general formula (N-03) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.
The lower limit of the preferable content of the compound represented by the general formula (N-04) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.
The lower limit of the preferable content of the compound represented by the formula (N-05) is 0%, 2%, 5%, 8%, 10%, 13%, 15%, 17%, 20% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%.
The liquid crystal composition of the present invention may further contain one or more compounds represented by the general formula (N-06).
[ solution 65]
(in the formula, R21And R22The same meanings as described above are indicated. )
The compound represented by the general formula (N-06) can exert its effect when various physical properties are to be adjusted, and can be used for obtaining a large refractive index anisotropy (. DELTA.n) and a high TNIAnd a large Δ ∈ are used.
The lower limit of the preferable content of the compound represented by the formula (N-06) is 0%, 2%, 5%, 8%, 10%, 13%, 15%, 17%, 20% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the content is preferably 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 5%.
The liquid crystal composition of the present invention contains one or more compounds selected from the group of compounds represented by general formulae (NU-01) to (NU-08).
[ solution 66]
(in the formula, RNU11、RNU12、RNU21、RNU22、RNU31、RNU32、RNU41、RNU42、RNU51、RNU52、RNU61、RNU62、RNU71、RNU72、RNU81And RNU82Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, 1 or 2 or more-CH groups not adjacent to each other2-may also be independently substituted with-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-. )
If more detailed, then RNU11、RNU12、RNU21、RNU22、RNU31、RNU32、RNU41、RNU42、RNU51、RNU52、RNU61、RNU62、RNU71、RNU72、RNU81And RNU82An alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. In the case where importance is attached to the response speed, at least 1R is preferableNU11、RNU21、RNU41And RNU51An alkenyl group having 2 to 3 carbon atoms, preferably represented by the formula (R2)The alkenyl radicals shown.
The content of the compound having an alkenyl group is preferably 30% or less, preferably 25% or less, preferably 20% or less, preferably 15% or less, preferably 10% or less, preferably 5% or less, relative to the total amount of the liquid crystal composition of the present invention. When high VHR is regarded as important, the alkenyl group-containing compound is preferably 10% or less, preferably 5% or less, preferably 1% or less, and preferably not contained.
If more detailed, then RNU11、RNU21、RNU31、RNU41、RNU51、RNU61、RNU71、RNU81Particularly preferably an alkyl group of 1 to 5 carbon atoms, RNU12、RNU22、RNU32、RNU42、RNU52、RNU62、RNU72And RNU82Particularly preferred is an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-02).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-03).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-03) and a compound represented by the general formula (NU-04).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-03) and a compound represented by the general formula (NU-05).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-06).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-07).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-08).
The liquid crystal composition of the present invention preferably further contains a compound represented by the general formula (NU-01), a compound represented by the general formula (NU-02), and a compound represented by the general formula (NU-04).
The liquid crystal composition of the present invention preferably further contains a compound represented by the general formula (NU-01), a compound represented by the general formula (NU-03), and a compound represented by the general formula (NU-05).
The liquid crystal composition of the present invention preferably further contains a compound represented by the general formula (NU-01), a compound represented by the general formula (NU-02), a compound represented by the general formula (NU-03), and a compound represented by the general formula (NU-05).
The content of the compound represented by the general formula (NU-01) is preferably 1 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass.
The content of the compound represented by the general formula (NU-02) is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, and still more preferably 5 to 20% by mass.
The content of the compound represented by the general formula (NU-03) is preferably 1 to 20% by mass, more preferably 0 to 15% by mass, and still more preferably 0 to 10% by mass.
The content of the compound represented by the general formula (NU-04) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.
The content of the compound represented by the general formula (NU-05) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 3 to 20% by mass.
The content of the compound represented by the general formula (NU-06) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.
The content of the compound represented by the general formula (NU-07) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.
The content of the compound represented by the general formula (NU-08) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.
The liquid crystal composition of the present invention may contain 1 or 2 or more compounds having positive dielectric anisotropy described in paragraphs 0236 to 0509 of patent document 4 (japanese patent No. 6233550).
The composition of the present invention preferably does not contain a compound having a structure in which oxygen atoms are linked to each other, such as a peracid (-CO-OO-) structure, in the molecule.
When importance is attached to the reliability and long-term stability of the composition, the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, and particularly preferably substantially not contained, based on the total mass of the composition.
When importance is attached to stability by UV irradiation, the content of the compound substituted with a chlorine atom is preferably 15% or less, preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially not contained, with respect to the total mass of the composition.
The content of the compound having all the ring structures in the molecule of a 6-membered ring is preferably large, and the content of the compound having all the ring structures in the molecule of a 6-membered ring is preferably 80% or more, more preferably 90% or more, further preferably 95% or more, and particularly preferably the composition is constituted by substantially only the compound having all the ring structures in the molecule of a 6-membered ring, based on the total mass of the composition.
In order to suppress deterioration due to oxidation of the composition, it is preferable that the content of the compound having a cyclohexenylene group as a ring structure is small, and the content of the compound having a cyclohexenylene group is preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially not contained, with respect to the total mass of the composition.
In the case where importance is attached to the improvement of viscosity and the improvement of TNI, it is preferable that the content of the compound having 2-methylbenzene-1, 4-diyl in which a hydrogen atom is substituted with halogen is small, and it is preferable that the content of the compound having 2-methylbenzene-1, 4-diyl in the molecule is 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially none, with respect to the total mass of the composition.
In the present application, substantially free means free of other than an unintentionally contained substance.
The liquid crystal composition of the present invention may contain, in addition to the above-mentioned compounds, ordinary nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, light stabilizer, infrared absorber, or the like.
The liquid crystal composition of the present invention preferably contains an antioxidant so that polymerization does not proceed in a heating treatment which is one of the steps of manufacturing a liquid crystal display element. When the antioxidant is not contained, polymerization proceeds during the heat treatment before the UV irradiation step, and the desired orientation cannot be obtained.
As the antioxidant, hindered phenols (hindered phenols) represented by general formulae (H-1) to (H-4) can be mentioned.
[ solution 67]
In the general formulae (H-1) to (H-3), RH1Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 2 to 10 carbon atoms. More specifically, RH1More preferably an alkyl group having 3 carbon atoms.
In the general formula (H-4), MH1Represents an alkylene group having 4 to 10 carbon atoms (one or two or more-CH groups in the alkylene group)2-may be substituted by-O-, -CO-, -COO-, -OCO-in such a manner that oxygen atoms are not directly adjacent to each other, -OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CF2CF2-, -CH ═ CH-COO-, -CH ═ CH-OCO-, -COO-CH ═ CH-, -OCO-CH ═ CH-, -C ≡ C-, single bond, 1, 4-phenylene (any hydrogen atom in the 1, 4-phenylene may be substituted with a fluorine atom), or trans-1, 4-cyclohexylene.
In the case where the liquid crystal composition of the present invention contains an antioxidant, the lower limit thereof is preferably 10 mass ppm, preferably 20 mass ppm, preferably 50 mass ppm, and the upper limit thereof is preferably 10000 mass ppm, preferably 1000 mass ppm, preferably 500 mass ppm, preferably 100 mass ppm.
Nematic phase-isotropic liquid phase transition temperature (T) of liquid crystal composition of the present inventionNI) From 60 ℃ to 120 ℃, more preferably from 70 ℃ to 100 ℃, and particularly preferably from 70 ℃ to 85 ℃. Wherein, in the present invention, T represents 60 ℃ or higherNIHigh.
In the case of liquid crystal television applications, TNIPreferably 70 to 80 ℃ and, in the case of carrying use, TNIPreferably 80 to 90 ℃ and T is used for outdoor display such as PID (public Information display)NIPreferably from 90 to 110 ℃.
The liquid crystal composition of the present invention has a refractive index anisotropy (. DELTA.n) at 20 ℃ of 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. In more detail, the thickness is preferably 0.10 to 0.13 in the case of a thin cell gap, and preferably 0.08 to 0.10 in the case of a thick cell gap. Among them, the liquid crystal composition of the present invention particularly preferably has a refractive index anisotropy (Δ n) at 20 ℃ of 0.098 to 0.118.
The liquid crystal composition of the present invention has a rotational viscosity (. gamma.) at 20 ℃1) Is from 50 to 160 mPas, preferably from 55 to 160 mPas, preferably from 60 to 160 mPas, preferably from 80 to 150 mPas, preferably from 90 to 140 mPas, preferably from 90 to 130 mPas, preferably from 90 to 115 mPas.
The liquid crystal composition of the present invention has a dielectric anisotropy (. DELTA.. di-elect cons.) at 20 ℃ of-1.7 to-4.0, preferably-1.7 to-3.5, more preferably-1.8 to-3.5, more preferably-1.9 to-3.3.
The liquid crystal composition of the present invention preferably contains the polymerizable compound of the first component and the polymerizable compound of the second component, further contains one or more compounds selected from the group consisting of compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04), (N-05) and (N-06), further contains one or more compounds selected from the group consisting of compounds represented by the general formulae (NU-01) to (NU-08), and the total upper limit of the contents is preferably 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%, the total lower limit of the contents thereof is preferably 78 mass%, 80 mass%, 81 mass%, 83 mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, 90 mass%, 91 mass%, 92 mass%, 93 mass%, 94 mass%, 95 mass%, 96 mass%, 97 mass%, 98 mass%, 99 mass%, 100 mass%.
The liquid crystal composition of the present invention particularly preferably contains the polymerizable compound of the first component and the polymerizable compound of the second component, further contains one or more compounds selected from the group consisting of compounds represented by the general formulae (N-01), (N-02), (N-03) and (N-04), and further contains one or more compounds selected from the group consisting of compounds represented by the general formulae (NU-01) to (NU-08), and the total upper limit of the contents is preferably 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass% and 84 mass%, and the total lower limit of the contents is preferably 78 mass%, (N-01), 99 mass%, 98 mass%, 97 mass%, and 84 mass%, respectively, 80 mass%, 81 mass%, 83 mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, 90 mass%, 91 mass%, 92 mass%, 93 mass%, 94 mass%, 95 mass%, 96 mass%, 97 mass%, 98 mass%, 99 mass%, 100 mass%.
The liquid crystal composition of the present invention can impart a sufficiently high polymerization rate and a sufficiently large pretilt angle. In addition, the liquid crystal display element using the liquid crystal composition of the present invention has a small amount of residual polymerizable compound in the polymerized liquid crystal display element, and display defects such as IS in high-definition PSA-type or PSVA-type liquid crystal display elements such as 4K and 8K do not occur or can be significantly suppressed. Therefore, the production efficiency of high-definition PSA-type or PSVA-type liquid crystal display elements such as 4K and 8K can be significantly improved, and the industrial value is very high.
The liquid crystal composition of the present invention is suitable for producing a PSA-type or PSVA-type liquid crystal display device, and is also suitable for producing an NPS-type liquid crystal display device. Further, the present invention is also suitable for manufacturing a PI-less (PI-less) type liquid crystal display device characterized by having no alignment film.
The liquid crystal composition of the present invention is also suitable for a liquid crystal display element having no alignment film, i.e., a mode generally referred to as PI-less. For example, it is preferable to use a compound having a spontaneous alignment property described in Japanese patent application Nos. 2013-552125, 2014-517515, 06081361, 2015-546888, 2017-12710, WO2017041893A, 06070973, WO17/047177, etc. in combination with the liquid crystal composition of the present invention.
The liquid crystal composition of the present invention is useful for liquid crystal display elements for active matrix driving, and can be used for liquid crystal display elements such as PSA, PSVA, PS-IPS, PS-FFS, and NPS.
The liquid crystal display element of the present invention preferably includes: a 1 st substrate and a 2 nd substrate disposed opposite to each other, a common electrode provided on the 1 st substrate or the 2 nd substrate, a pixel electrode provided on the 1 st substrate or the 2 nd substrate and having a thin film transistor, and a liquid crystal layer provided between the 1 st substrate and the 2 nd substrate and containing a liquid crystal composition. If necessary, an alignment film for controlling the alignment direction of liquid crystal molecules may be provided on the side facing at least one of the 1 st substrate and/or the 2 nd substrate so as to be in contact with the liquid crystal layer. As the alignment film, a vertical alignment film, a horizontal alignment film, or the like can be appropriately selected depending on the driving mode of the liquid crystal display element, and a known alignment film such as a rubbing alignment film (for example, polyimide), a photo alignment film (for example, decomposed polyimide), or the like can be used. Further, a color filter may be provided on the 1 st substrate or the 2 nd substrate as appropriate, and a color filter may be provided on the pixel electrode or the common electrode.
As the 2-piece substrate of the liquid crystal cell used in the liquid crystal display device of the present invention, a transparent material having flexibility such as glass or plastic, or an opaque material such as silicon may be used. The transparent substrate having the transparent electrode layer can be obtained by, for example, sputtering Indium Tin Oxide (ITO) on a transparent substrate such as a glass plate.
The color filter can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like. In the case of a method of producing a color filter by a pigment dispersion method, a curable color composition for a color filter is applied to the transparent substrate, subjected to patterning treatment, and then cured by heating or irradiation with light. This process is performed for 3 colors of red, green, and blue, respectively, whereby a pixel portion for a color filter can be manufactured. Further, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal resistivity element may be provided on the substrate.
Preferably, the 1 st substrate and the 2 nd substrate are opposed to each other so that the common electrode and the pixel electrode layer are on the inner side.
The interval between the 1 st substrate and the 2 nd substrate can be adjusted by the spacer. In this case, the thickness of the light control layer is preferably adjusted to 1 to 100 μm. More preferably 1.5 to 10 μm, and when a polarizing plate is used, the product of the refractive index anisotropy Δ n of the liquid crystal and the cell thickness d is preferably adjusted so that the contrast becomes maximum. In the case of two polarizing plates, the polarizing axes of the polarizing plates may be adjusted to provide a good viewing angle and contrast. Further, a retardation film for extending the viewing angle may be used. Examples of the spacer include: glass particles, plastic particles, alumina particles, photoresist materials, and the like. Then, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates by using a mold provided with a liquid crystal injection port as necessary, the substrates are bonded to each other, and the sealant is thermally cured by heating.
As a method for sandwiching the liquid crystal composition between 2 substrates, a general vacuum injection method, ODF method or the like can be used.
The polymerizable compound contained in the liquid crystal composition of the present invention is preferably polymerized at an appropriate polymerization rate in order to obtain good alignment properties of the liquid crystal, and therefore, it is preferably polymerized by using the polymerizable compound singly or in combination or by sequentially irradiating the polymerizable compound with active energy rays such as ultraviolet rays or electron beams. When ultraviolet light is used, a polarized light source may be used, and a non-polarized light source may be used. In addition, when polymerization is performed in a state where the liquid crystal composition is sandwiched between 2 substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency to the active energy ray. In addition, the following means may be used: in the irradiation, only a specific portion is polymerized using a mask, and then the orientation state of the unpolymerized portion is changed by changing the conditions such as an electric field, a magnetic field, or temperature, and further irradiated with an active energy ray to be polymerized. In particular, when ultraviolet exposure is performed, it is preferable to apply a direct current electric field or an alternating current electric field to the liquid crystal composition and perform ultraviolet exposure at the same time. Among them, the applied alternating electric field is preferably alternating current of a frequency of 1Hz to 10kHz, more preferably a frequency of 60Hz to 10kHz, and the voltage is selected depending on the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the PSA or PSVA liquid crystal display device, the pretilt angle is preferably controlled to 80 degrees to 89.9 degrees from the viewpoints of alignment stability and contrast.
In a PSA-type or PSVA-type liquid crystal display device, if a polymerizable compound remains as it IS without being polymerized after the device IS manufactured, IS occurs. The amount of the residual polymerizable compound is preferably 100ppm or less, more preferably 50ppm or less, particularly preferably 20ppm or less, and particularly preferably 0 or less as the lower limit of detection.
The temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron beams used for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention is not particularly limited. For example, when the liquid crystal composition of the present invention is applied to a liquid crystal display element having a substrate with an alignment film, the liquid crystal composition is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. That is, it is preferable to polymerize the monomer at 15 to 50 ℃.
As the lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and the like can be used, and an ultrahigh-pressure UV lamp by usio corporation and a fluorescent ultraviolet lamp by TOSHIBA corporation are preferable. The wavelength of the ultraviolet light to be irradiated is preferably ultraviolet light whose irradiation wavelength range is not in the absorption wavelength range of the liquid crystal composition, and the ultraviolet light is preferably used by being filtered off as necessary. The intensity of the ultraviolet ray to be irradiated is preferably 0.1mW/cm2～100W/cm2More preferably 2mW/cm2～50W/cm2. The energy of the ultraviolet ray to be irradiated may be appropriately adjusted, and is preferably 10mJ/cm2To 500J/cm2More preferably 100mJ/cm2To 200J/cm2。
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the compositions of examples and comparative examples below, "%" means "% by mass". In the examples, the following abbreviations are used for the description of the compounds.
(side chain)
-n-CnH2n+1Straight-chain alkyl group having n carbon atoms
n-CnH2n+1-a linear alkyl group having n carbon atoms
-On-OCnH2n+1Straight-chain alkoxy group having n carbon atoms
nO-CnH2n+1O-straight-chain alkoxy group having n carbon atoms
-V-CH＝CH2
V-CH2＝CH-
-V--CH＝CH-
-O1V-O-CH2-V
-V1-CH＝CH-CH3
1V-CH3-CH＝CH-
-2V-CH2-CH2-CH＝CH2
V2-CH2＝CH-CH2-CH2-
-2V1-CH2-CH2-CH＝CH-CH3
1V2-CH3-CH＝CH-CH2-CH2-
-F-F
-OCF3-OCF3
(linker)
-CF2O--CF2-O-
-OCF2--O-CF2-
-1O--CH2-O-
-O1--O-CH2-
-COO--COO-
-OCO--OCO-
(Ring structure)
[ solution 68]
In the examples, the measured properties are as follows.
Tni: nematic phase-isotropic liquid phase transition temperature (. degree.C.)
Δ n: refractive index anisotropy at 20 DEG C
Eta: viscosity (mPa. s) at 20 DEG C
γ1: rotational viscosity (mPa. s) at 20 DEG C
Δ ε: dielectric anisotropy of 20 DEG C
K33: elastic constant K at 20 DEG C33(pN)
(method of manufacturing liquid Crystal display device and method of evaluating the same)
(evaluation of amount of Change in pretilt)
First, the pretilt angle of the liquid crystal display element was measured and set as the pretilt angle (initial).
Next, a rectangular voltage of 30V was applied to the liquid crystal display element at a frequency of 100Hz, and the liquid crystal display element was continuously irradiated with light from a backlight (back light) for 10 hours. Then, the pretilt angle was measured and set as the pretilt angle (after the test).
A value obtained by subtracting the pretilt angle (after the test) from the measured pretilt angle (initial) is set as a pretilt angle variation amount (═ absolute value of pretilt angle variation) [ ° ].
The pretilt angle was measured using a pretilt angle measurement system ("OPTIPRO" manufactured by Shintec corporation). The magnitude of the applied voltage (30V) is several times larger than the normal drive voltage, and this evaluation test is an accelerated test.
The closer the amount of change in the pretilt is to 0 DEG, the lower the possibility that display defects will occur due to the change in the pretilt becomes.
In this evaluation, the variation amount of 0.3[ ° ] is set as an allowable limit range of display failure.
(evaluation of residual monomer amount)
First, a liquid crystal composition containing a polymerizable compound was injected into a liquid crystal cell having a cell gap of 3.5 μm, which includes an ITO-equipped substrate obtained by applying a polyimide alignment film inducing vertical alignment and rubbing the film, by a vacuum injection method.
Then, the luminance of the liquid crystal cell injected with the liquid crystal composition containing the polymerizable compound was adjusted to 3.5mW/cm using a fluorescent UV lamp under the condition that the center wavelength was 365nm2Ultraviolet rays were irradiated for 120 minutes, thereby obtaining a liquid crystal display element (wherein evaluation of each characteristic value of the liquid crystal display element was performed using a liquid crystal display element produced by the same method).
The residual amount [ ppm ] of the polymerizable compound in the liquid crystal display element after irradiation was measured under the above irradiation conditions. The method for measuring the residual amount of the polymerizable compound will be described. First, the liquid crystal display element was decomposed to obtain an acetonitrile solution containing the liquid crystal composition, the polymer, and the elution components of the unreacted polymerizable compound. The peak areas of the components are measured by analyzing the components by using high performance liquid chromatography. The amount of the remaining polymerizable compound is determined by the ratio of the peak area of the liquid crystal compound to the peak area of the unreacted polymerizable compound as an index. The residual amount of the polymerizable compound is determined from this value and the amount of the polymerizable compound to be initially added. Wherein the detection limit of the residual amount of the polymerizable compound was 10 ppm. In this evaluation, the residual amount of 100ppm was set as an allowable limit range of display failure.
(evaluation of Voltage holding ratio)
First, a liquid crystal composition containing a polymerizable compound was injected into a liquid crystal cell having a cell gap of 3.5 μm containing an ITO-attached substrate having no polyimide alignment film by a vacuum injection method.
Subsequently, the resultant was heated at 120 ℃ for 1 hour, and then, the illuminance was adjusted to 3.5mW/cm using a fluorescent UV lamp under the condition that the central wavelength was 365nm2Then, ultraviolet rays were irradiated for 120 minutes to obtain a liquid crystal display element. The measurement conditions were 1V, 0.6Hz, and 60 ℃.
(preparation of liquid Crystal composition and evaluation results)
LC-1 and LC-2 liquid crystal compositions were prepared, and their physical property values were measured. The results of the composition and the physical properties of the liquid crystal composition are shown in table 1.
[ Table 1]
[ solution 69]
[ solution 70]
[ solution 71]
Comparative examples 1 and 2 and examples 1 to 5
The polymerizable compounds were added in the following amounts by mass to 100 parts by mass of the liquid crystal compositions (LC-1 and LC-2) to obtain polymerizable liquid crystal compositions. Using this polymerizable liquid crystal composition, a liquid crystal display element was produced by the above-mentioned method, and each value was measured.
The polymerizable compound-containing liquid crystal composition obtained by adding 0.2 parts by mass of the compound represented by the formula (SAL-X1), 0.4 parts by mass of the compound represented by the formula (SAL-X2) and 0.6 parts by mass of the compound represented by the formula (RM-R1) to 100 parts by mass of the liquid crystal composition LC-1 was referred to as comparative example 1.
Comparative example 2 was prepared by adding 0.2 part by mass of the compound represented by formula (SAL-X1), 0.4 part by mass of the compound represented by formula (SAL-X2), and 0.6 part by mass of the compound represented by formula (RM-R2) to 100 parts by mass of the liquid crystal composition LC-1.
The polymerizable compound-containing liquid crystal composition obtained in example 1 was prepared by adding 0.2 part by mass of the compound represented by the formula (SAL-X1), 0.4 part by mass of the compound represented by the formula (SAL-X2) and 0.6 part by mass of the compound represented by the formula (RM-11) to 100 parts by mass of the liquid crystal composition LC-1.
The polymerizable compound-containing liquid crystal composition obtained in example 2 was prepared by adding 0.2 part by mass of the compound represented by the formula (SAL-X1), 0.4 part by mass of the compound represented by the formula (SAL-X2) and 0.6 part by mass of the compound represented by the formula (RM-3) to 100 parts by mass of the liquid crystal composition LC-1.
The polymerizable compound-containing liquid crystal composition obtained in example 3 was prepared by adding 0.2 part by mass of the compound represented by the formula (SAL-X1), 0.4 part by mass of the compound represented by the formula (SAL-X2) and 0.6 part by mass of the compound represented by the formula (RM-4) to 100 parts by mass of the liquid crystal composition LC-1.
The polymerizable compound-containing liquid crystal composition obtained in example 4 was prepared by adding 0.2 part by mass of the compound represented by formula (SAL-X1), 0.4 part by mass of the compound represented by formula (SAL-X2), 0.3 part by mass of the compound represented by formula (RM-1), and 0.3 part by mass of the compound represented by formula (RM-11) to 100 parts by mass of liquid crystal composition LC-1.
The polymerizable compound-containing liquid crystal composition obtained in example 5 was prepared by adding 0.2 part by mass of the compound represented by formula (SAL-X1), 0.4 part by mass of the compound represented by formula (SAL-X2), 0.3 part by mass of the compound represented by formula (RM-1), and 0.3 part by mass of the compound represented by formula (RM-3) to 100 parts by mass of liquid crystal composition LC-1.
The voltage holding ratio, the pretilt angle change amount, and the total polymerizable compound residual amount after ultraviolet irradiation in comparative examples 1 to 2 and examples 1 to 5 are shown in table 2 below.
[ Table 2]
It is understood that the liquid crystal compositions of examples 1 to 3 of the present invention showed significantly higher voltage holding ratios than those of comparative examples 1 and 2. As described above, by using the compound represented by the general formula (i), burn-in and the like can be prevented.
It is further understood that the voltage holding ratios of examples 4 and 5 are higher than those of comparative example 1.
As described above, it was found that even when a part of the polymerizable compound represented by the general formula (L) was replaced with the compound represented by the general formula (i), a high retention rate was exhibited.
It is clear that the pretilt angle change amount is sufficiently small in examples 1 to 5.
It is found that the residual amount of the polymeric compounds of examples 1 to 5 is sufficiently small.
In addition, even if the polymerizable liquid crystal compositions prepared in examples 1 to 3 were stored at-20 ℃ for 240 hours, the nematic liquid crystal phase was maintained, and no precipitation of the polymerizable compound was observed.
From the above, it was confirmed that the liquid crystal composition of the present invention has a sufficiently high voltage holding ratio, hardly causes display defects due to a change in pretilt angle, and does not cause precipitation of a polymerizable compound.
(comparative examples 3 and 4, examples 6 to 10)
Comparative example 3 was prepared by adding 0.4 part by mass of the compound represented by formula (SAL-X2), 0.5 part by mass of the compound represented by formula (SAL-X3), and 0.6 part by mass of the compound represented by formula (RM-R3) to 100 parts by mass of the liquid crystal composition LC-2.
The polymerizable compound-containing liquid crystal composition obtained by adding 0.4 parts by mass of the compound represented by the formula (SAL-X2), 0.5 parts by mass of the compound represented by the formula (SAL-X3) and 0.6 parts by mass of the compound represented by the formula (RM-R3) to 100 parts by mass of the liquid crystal composition LC-2 was defined as comparative example 4.
The polymerizable compound-containing liquid crystal composition obtained in example 6 was prepared by adding 0.4 part by mass of the compound represented by the formula (SAL-X2), 0.5 part by mass of the compound represented by the formula (SAL-X3) and 0.6 part by mass of the compound represented by the formula (RM-25) to 100 parts by mass of the liquid crystal composition LC-2.
The polymerizable compound-containing liquid crystal composition obtained in example 7 was prepared by adding 0.4 part by mass of the compound represented by the formula (SAL-X2), 0.5 part by mass of the compound represented by the formula (SAL-X3) and 0.6 part by mass of the compound represented by the formula (RM-28) to 100 parts by mass of the liquid crystal composition LC-2.
The polymerizable compound-containing liquid crystal composition obtained in example 8 was prepared by adding 0.4 part by mass of the compound represented by the formula (SAL-X2), 0.5 part by mass of the compound represented by the formula (SAL-X3) and 0.6 part by mass of the compound represented by the formula (RM-23) to 100 parts by mass of the liquid crystal composition LC-2.
The polymerizable compound-containing liquid crystal composition obtained in example 9 was prepared by adding 0.4 part by mass of the compound represented by the formula (SAL-X2), 0.5 part by mass of the compound represented by the formula (SAL-X3) and 0.6 part by mass of the compound represented by the formula (RM-33) to 100 parts by mass of the liquid crystal composition LC-2.
The polymerizable compound-containing liquid crystal composition obtained in example 10 was prepared by adding 0.4 part by mass of the compound represented by formula (SAL-X2), 0.5 part by mass of the compound represented by formula (SAL-X3), 0.3 part by mass of the compound represented by formula (RM-25), and 0.3 part by mass of the compound represented by formula (RM-28) to 100 parts by mass of liquid crystal composition LC-2.
The polymerizable compound-containing liquid crystal composition obtained in example 11 was prepared by adding 0.4 part by mass of the compound represented by formula (SAL-X2), 0.5 part by mass of the compound represented by formula (SAL-X3), 0.3 part by mass of the compound represented by formula (RM-25), and 0.3 part by mass of the compound represented by formula (RM-23) to 100 parts by mass of liquid crystal composition LC-2.
The voltage holding ratio, the pretilt angle change amount, and the total polymerizable compound remaining amount after ultraviolet irradiation in comparative examples 3 and 4 and examples 6 to 11 are shown in the table.
[ Table 3]
| Comparative example 3 | Comparative example 4 | |
| Liquid crystal composition | LC-B | LC-B |
| SAL-X2 | 0.4 | 0.4 |
| SAL-X3 | 0.5 | 0.5 |
| RM-R3 | 0.6 | |
| RM-R4 | 0.6 | |
| RM-25 | ||
| RM-28 | ||
| RM-23 | ||
| RM-33 | ||
| Voltage holding ratio | 84.6 | 85.3 |
| Variation of pretilt angle | 3.4 | 2.5 |
| Residual amount of polymerizable compound | 25 | 35 |
[ Table 4]
| Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | |
| Liquid crystal composition | LC-B | LC-B | LC-B | LC-B | LC-B | LC-B |
| SAL-X2 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| SAL-X3 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| RM-R3 | ||||||
| RM-R4 | ||||||
| RM-25 | 0.6 | 0.3 | 0.3 | |||
| RM-28 | 0.6 | 0.3 | ||||
| RM-23 | 0.6 | 0.3 | ||||
| RM-33 | 0.6 | |||||
| Voltage holding ratio | 97.5 | 97.2 | 97.8 | 96.5 | 96.5 | 93.8 |
| Variation of pretilt angle | 0.1 | 0.1 | 0.2 | 0.1 | 0.1 | 0.1 |
| Residual amount of polymerizable compound | 55 | 43 | 23 | 70 | 34 | 32 |
It is understood that the voltage holding ratios of examples 6 to 9, which are the polymerizable liquid crystal compositions of the present invention, are significantly higher than those of comparative examples 3 and 4. As described above, by using the compound represented by the general formula (i), display defects such as burn-in can be prevented.
It is understood that the voltage holding ratios of examples 10 and 11 are also higher than those of comparative examples 3 and 4.
As described above, it was found that even when 2 or more compounds represented by the general formula (i) were used, a high voltage holding ratio was exhibited.
It is clear that the pretilt angle change amounts in examples 6 to 11 are sufficiently small.
It is found that the residual amount of the polymeric compounds of examples 6 to 11 is sufficiently small.
In addition, even when the polymerizable liquid crystal compositions obtained in examples 6 to 11 were stored at-20 ℃ for 240 hours, the nematic liquid crystal phase was maintained, and no precipitation of the polymerizable compound was observed.
As described above, it was confirmed that by using the polymerizable liquid crystal composition of the present invention, a liquid crystal display element having a sufficiently high voltage holding ratio, in which display defects due to a change in pretilt angle are less likely to occur, and in which no polymerizable compound remains, can be obtained.
Claims (19)
1. A polymerizable liquid crystal composition comprising a liquid crystal composition and 1 or 2 or more kinds of polymerizable compounds represented by the general formula (i),
[ solution 1]
In the formula, Xi1、Xi2、Xi3、Xi4、Xi5、Xi6、Xi7、Xi8、Xi9、Xi10、Xi11And Xi12Each independently represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom,
is selected from Xi1～Xi12At least two of (a) each independently represent an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a halogen atom,
Pi1and Pi2Each independently represents any one of the following formulae (R-I) to (R-IX),
[ solution 2]
In the formula, R21、R31、R41、R51And R61Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, W represents a single bond, -O-or methylene, T represents a single bond or-COO-, p, T and q each independently represent0.1 or 2 of the total number of the first and second groups,
Spi1and Spi2Each independently represents a single bond or an alkylene group having 1 to 15 carbon atoms, and 1 or 2 or more-CH in the alkylene group2Can be substituted by-O-, -OCO-or-COO-in such a way that the oxygen atoms are not directly adjacent,
ni1represents a number of 0, 1 or 2,
Li1and Li2Each independently represents a single bond, -OCH2-、-CH2O-、-C2H4-、-OC2H4O-、-COO-、-OCO-、-CH＝CRa-COO-、-CH＝CRa-OCO-、-COO-CRa＝CH-、-OCO-CRa＝CH-、-(CH2)z-COO-、-(CH2)z-OCO-、-OCO-(CH2)z-、-COO-(CH2)z-、-CH＝CH-、-CF2O-、-OCF2-or-C ≡ C-, wherein R isaRepresents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, z represents an integer of 1 to 4,
when there are a plurality of Xi5、Xi6、Xi7、Xi8And/or Li2In the case of (3), they may be the same or different.
2. The polymerizable liquid crystal composition according to claim 1, wherein in the general formula (i), X is selected fromi5、Xi6、Xi7、Xi8、Xi9、Xi10、Xi11And Xi12At least two of (a) each independently represent an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom.
3. The polymerizable liquid crystal composition according to claim 1 or 2, wherein in the general formula (i), X is selected from the group consisting ofi5、Xi6、Xi7、Xi8、Xi9、Xi10、Xi11And Xi12At least two of (a) are each independently an alkyl group having 1 to 18 carbon atoms or a halogen atom.
4. The polymerizable liquid crystal composition according to any one of claims 1 to 3, comprising:
a polymerizable compound represented by the general formula (i), and
an orientation aid having a chemical structure different from that of the polymerizable compound represented by the general formula (i) and having an adsorption group.
5. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein n in the general formula (i)i1Is 0 and is selected from Xi9、Xi10、Xi11And Xi12At least 1 of (a) are each independently an alkyl group having 1 to 18 carbon atoms.
6. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein n in the general formula (i)i1Is 1 or 2 and is selected from Xi5、Xi6、Xi7、Xi8、Xi9、Xi10、Xi11And Xi12At least 1 of (a) are each independently an alkyl group having 1 to 18 carbon atoms.
7. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein n in the general formula (i)i1Is 0 and is selected from Xi9、Xi10、Xi11And Xi12Each of 2 of (a) is independently an alkyl group having 1 to 3 carbon atoms or a halogen atom.
8. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein n in the general formula (i)i1Is 1 or 2 and is selected from Xi5、Xi6、Xi7And Xi82 are each independently an alkyl group having 1 to 18 carbon atoms, a halogen atom, or Xi9、Xi10、Xi11And Xi122 of (b) are an alkyl group having 1 to 18 carbon atoms or a halogen atom.
9. According to any one of claims 1 to 4The polymerizable liquid crystal composition according to (i), wherein n isi1Is 0 or 1.
10. The polymerizable liquid crystal composition according to any one of claims 1 to 9, wherein in the general formula (i), Xi12Or Xi11Is a hydrogen atom.
11. The polymerizable liquid crystal composition according to any one of claims 1 to 10, wherein in the general formula (i), Li1And Li2Is a single bond.
12. The polymerizable liquid crystal composition according to any one of claims 1 to 11, wherein the amount of the polymerizable compound represented by the general formula (i) added is 0.20 to 1.0 mass%.
13. The polymerizable liquid crystal composition according to any one of claims 1 to 12, which comprises 1 or 2 or more compounds selected from the group of compounds represented by general formulae (N-01) to (N-05),
[ solution 3]
In the formula, R21And R22Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, 1 or 2 or more-CH groups not adjacent to each other2-may also be independently substituted by-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-, Z1Each independently represents a single bond, -CH2CH2-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-, -CH ═ CH-, -CF ═ CF-or-C ≡ C-, and m independently represents 1 or 2, respectively.
14. The polymerizable liquid crystal composition according to any one of claims 1 to 13, which comprises 1 or 2 or more compounds selected from the group of compounds represented by general formulae (NU-01) to (NU-08),
[ solution 4]
In the formula, RNU11、RNU12、RNU21、RNU22、RNU31、RNU32、RNU41、RNU42、RNU51、RNU52、RNU61、RNU62、RNU71、RNU72、RNU81And RNU82Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, 1 or 2 or more-CH groups not adjacent to each other2-may also be independently substituted with-CH ═ CH-, -C ≡ C-, -O-, -CO-, -COO-, or-OCO-.
15. The polymerizable liquid crystal composition according to any one of claims 4 to 14, wherein the alignment aid is a compound having a polymerizable group for polymerization, a mesogen group similar to liquid crystal molecules, an adsorbing group capable of interacting with a member directly abutting against the liquid crystal layer, and an alignment-inducing group that induces alignment of the liquid crystal molecules.
16. A liquid crystal display element using the polymerizable liquid crystal composition according to any one of claims 1 to 15.
17. A liquid crystal display element for active matrix driving, which uses the polymerizable liquid crystal composition according to any one of claims 1 to 15.
18. A liquid crystal display device for PSA mode, PSVA mode, PS-IPS mode, or PS-FSS mode, which uses the polymerizable liquid crystal composition according to any one of claims 1 to 15.
19. The polymerizable liquid crystal composition according to any one of claims 1 to 15, which is used for a liquid crystal display element having no alignment film on at least one of a pair of substrates.
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| PCT/JP2019/037807 WO2020075509A1 (en) | 2018-10-11 | 2019-09-26 | Polymerizable liquid-crystal composition and liquid-crystal display element |
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07101900A (en) * | 1993-02-15 | 1995-04-18 | Seiko Epson Corp | Terphenyl methacrylate derivative and polymer dispersion type liquid crystal display element using the same |
| US20100283951A1 (en) * | 2009-05-07 | 2010-11-11 | Lee Jun-Hyup | Liquid crystal display, a method for manufacturing a liquid crystal display and a liquid crystal composition |
| JP2012180484A (en) * | 2011-03-02 | 2012-09-20 | Jnc Corp | Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display device, novel maleimide-based polymer, and novel bismaleimide |
| KR20150004204A (en) * | 2013-07-02 | 2015-01-12 | 한국화학연구원 | Polymerizable mesogen compound having improved solubility, preparation of thereof and polymerizable liquid crystal compositions containing the same |
| CN104342170A (en) * | 2013-08-02 | 2015-02-11 | 江苏和成显示科技股份有限公司 | Polymerizable liquid crystal composition and display device |
| US20160170269A1 (en) * | 2012-10-19 | 2016-06-16 | Sharp Kabushiki Kaisha | Liquid-crystal display device and process for producing liquid-crystal display device |
| US20160349574A1 (en) * | 2013-10-30 | 2016-12-01 | Dic Corporation | Liquid-crystal display element |
| CN107109233A (en) * | 2015-01-20 | 2017-08-29 | 捷恩智株式会社 | Liquid-crystal composition and liquid crystal display cells |
| CN107850810A (en) * | 2015-08-11 | 2018-03-27 | Dic株式会社 | Liquid crystal display cells |
| CN107841316A (en) * | 2016-09-20 | 2018-03-27 | Dic株式会社 | The spontaneous orientation auxiliary agent of liquid-crystal composition |
| CN107924089A (en) * | 2015-08-11 | 2018-04-17 | Dic株式会社 | Liquid crystal display element |
| WO2018079333A1 (en) * | 2016-10-26 | 2018-05-03 | Dic株式会社 | Spontaneous alignment assistant for liquid crystal compositions |
| WO2018084019A1 (en) * | 2016-11-01 | 2018-05-11 | Dic株式会社 | Spontaneous orientation aid for liquid crystal composition |
| CN108179014A (en) * | 2016-12-08 | 2018-06-19 | 默克专利股份有限公司 | Polymerizable compound and its purposes in a liquid crystal display |
| CN108192642A (en) * | 2018-01-30 | 2018-06-22 | 石家庄诚志永华显示材料有限公司 | The display of liquid-crystal composition and application the composition |
| WO2018117213A1 (en) * | 2016-12-22 | 2018-06-28 | Dic株式会社 | Liquid crystal display element |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9234136B2 (en) * | 2011-07-07 | 2016-01-12 | Merck Patent Gmbh | Liquid-crystalline medium |
| CN110651022A (en) * | 2017-06-01 | 2020-01-03 | Dic株式会社 | Polymerizable monomer, liquid crystal composition using same, and liquid crystal display element |
| TWI774891B (en) * | 2017-12-22 | 2022-08-21 | 日商迪愛生股份有限公司 | Liquid crystal composition and liquid crystal display element |
-
2019
- 2019-09-26 JP JP2020524254A patent/JP6844749B2/en active Active
- 2019-09-26 CN CN201980051672.6A patent/CN112534022A/en active Pending
- 2019-09-26 WO PCT/JP2019/037807 patent/WO2020075509A1/en active Application Filing
- 2019-09-27 TW TW108135187A patent/TWI828769B/en active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07101900A (en) * | 1993-02-15 | 1995-04-18 | Seiko Epson Corp | Terphenyl methacrylate derivative and polymer dispersion type liquid crystal display element using the same |
| US20100283951A1 (en) * | 2009-05-07 | 2010-11-11 | Lee Jun-Hyup | Liquid crystal display, a method for manufacturing a liquid crystal display and a liquid crystal composition |
| JP2012180484A (en) * | 2011-03-02 | 2012-09-20 | Jnc Corp | Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display device, novel maleimide-based polymer, and novel bismaleimide |
| US20160170269A1 (en) * | 2012-10-19 | 2016-06-16 | Sharp Kabushiki Kaisha | Liquid-crystal display device and process for producing liquid-crystal display device |
| KR20150004204A (en) * | 2013-07-02 | 2015-01-12 | 한국화학연구원 | Polymerizable mesogen compound having improved solubility, preparation of thereof and polymerizable liquid crystal compositions containing the same |
| CN104342170A (en) * | 2013-08-02 | 2015-02-11 | 江苏和成显示科技股份有限公司 | Polymerizable liquid crystal composition and display device |
| US20160349574A1 (en) * | 2013-10-30 | 2016-12-01 | Dic Corporation | Liquid-crystal display element |
| CN107109233A (en) * | 2015-01-20 | 2017-08-29 | 捷恩智株式会社 | Liquid-crystal composition and liquid crystal display cells |
| CN107850810A (en) * | 2015-08-11 | 2018-03-27 | Dic株式会社 | Liquid crystal display cells |
| CN107924089A (en) * | 2015-08-11 | 2018-04-17 | Dic株式会社 | Liquid crystal display element |
| CN107841316A (en) * | 2016-09-20 | 2018-03-27 | Dic株式会社 | The spontaneous orientation auxiliary agent of liquid-crystal composition |
| WO2018079333A1 (en) * | 2016-10-26 | 2018-05-03 | Dic株式会社 | Spontaneous alignment assistant for liquid crystal compositions |
| WO2018084019A1 (en) * | 2016-11-01 | 2018-05-11 | Dic株式会社 | Spontaneous orientation aid for liquid crystal composition |
| CN108179014A (en) * | 2016-12-08 | 2018-06-19 | 默克专利股份有限公司 | Polymerizable compound and its purposes in a liquid crystal display |
| WO2018117213A1 (en) * | 2016-12-22 | 2018-06-28 | Dic株式会社 | Liquid crystal display element |
| CN108192642A (en) * | 2018-01-30 | 2018-06-22 | 石家庄诚志永华显示材料有限公司 | The display of liquid-crystal composition and application the composition |
Non-Patent Citations (2)
| Title |
|---|
| ST WU，等: "FLUORINATED DIPHENYL-DIACETYLENE AND TOLANE LIQUID-CRYSTALS WITH LOW THRESHOLD VOLTAGE", 《APPLIED PHYSICS LETTERS》, vol. 61, no. 19, 9 November 1992 (1992-11-09), pages 2275 - 2277, XP000324723, DOI: 10.1063/1.108263 * |
| 彭增辉，等: "光敏小分子单体链聚合诱导液晶分子排列的研究", 《液晶与显示》, no. 1, 31 December 2003 (2003-12-31), pages 14 - 17 * |
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| JP6844749B2 (en) | 2021-03-17 |
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