CN118139946A - Liquid-crystalline medium comprising a polymerisable compound - Google Patents
Liquid-crystalline medium comprising a polymerisable compound Download PDFInfo
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- CN118139946A CN118139946A CN202280069607.8A CN202280069607A CN118139946A CN 118139946 A CN118139946 A CN 118139946A CN 202280069607 A CN202280069607 A CN 202280069607A CN 118139946 A CN118139946 A CN 118139946A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 393
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 125000004429 atom Chemical group 0.000 claims description 108
- 125000000217 alkyl group Chemical group 0.000 claims description 90
- 238000000034 method Methods 0.000 claims description 62
- 239000003381 stabilizer Substances 0.000 claims description 61
- 229910052731 fluorine Inorganic materials 0.000 claims description 60
- -1 naphthalene-2, 6-diyl Chemical group 0.000 claims description 50
- 125000003545 alkoxy group Chemical group 0.000 claims description 49
- 239000000654 additive Substances 0.000 claims description 45
- 125000003342 alkenyl group Chemical group 0.000 claims description 45
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 25
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000003254 radicals Chemical class 0.000 claims description 13
- 125000006850 spacer group Chemical group 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 12
- 125000004434 sulfur atom Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000002019 doping agent Substances 0.000 claims description 10
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 claims description 9
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 8
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 7
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 6
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 6
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 4
- SZTBMYHIYNGYIA-UHFFFAOYSA-M 2-chloroacrylate Chemical compound [O-]C(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-M 0.000 claims description 4
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 claims description 4
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000014509 gene expression Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000003566 oxetanyl group Chemical group 0.000 claims description 3
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000006017 1-propenyl group Chemical group 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 125000005755 decalin-2,6-ylene group Chemical group [H]C1([H])C([H])([H])C2([H])C([H])([H])C([H])([*:2])C([H])([H])C([H])([H])C2([H])C([H])([H])C1([H])[*:1] 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 19
- 238000010521 absorption reaction Methods 0.000 abstract description 16
- 230000003287 optical effect Effects 0.000 abstract description 10
- 239000004973 liquid crystal related substance Substances 0.000 description 351
- 239000000203 mixture Substances 0.000 description 268
- 238000006116 polymerization reaction Methods 0.000 description 42
- 229940125904 compound 1 Drugs 0.000 description 40
- 239000010410 layer Substances 0.000 description 31
- 230000000996 additive effect Effects 0.000 description 25
- 229940125782 compound 2 Drugs 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 125000006193 alkinyl group Chemical group 0.000 description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 239000004990 Smectic liquid crystal Substances 0.000 description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000008033 biological extinction Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 101000767534 Arabidopsis thaliana Chorismate mutase 2 Proteins 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- 101000986989 Naja kaouthia Acidic phospholipase A2 CM-II Proteins 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 150000004074 biphenyls Chemical class 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 2
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 2
- 230000000254 damaging effect Effects 0.000 description 2
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PKORYTIUMAOPED-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinazoline Chemical class C1=CC=C2NCNCC2=C1 PKORYTIUMAOPED-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical group C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- GRZJZRHVJAXMRR-UHFFFAOYSA-N 1-cyclohexyl-2-phenylbenzene Chemical group C1CCCCC1C1=CC=CC=C1C1=CC=CC=C1 GRZJZRHVJAXMRR-UHFFFAOYSA-N 0.000 description 1
- RAYZALBEMJMGEA-UHFFFAOYSA-N 1-cyclohexylnaphthalene Chemical compound C1CCCCC1C1=CC=CC2=CC=CC=C12 RAYZALBEMJMGEA-UHFFFAOYSA-N 0.000 description 1
- GVQIKUVVJFKEDH-UHFFFAOYSA-N 2,5-dicyclohexyl-5-phenylcyclohexa-1,3-diene Chemical group C1(CCCCC1)C1(CC=C(C=C1)C1CCCCC1)C1=CC=CC=C1 GVQIKUVVJFKEDH-UHFFFAOYSA-N 0.000 description 1
- SMHSPYVJAUGNOI-UHFFFAOYSA-N 2-cyclohexyl-1,4-dioxane Chemical compound C1CCCCC1C1OCCOC1 SMHSPYVJAUGNOI-UHFFFAOYSA-N 0.000 description 1
- YJDDXMSIMBMMGY-UHFFFAOYSA-N 2-cyclohexylpyrimidine Chemical compound C1CCCCC1C1=NC=CC=N1 YJDDXMSIMBMMGY-UHFFFAOYSA-N 0.000 description 1
- WLNDDIWESXCXHM-UHFFFAOYSA-N 2-phenyl-1,4-dioxane Chemical compound C1OCCOC1C1=CC=CC=C1 WLNDDIWESXCXHM-UHFFFAOYSA-N 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- 241001270131 Agaricus moelleri Species 0.000 description 1
- 241000284466 Antarctothoa delta Species 0.000 description 1
- OPPSKSYJWWRRAK-UHFFFAOYSA-N CCCCCCCCCCCCC1=C(C(O)=O)C(CC)=C(C)C(OCCCCCC)=C1C.N Chemical compound CCCCCCCCCCCCC1=C(C(O)=O)C(CC)=C(C)C(OCCCCCC)=C1C.N OPPSKSYJWWRRAK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004890 Hydrophobing Agent Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004850 cyclobutylmethyl group Chemical group C1(CCC1)C* 0.000 description 1
- DQZKGSRJOUYVPL-UHFFFAOYSA-N cyclohexyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1CCCCC1 DQZKGSRJOUYVPL-UHFFFAOYSA-N 0.000 description 1
- VJCWGXGMXAVKJU-UHFFFAOYSA-N cyclohexyl cyclohexanecarboxylate Chemical compound C1CCCCC1C(=O)OC1CCCCC1 VJCWGXGMXAVKJU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003392 indanyl group Chemical class C1(CCC2=CC=CC=C12)* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical compound C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical class N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical class C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000004862 thiobutyl group Chemical group 0.000 description 1
- 125000004014 thioethyl group Chemical group [H]SC([H])([H])C([H])([H])* 0.000 description 1
- 125000004055 thiomethyl group Chemical group [H]SC([H])([H])* 0.000 description 1
- 125000004035 thiopropyl group Chemical group [H]SC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QZNXARNIBFGRRC-UHFFFAOYSA-N triphenyl-(2,3,4,5-tetrabutylphenyl)azanium borate Chemical compound B([O-])([O-])[O-].C(CCC)C=1C(=C(C(=C(C1)[N+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)CCCC)CCCC)CCCC.C(CCC)C=1C(=C(C(=C(C1)[N+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)CCCC)CCCC)CCCC.C(CCC)C=1C(=C(C(=C(C1)[N+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)CCCC)CCCC)CCCC QZNXARNIBFGRRC-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to LC media comprising two or more polymerisable compounds, at least one of which has absorption in the long UV wavelength range, to the use for optical, electro-optical and electronic purposes, in particular in LC displays, in particular in PSA (polymer stabilised alignment) or SA (self alignment) mode LC displays, to PSA or SA mode LC displays comprising said LC media, and to a method of manufacturing said LC displays, enabling to minimize production costs and energy savings.
Description
The present invention relates to LC media comprising two or more polymerisable compounds, at least one of which is absorbing in the long UV wavelength range, for optical, electro-optical and electronic purposes, in particular for use in LC displays, especially in PSA (polymer stabilised alignment) or SA (self alignment) mode LC displays, PSA or SA mode LC displays comprising said LC media, and a method of manufacturing said LC displays, which method enables to minimize production costs and energy savings.
The popularity of 8K and game monitors has led to an increase in demand for LC display (LCD) panels with higher refresh rates, and therefore, for LC media with faster response times. Many of these LCD panels use a Polymer Stabilized (PS) or polymer stabilized alignment mode (PSA) mode, such as PS-VA (vertical alignment), PS-IPS (in-plane switching) or PS-FFS (fringe field switching) mode or derivative thereof, or a self-alignment (SA) mode, such as SA-VA, which is polymer stabilized.
In PS or PSA mode, a small amount, typically 0.1-1%, of one or more polymerizable mesogenic compounds (also called RM (reactive mesogens)) is added to the LC medium. After filling the LC medium into the display, the RM is then polymerized in situ by UV photopolymerization while applying a voltage to the electrodes of the display. Thereby, a small tilt angle is created in the LC molecules of the LC medium, which is stabilized by the polymerized RM. The UV polymerization process (also known as the "PSA process") is typically performed in two steps: a first UV exposure step ("UV 1 step") to which a voltage is applied to create a tilt angle, and a second UV exposure step ("UV 2 step") to which no voltage is applied to complete RM polymerization.
In the SA-VA mode, the alignment layer is omitted in the display. Instead, small amounts, typically 0.1-2.5%, of self-alignment (SA) additives are added to the LC medium, which will induce the desired alignment in situ by self-assembly mechanisms, such as homeotropic or planar alignment. The SA additive typically contains an organic mesogenic core group to which one or more polar anchoring groups, such as hydroxyl, carboxyl, amino or thiol groups, are attached, which are capable of interacting with the substrate surface, resulting in alignment of the additive on the substrate surface and inducing the desired alignment in the LC molecules. The SA additive may also contain one or more polymerizable groups, which can polymerize under similar conditions as the RM used in the PSA process. In addition to the SA additive, the LC medium contains one or more RMs.
One way to reduce the response time of LC media to PSA mode is, for example, by using a compound with alkenyl groups as a component of the LC host mixture. However, this may lead to reduced reliability of the mixture when exposed to UV light required to polymerize the RM additives, which is believed to be caused by the polyimide reaction of the alkenyl compound with the alignment layer, especially problematic when using shorter UV wavelengths of less than 320 nm. Thus, there is a trend to use longer UV wavelengths for PSA processes.
UV-LED lamps have also been suggested for use in PSA processes because they exhibit less energy consumption, longer lifetime and more efficient transfer of light energy to the LC medium due to narrower emission peaks, which results in reduced UV intensity and/or UV irradiation time. This can shorten the takt time and save energy and production costs. Currently available UV lamps have higher wavelength emissions, for example at 365 nm.
Thus, there is a need for polymerizable LC media containing RMs that can polymerize efficiently at longer UV wavelengths.
In addition, there is a great need for PSA or SA displays and LC media and polymerizable compounds for such PSA or SA displays that are capable of having high specific resistance, while having a large operating temperature range, short response time, even at low temperatures, and low threshold voltages, low tilt angles, high tilt stability, multiple gray scales, high contrast and wide viewing angles, high reliability and high VHR values after UV exposure, and in the case of polymerizable compounds, low melting points and high solubility in LC host mixtures. In displays for mobile applications, it is particularly desirable to have available LC media that exhibit low threshold voltages and high birefringence.
The invention aims at: novel suitable materials are provided, in particular RM and LC media comprising RM, for use in PSA or SA displays, which do not have the above-mentioned disadvantages or have them to a reduced extent.
In particular, the invention aims at: providing an LC medium for use in PSA or SA displays comprising an RM, said medium being capable of having a very high specific resistance value, a high VHR value, high reliability, a low threshold voltage, a short response time, a high birefringence, showing good UV absorption (especially at longer UV wavelengths, preferably 340-380 nm), enabling rapid and complete polymerization of the RM, allowing low tilt angles to occur (preferably as fast as possible), being capable of having a high tilt angle stability (even after longer and/or UV exposure), reducing or preventing the occurrence of "image sticking" and "ODF non-uniformity (mura)" in the display, and showing high solubility in the LC medium in case of rapid and complete polymerization of the RM (said LC medium is typically used as a host mixture for PSA or SA displays).
It is another object of the present invention to provide LC media for PSA displays wherein RM shows both fast polymerization speed and good reliability parameters like high VHR or tilt stability.
It is a further object of the present invention to provide novel LC media containing RM, in particular for optical, electro-optical and electronic applications, as well as suitable methods and intermediates for preparing said LC media.
It is a further object of the present invention to provide an RM-containing LC medium which exhibits one or more of the following advantageous effects:
They produce a tilt angle of the desired angle upon exposure to UV light,
They lead to a high tilt stability,
They exhibit good UV absorption, especially at higher UV wavelengths, especially at 340-400nm, and RM is capable of rapid and complete polymerization at these wavelengths,
They are suitable for PSA displays prepared by polymerization processes using UV B-type or UV-LED lamps, in particular using longer wavelengths than the UV C-type lamps currently used, in particular in the second UV step of the PSA process, which requires longer irradiation times, in order to reduce damage to the LC medium molecules,
They enable a good control of the first UV step time range, wherein the tilt angle is generated during the UV process,
They enable the use of UV-LED lamps which have a longer lifetime, lower energy consumption and more efficient light energy transfer than the fluorescent UV lamps commonly used,
They are able and maintain the time frame of the second UV step, in which any residual RM is polymerized and the tilt angle is stabilized, minimizing production costs and energy consumption as much as possible
After the first and second UV exposure step, the residual RM has little or no negative influence on the performance parameters of the LC mixture (e.g. VHR, tilt stability, etc.),
They exhibit good solubility and stability in LC mixtures over a wide temperature range, preferably-40 to 140 ℃.
It has been found that one or more of these objects can be achieved by providing an LC medium comprising a polymerisable compound as described and claimed herein.
The present invention relates to LC media comprising two or more polymerisable compounds, wherein at least one polymerisable compound is selected from the group of formula I
Wherein each group, independently of the other and identically or differently for each occurrence, has the following meanings:
R a,Rb is P-Sp-or R, wherein at least one of R a and R b represents P-Sp-,
A a,Ab is phenylene-1, 4-diyl or naphthalene-2-6-diyl, which is optionally substituted by one or more radicals L,
Z a,Zb is-CH=CH-, -CF=CF-, C.ident.C-or a single bond, preferably a single bond,
P is a polymerizable group and is preferably a polymerizable group,
Sp is a spacer group optionally substituted by one or more groups P, or a single bond,
R is a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, wherein one or more non-adjacent CH 2 groups are optionally substituted by-O-, in such a way that the O-and/or S-atoms are not directly linked to each other-S-, -CO-O-, -O-CO-O-, CR 0＝CR00 -, -C≡C-, and,Substituted, and wherein one or more H atoms are each optionally replaced by F or Cl,
L is F, cl, br, -CN or a linear, branched or cyclic alkyl having 1 to 25C atoms, wherein one or more non-adjacent CH 2 groups are optionally substituted by-O-, in such a way that the O-and/or S-atoms are not directly linked to each other-S-, -CO-O-, -O-CO-O-, -N (R 0)-、-Si(R0R00) -, -CH=CH-, or-C≡C-substitution, and wherein one or more H atoms are each optionally replaced by F or Cl,
R 0,R00 is H or alkyl having 1 to 12 carbon atoms,
A, b is 0, 1 or 2, preferably 0 or 1,
R4 is 0,1, 2, 3 or 4, preferably 0,1 or 2.
The invention also relates to LC media having negative dielectric anisotropy and comprising two or more polymerisable compounds, wherein at least one polymerisable compound is a compound of formula I and preferably exhibits absorption in the range of 340 to 400nm, very preferably 350 to 380nm, and further comprising one or more compounds of formula II
Wherein each group, independently of the other and identically or differently for each occurrence, has the following meanings:
r 1 and R 2 are straight-chain, branched or cyclic alkyl having 1to 25C atoms, wherein one or more non-adjacent CH 2 groups are optionally interrupted by-O-, in such a way that the O-and/or S-atoms are not directly linked to each other-S-, -CO-O-, -O-CO-O-, CR 0＝CR00 -, -C≡C-, and, Substituted, and wherein one or more H atoms are each optionally replaced by F or Cl, preferably alkyl or alkoxy having 1 to 6C atoms,
R 0,R00 is H or alkyl having 1 to 12C atoms, preferably H,
A 1 and A 2 are selected from the group of the formula
Preferably selected from the formulae A1, A2, A3, A4, A5, A6, A9 and A10, very preferably selected from the formulae A1, A2, A3, A4, A5, A9 and A10,
Z 1 and Z 2 are -CH2CH2-、-CH＝CH-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、-CO-O-、-O-CO-、-C2F4-、-CF＝CF-、-CH＝CH-CH2O- or a single bond, preferably a single bond,
L 1,L2,L3 and L 4 are F, cl, OCF 3、CF3、CH3、CH2 F or CHF 2, preferably F or Cl, very preferably F,
Y is H, F, cl, CF 3、CHF2 or CH 3, preferably H or CH 3, very preferably H,
L C is CH 3 or OCH 3, preferably CH 3,
A1 Is a number of 1 or 2, and the number of the groups is 1 or 2,
A2 0 or 1.
The invention also relates to the use of an LC medium as described above and below in a PSA or SA mode LC display.
The invention further relates to a method for preparing an LC medium as described above and below, comprising the steps of: one or more polymerizable compounds of formula I are mixed with one or more compounds of formula II, and optionally with other LC compounds and/or additives.
The invention further relates to LC displays comprising an LC medium as described above and below, wherein the polymerisable compounds are present in polymerized form, preferably PSA or SA displays, very preferably PS-VA, PS-IPS, PS-FFS or SA-VA displays.
The invention further relates to an LC display comprising an LC medium according to the invention as described above and below, which is a PSA or SA display, preferably a PS-VA, PS-IPS, PS-FFS or SA-VA display.
The invention further relates to a PSA-type LC display comprising two substrates, at least one transparent to light, one electrode provided on each substrate or two electrodes provided on only one substrate, and a layer of LC medium as described above and below between the substrates, wherein the polymerisable compound is polymerised between the substrates of the display by UV photopolymerization.
The invention further relates to a method of producing an LC display as described above and below, comprising the steps of: the LC medium as described above and below is filled or otherwise provided between the substrates of the display, and the polymerizable compound is polymerized, preferably by irradiation with UV light, preferably having a wavelength >340nm, preferably >360nm, preferably in the range 340-400nm, more preferably in the range 350-390nm, very preferably in the range 360-380nm, most preferably in the range 360-368nm, and preferably simultaneously applying a voltage to the electrodes of the display.
The invention further relates to a method for producing an LC display as described above and below, wherein the irradiation of the polymerizable compound is performed using a UV B-lamp or a UV-LED lamp, preferably a UV-LED lamp.
The invention further relates to a power saving method for producing an LC display as described above and below.
When used in PSA displays, the LC media of the present invention exhibit the following advantageous properties:
a suitable tilt within a certain process window,
Rapid polymerization, so that the RM residual after UV treatment is minimized,
High voltage retention after UV treatment,
A good stability of the inclination,
A sufficient thermal stability resistance to heat,
Have sufficient solubility in organic solvents typically used in display manufacturing.
In addition, LC media according to the present invention exhibit one or more of the following advantageous characteristics:
they produce a tilt angle of the desired angle upon UV exposure,
They provide a high tilt stability,
They exhibit good UV absorption, in particular at longer UV wavelengths, preferably in the range from 340 to 400nm, more preferably in the range from 350 to 390nm, very preferably in the range from 360 to 380nm, most preferably in the range from 360 to 368nm, and are capable of rapidly and completely polymerizing RM at these wavelengths,
They are suitable for PSA displays prepared by polymerization processes using UV-LED lamps, which have a longer lifetime, lower energy consumption and more efficient light energy transfer than conventional UV lamps,
During the UV treatment they are able to control the time frame of the first UV step of producing the tilt angle,
They shorten the time frame of the second UV step as much as possible, to minimize production costs and energy consumption,
They enable the use of UV B lamps with longer emission wavelengths than UV C lamps in the second longer UV step, to minimize damage to the compounds in the LC medium,
They reduce or avoid any negative influence of residual RM on LC mixture performance parameters such as VHR, tilt stability etc. after the first and second UV exposure step,
They have high stability, and high and Low Temperature Stability (LTS) against crystallization, over a wide temperature range, preferably from-40 ℃ to about 140 ℃.
As described below, alkenyl groups in the compounds of formula II or other components of the LC medium are not considered to be within the meaning of the term "polymerizable group" as used herein. The polymerization conditions of the polymerizable compound of the LC medium are preferably selected such that the alkenyl substituent does not participate in the polymerization reaction. Preferably, the LC media disclosed and claimed in the present application do not contain an addition to initiate or enhance the participation of alkenyl groups in the polymerization reaction
The polymerizable compound and the compound of formula II are preferably selected from achiral compounds unless otherwise indicated.
As used herein, the expression "UV light of wavelength..a given range of wavelengths (in nm) is followed by a given lower or upper wavelength limit (in nm), means that the UV emission spectrum of the respective irradiation source has an emission peak, which is preferably the highest peak in the respective spectrum, either in the given wavelength range or above or below the given lower wavelength limit, and/or the UV absorption spectrum of the respective chemical compound has a long wavelength tail or a short wavelength tail extending into the given wavelength range or above or below the given lower wavelength limit.
As used herein, the term "full width half maximum" or "FWHM" refers to the width of a spectral curve measured between those points on the y-axis that are half of the maximum amplitude.
As used herein, the term "substantially transmissive" means that the filter transmits a substantial portion, preferably at least 50% of the intensity, of incident light of the desired wavelength. As used herein, the term "substantially block" means that the filter does not transmit a substantial portion, preferably at least 50% of the intensity, of incident light of an undesired wavelength. As used herein, the term "desired (undesired) wavelength" means, for example, for a bandpass filter, wavelengths within (outside) a given range λ, and for a cutoff filter, wavelengths above (below) a given λ value.
As used herein, the terms "active layer" and "switchable layer" refer to layers in electro-optic displays, such as LC displays, that contain one or more molecules, such as LC molecules, that have structural and optical anisotropies that change their orientation when subjected to an external stimulus, such as an electric or magnetic field, resulting in a change in the transmittance of the layer for polarized or unpolarized light.
As used herein, the terms "tilt" and "tilt angle" are understood to mean the tilted alignment of LC molecules of the LC medium relative to the cell surfaces in the LC display (preferably PSA display herein), and are understood to include "pre-tilt" and "pre-tilt angle". The tilt angle herein means the average angle (< 90 °) between the longitudinal molecular axis of the LC molecules (LC director) and the planar parallel outer plate surfaces forming the LC cell. A low absolute tilt angle (i.e., substantially offset from a 90 angle) herein corresponds to a large tilt. Suitable methods of measuring tilt angle are given in the examples. The tilt angle values disclosed in the context relate to such measurement methods, unless otherwise indicated.
As used herein, the terms "reactive mesogen" and "RM" are understood to mean a compound containing a mesogen or liquid crystal backbone, and one or more functional groups suitable for polymerization attached thereto, and also referred to as "polymerizable groups" or "P".
The term "polymerizable compound" as used herein is understood to mean a polymerizable monomer compound unless otherwise indicated.
The SA-VA display according to the invention will be polymer stable mode as it comprises or is manufactured by using LC media containing RMs of formula I and II. Thus, as used herein, the term "SA-VA display" when referring to a display according to the present invention is understood to mean a polymer stabilized SA-VA display, even if not explicitly mentioned.
As used herein, the term "low molecular weight compound" is understood to mean a monomer and/or a compound that is not prepared by polymerization, as opposed to "polymeric compound" or "polymer".
As used herein, the term "non-polymerizable compound" will be understood to mean a compound that does not contain functional groups suitable for polymerization under the conditions typically applied to RM polymerization.
As used herein, the term "mesogenic group" is known to those skilled in the art and described in the literature, and refers to a group that substantially contributes to the production of a Liquid Crystal (LC) phase in a low molecular weight or polymeric species due to the anisotropy of its attractive and repulsive interactions. The compound containing mesogenic groups (mesogenic compound) does not necessarily have to have an LC phase per se. The mesogenic compounds are capable of exhibiting LC phase behaviour only after mixing with other compounds and/or after polymerization. Typical mesogenic groups are for example rigid rod-like or disk-like units. The terms and definitions used in connection with mesogenic or LC compounds are given in Pure appl.chem.2001,73 (5), 888 and C.Tschierske, G.Pelzl, S.Diele, angew.Chem.2004,116,6340-6368.
As used herein, the term "spacer group" (hereinafter also referred to as "Sp") is known to those skilled in the art and is described in the literature, see, e.g., pure appl. Chem.2001,73 (5), 888 and C.Tschierske, G.Pelzl, S.Diele, angew.Chem.2004,116,6340-6368. As used herein, the term "spacer group" or "spacer group" means a flexible group, e.g., it is an alkylene group, which is attached to a mesogenic group or a polymerizable group in a polymerizable mesogenic compound.
In the context of the present context, it is intended that,Represents a trans-1, 4-cyclohexylidene ring, and/>Represents a1, 4-phenylene ring.
At a groupIn (2), the single bond between the two ring atoms may be attached to any free position of the benzene ring.
If the groups R1-13,R51,R52,RQ,R,R2A,R2B,RIIIA,R1N,R2N,RB1,RB2,RCR1,RCR2,R or L in the formulae indicated above and below represent alkyl and/or alkoxy groups, they may be straight-chain or branched. It is preferably straight-chain, has 2,3, 4, 5, 6 or 7C atoms and accordingly preferably represents ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, as well as methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, nonoxy, decyloxy, undecyloxy, dodecoxy, tridecyloxy or tetradecyloxy.
If the group R1-13,R51,R52,RQ,R,R2A,R2B,RIIIA,R1N,R2N,RB1,RB2,RCR1,RCR2,R or L in the formula shown in the context represents an alkyl group in which one or more CH 2 groups are replaced by S, it may be linear or branched. It is preferably straight-chain, has 1,2,3,4, 5, 6 or 7C atoms and accordingly preferably represents a thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl or thioheptyl group.
The oxaalkyl preferably represents a linear 2-oxapropyl (=methoxymethyl), 2-oxabutyl (=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3-or 4-oxapentyl, 2-,3-, 4-or 5-oxahexyl, 2-,3-,4-, 5-or 6-oxaheptyl, 2-,3-,4-,5-, 6-or 7-oxaoctyl, 2-,3-,4-,5-,6-, 7-or 8-oxanonyl, 2-,3-,4-,5-,6-,7-, 8-or 9-oxadecyl.
If the groups R1-13,R51,R52,RQ,R,R2A,R2B,RIIIA,R1N,R2N,RB1,RB2,RCR1,RCR2,R or L in the formulae indicated above and below represent alkoxy or oxaalkyl groups, they may also contain one or more additional oxygen atoms, provided that the oxygen atoms are not directly connected to one another.
In another preferred embodiment one or more of ,R1-13,R51,R52,RQ,R,R2A,R2B,RIIIA,R1N,R2N,RB1,RB2,RCR1,RCR2,R or L is selected from -S 1-F、-O-S1-F、-O-S1-O-S2, wherein S 1 is C 1-12 -alkylene or C 2-12 -alkenylene and S 2 is H, C 1-12 -alkyl or C 2-12 -alkenyl, and is very preferably selected from/> -OCH2OCH3、-O(CH2)2OCH3、-O(CH2)3OCH3、-O(CH2)4OCH3、-O(CH2)2F、-O(CH2)3F、-O(CH2)4F.
If the group R1-13,R51,R52,RQ,R,R2A,R2B,RIIIA,R1N,R2N,RB1,RB2,RCR1,RCR2,R or L in the formula shown in the context represents an alkyl group in which one CH 2 group has been replaced by-ch=ch-, it may be linear or branched. It is preferably linear and has 2 to 10C atoms. Accordingly, it means, in particular, vinyl, prop-1-or-2-enyl, but-1-, -2-or-3-enyl, pent-1-, -2-, -3-or-4-enyl, hex-1-, -2-, -3-, -4-or-5-enyl, hept-1-, -2-, -3-, -4-, -5-or-6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6-or-7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7-or-8-enyl, dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8-or-9-enyl.
If in the formulae indicated above and below the group R1-13,R51,R52,RQ,R,R2A,R2B,RIIIA,R1N,R2N,RB1,RB2,RCR1,RCR2,R or L represents an alkyl or alkenyl group which is at least monosubstituted by halogen, the group is preferably straight-chain and the halogen is preferably F or Cl. In the case of polysubstitution, halogen is preferably F. The resulting groups also include perfluorinated groups. In the case of monosubstituted, the fluoro or chloro substituent may be in any desired position, but is preferably in the ω -position.
Halogen is preferably F or Cl, very preferably F.
The group-CR 0＝CR00 -is preferably-CH=CH-.
-CO-, -C (=o) -and-C (O) -represent carbonyl, i.e
Preferred substituents L are, for example, F、Cl、Br、I、-CN、-NO2、-NCO、-NCS、-OCN、-SCN、-C(＝O)N(Rx)2、-C(＝O)Y1、-C(＝O)Rx、-N(Rx)2、 straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy each having 1 to 25C atoms, where one or more H atoms may optionally be replaced by F or Cl, optionally substituted silyl having 1 to 20 Si atoms, or optionally substituted aryl having 6 to 25, preferably 6 to 15C atoms,
Wherein R x represents H, F, cl, CN, or a linear, branched or cyclic alkyl group having 1 to 25C atoms, wherein one or more non-adjacent CH 2 groups are optionally interrupted by-O-, in such a way that the O-and/or S-atoms are not directly linked to each other-S-, -CO-O-, -O-CO-O-substitution, and wherein one or more H atoms are each optionally replaced by F, cl, P-or P-Sp-, and
Y 1 represents halogen.
Particularly preferred substituents L are, for example, F、Cl、CN、NO2、CH3、C2H5、OCH3、OC2H5、COCH3、COC2H5、COOCH3、COOC2H5、CF3、OCF3、OCHF2、OC2F5、 and phenyl.
Preferably/>Wherein L has one of the meanings mentioned above.
The polymerizable group P is a group suitable for polymerization, such as radical or ionic chain polymerization, addition polymerization or condensation polymerization, or a group suitable for polymer-like reactions, such as addition or condensation on the polymer backbone. Particularly preferred are groups for chain polymerization, in particular those containing a c=c double bond or-c≡c-triple bond, and groups suitable for ring-opening polymerization, such as oxetanyl or epoxy groups.
Preferred groups P are selected from CH 2＝CW1-CO-O-、CH2＝CW1 -CO-,CH2＝CW2-(O)k3-、CW1＝CH-CO-(O)k3-、CW1＝CH-CO-NH-、CH2＝CW1-CO-NH-、CH3-CH＝CH-O-、(CH2＝CH)2CH-OCO-、(CH2＝CH-CH2)2CH-OCO-、(CH2＝CH)2CH-O-、(CH2＝CH-CH2)2N-、(CH2＝CH-CH2)2N-CO-、HO-CW2W3-、HS-CW2W3-、HW2N-、HO-CW2W3-NH-、CH2＝CW1-CO-NH-、CH2＝CH-(COO)k1-Phe-(O)k2-、CH2＝CH-(CO)k1-Phe-(O)k2-、Phe-CH＝CH-、HOOC-、OCN- And W 4W5W6 Si-, wherein W 1 represents H, F, cl, CN, CF 3, phenyl or alkyl having 1 to 5C atoms, in particular H, F, cl or CH 3,W2 and W 3 each independently of the other represent H or alkyl having 1 to 5C atoms, in particular H, methyl, ethyl or n-propyl, W 4,W5 and W 6 each independently of the other represent Cl, oxaalkyl having 1 to 5C atoms or oxacarbonylalkyl, W 7 and W 8 each independently of the other represent H, cl or alkyl having 1 to 5C atoms, phe represents 1, 4-phenylene, which is optionally substituted by one or more groups L other than P-Sp-as defined above, k 1,k2 and k 3 each independently of the other represent 0 or 1, k 3 preferably represents 1, and k 4 represents an integer from 1 to 10.
Very preferred groups P are selected from CH 2＝CW1-CO-O-、CH2＝CW1 -CO-,CH2＝CW2-O-、CH2＝CW2-、CW1＝CH-CO-(O)k3-、CW1＝CH-CO-NH-、CH2＝CW1-CO-NH-、(CH2＝CH)2CH-OCO-、(CH2＝CH-CH2)2CH-OCO-、(CH2＝CH)2CH-O-、(CH2＝CH-CH2)2N-、(CH2＝CH-CH2)2N-CO-、CH2＝CW1-CO-NH-、CH2＝CH-(COO)k1-Phe-(O)k2-、CH2＝CH-(CO)k1-Phe-(O)k2-、Phe-CH＝CH- And W 4W5W6 Si-, wherein W 1 represents H, F, cl, CN, CF 3, phenyl or alkyl having 1 to 5C atoms, in particular H, F, cl or CH 3,W2 and W 3 each independently of the other represent H or alkyl having 1 to 5C atoms, in particular H, methyl, ethyl or n-propyl, W 4,W5 and W 6 each independently of the other represent Cl, oxaalkyl having 1 to 5C atoms or oxacarbonylalkyl, W 7 and W 8 each independently of the other represent H, cl or alkyl having 1 to 5C atoms, phe represents 1, 4-phenylene, k 1,k2 and k 3 each independently of the other represent 0 or 1, k 3 preferably represents 1, and k 4 represents an integer from 1 to 10.
Very particularly preferred groups P are selected from the group CH 2＝CW1 -CO-O-, in particular CH 2＝CH-CO-O-、CH2＝C(CH3) -CO-O-and CH 2 =CF-CO-O-, CH 2＝CH-O-、(CH2＝CH)2CH-O-CO-、(CH2＝CH)2 CH-O-,And/>
Further preferred polymerizable groups P are selected from ethyleneoxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxy groups, most preferred acrylate and methacrylate groups.
It is highly preferred that all polymerizable groups in the polymerizable compound have the same meaning.
If the spacer group Sp is different from a single bond, it is preferably of the formula Sp "-X" such that the individual groups P-Sp-correspond to the formula P-Sp "-X" -, where
Sp "represents a linear or branched alkylene radical having from 1 to 20, preferably from 1 to 12, C atoms, which is optionally mono-or polysubstituted by F, cl, br, I or CN and in which, in addition, one or more non-adjacent CH 2 groups can each be replaced, independently of one another, by -O-、-S-、-NH-、-N(R0)-、-Si(R0R00)-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-S-CO-、-CO-S-、-N(R00)-CO-O-、-O-CO-N(R0)-、-N(R0)-CO-N(R00)-、-CH＝CH- or-C.ident.C-in such a way that O and/or S atoms are not directly linked to one another,
X' represents -O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-CO-N(R0)-、-N(R0)-CO-、-N(R0)-CO-N(R00)-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CH＝N-、-N＝CH-、-N＝N-、-CH＝CR0-、-CY2＝CY3-、-C≡C-、-CH＝CH-CO-O-、-O-CO-CH＝CH- or a single bond,
R 0 and R 00 each independently of one another represent H or alkyl having 1 to 20C atoms, and
Y 2 and Y 3 each independently represent H, F, cl or CN.
X' is preferably-O-, -S-; -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0-、-NR0-CO-、-NR0-CO-NR00 -, or a single bond.
Typical spacer groups Sp and-Sp "-X" -are for example -(CH2)p1-、-(CH2)p1-O-、-(CH2)p1-O-CO-、-(CH2)p1-CO-O-、-(CH2)p1-O-CO-O-、-(CH2CH2O)q1-CH2CH2-、-CH2CH2-S-CH2CH2-、-CH2CH2-NH-CH2CH2- or- (SiR 0R00-O)p1 -, where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R 0 and R 00 have the meanings as described above.
Particularly preferred groups Sp and-Sp "-X" -are -(CH2)p1-、-(CH2)p1-O-、-(CH2)p1-O-CO-、-(CH2)p1-CO-O-、-(CH2)p1-O-CO-O-, wherein p1 and q1 have the meanings as described above.
Particularly preferred groups Sp' are in each case straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxy ethylene, methyleneoxy butylene, ethylenethio ethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethylene, propylene and butylene groups.
In a preferred embodiment of the invention, the compounds of formula I and their subformulae contain a spacer group Sp substituted by one or more polymerizable groups P, so that the group Sp-P corresponds to Sp (P) s, where s is ≡2 (branched polymerizable groups).
Preferred compounds of formula I according to this preferred embodiment are those in which s is 2, i.e. compounds containing the group Sp (P) 2. Very preferred compounds of formula I according to this preferred embodiment contain a group selected from the following formulae:
-X-alkyl-CHPP S1
-X-alkyl-CH((CH2)aaP)((CH2)bbP) S2
-X-N((CH2)aaP)((CH2)bbP) S3
-X-alkyl-CHP-CH2-CH2P S4
-X-alkyl-C(CH2P)(CH2P)-CaaH2aa+1 S5
-X-alkyl-CHP-CH2P S6
-X-alkyl-CPP-CaaH2aa+1 S7
-X-alkyl-CHPCHP-CaaH2aa+1 S8
wherein P is as defined for formula I,
Alkyl represents a single bond or a straight or branched alkylene group having 1 to 12C atoms, which are unsubstituted or mono-or polysubstituted by F, cl or CN and in which one or more non-adjacent CH 2 groups can each be, independently of one another, substituted by-C (R 0)＝C(R0)-、-C≡C-、-N(R0) -, in such a way that O and/or S atoms are not directly connected to one another-O-, -S-, -CO-O-, -O-CO-O-substitution, wherein R 0 has the meaning as described above,
Aa and bb each independently of one another represent 0,1, 2, 3, 4, 5 or 6,
X has one of the meanings stated for X ", and is preferably O, CO, SO 2, O-CO-, CO-O or a single bond.
Preferred spacer groups Sp (P) 2 are selected from formulas S1, S2 and S3.
Very preferred spacer groups Sp (P) 2 are selected from the following subformulae:
-CHPP S1a
-O-CHPP S1b
-CH2-CHPP S1c
-OCH2-CHPP S1d
-CH(CH2-P)(CH2-P) S2a
-OCH(CH2-P)(CH2-P) S2b
-CH2-CH(CH2-P)(CH2-P) S2c
-OCH2-CH(CH2-P)(CH2-P) S2d
-CO-NH((CH2)2P)((CH2)2P) S3a
p is preferably selected from the group consisting of ethyleneoxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxy groups, very preferably acrylate and methacrylate groups, most preferably methacrylate groups.
It is further preferred that all polymerizable groups P present in the same compound have the same meaning, and very preferably represent acrylate groups or methacrylate groups, most preferably methacrylate groups.
Sp preferably represents a single bond or -(CH2)p1-、-(CH2)p2-CH＝CH-(CH2)p3-、-O-(CH2)p1-、-O-CO-(CH2)p1、 or-CO-O- (CH 2)p1) in which p1 is 2,3, 4, 5 or 6, preferably 2 or 3, p2 and p3 independently of one another are 0, 1,2 or 3 and, if Sp is-O- (CH 2)p1-、-O-CO-(CH2)p1) or-CO-O- (CH 2)p1), the O-atom or CO-group, respectively, is attached to the benzene ring.
It is further preferred that at least one group Sp is a single bond.
It is further preferred that at least one group Sp is different from a single bond and is preferably selected from -(CH2)p1-、-(CH2)p2-CH＝CH-(CH2)p3-、-O-(CH2)p1-、-O-CO-(CH2)p1、 or-CO-O- (CH 2)p1) wherein p1 is 2, 3, 4, 5 or 6, preferably 2 or 3, p2 and p3 are independently of each other 0, 1, 2 or 3 and, if Sp is-O- (CH 2)p1-、-O-CO-(CH2)p1) or-CO-O- (CH 2)p1), an O-atom or a CO-group is attached to the benzene ring, respectively.
Very preferably Sp is different from a single bond and is selected from -(CH2)2-、-(CH2)3-、-(CH2)4-、-O-(CH2)2-、-O-(CH2)3-、-O-CO-(CH2)2 and-CO-O- (CH) 2 -, wherein the O atom or CO group is attached to the benzene ring.
Preferably, the polymerizable compound of formula I has an absorbance in the range of 330-390 nm. Very preferably they have an extinction coefficient of at least 0.5 in the wavelength range 330-390nm, more preferably 340-380nm, very preferably 350-370nm, most preferably 355-365nm. The extinction coefficient and absorption wavelength were measured in a solution of the compound at a concentration of 3g/L in DCM unless otherwise indicated.
Preferably, in the compounds of formula I, a and b are each independently 0 or 1. In a preferred embodiment of the invention, a+b=1 or 2.
Preferred compounds of formula I are selected from formula I1
Wherein P, sp, L and r4 independently of each other have one of the meanings given in formula I1 or one of their preferred meanings given in the context. P is preferably an acrylate group or a methacrylate group, very preferably a methacrylate group. Sp is preferably a single bond. r4 is preferably 0, 1 or 2, very preferably 0 or 1.L is preferably F or OCH 3. Preferably, all groups P in formulae I1 and I1-1 have the same meaning and very preferably represent methacrylate groups.
Highly preferred compounds of formulae I and I1 are selected from the following subformulae.
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Further preferred compounds of formulae I and I1 are those selected from one or more of the following embodiments:
the groups P represent, independently of one another, acrylate groups or methacrylate groups, very preferably methacrylate groups,
All groups P in one compound have the same meaning,
Sp is a single bond,
At least one, preferably one or both, of the groups Sp is a single bond and the other groups Sp are different from the single bond,
-When Sp is different from a single bond, sp and Sp' are selected from -(CH2)p1-、-(CH2)p2-CH＝CH-(CH2)p3-、-O-(CH2)p1-、-O-CO-(CH2)p1 or-CO-O- (CH 2)p1, wherein p1 is 2,3, 4, 5 or 6, preferably 2 or 3, p2 and p3 are independently of each other 0, 1, 2 or 3; and if Sp is-O- (CH 2)p1-、-O-CO-(CH2)p1) or-CO-O- (CH 2)p1), the O-atom or CO-group is respectively attached to the benzene ring,
When Sp is different from a single bond, sp and Sp' are selected from -(CH2)2-、-(CH2)3-、-(CH2)4-、-O-(CH2)2-、-O-(CH2)3-、-O-CO-(CH2)2 and-CO-O- (CH) 2 -, wherein the O atom or CO group is attached to the benzene ring,
-a＝b＝0，
-R4 is either 0 or 1,
L is selected from F, cl, br, CN, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy each having 1 to 6C atoms, or alkenyl having 2 to 6C atoms, wherein one or more H atoms are optionally replaced by F or Cl,
L is selected from F, CH 3、OCH3、OC2H5、C2H5、CH＝CH2 and C (CH 3)＝CH2, very preferably from F and OCH 3).
For use in PSA displays, the total proportion of polymerizable compounds of formula I or subformulae thereof in the LC medium is preferably from 0.01 to 2.0%, more preferably from 0.02 to 1.5%, very preferably from 0.025 to 1.0%.
For use in SA-VA displays, the total proportion of polymerizable compounds of formula I or subformulae thereof in the LC medium is preferably >0 to <3%, very preferably >0 to <2%, more preferably 0.05-2.5%, most preferably 0.05-1.5%.
In addition to the polymerizable compounds of formula I or sub-formulae thereof, the LC medium comprises at least one further polymerizable compound.
In a preferred embodiment, the at least one further polymerizable compound is a compound of formula I or a subformula thereof, more preferably selected from formula I1, very preferably selected from formulae I1-1 to I1-18, or selected from formula I and a subformula thereof as disclosed above and below.
In another preferred embodiment, the LC medium comprises, in addition to the polymerizable compound of formula I or its subformulae, at least one further polymerizable compound selected from the group consisting of:
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wherein each group, independently of the other and identically or differently for each occurrence, has the following meanings:
P 1、P2、P3 is a polymerizable group, preferably selected from the group consisting of ethyleneoxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetanyl and epoxy,
Sp 1,Sp2,Sp3 is a single bond or a spacer group, wherein, in addition, one or more of the groups P 1-Sp1-、P2-Sp2 -and P 3-Sp3 -may represent R aa, provided that at least one of P 1-Sp1-、P2-Sp2 -and P 3-Sp3 -is present other than R aa, preferably- (CH 2)p1-,-(CH2)p1-O-,-(CH2)p1 -CO-O-or- (CH 2)p1 -O-CO-O-, wherein P1 is an integer of 1 to 12,
R aa is H, F, cl, CN or a linear or branched alkyl radical having 1 to 25C atoms, where in addition, one or more non-adjacent CH 2 groups can each be replaced by-C (R 0)＝C(R00)-、-C≡C-、-N(R0) -, -O-, -S-, -CO-O-, -O-CO-O-in such a way that O and/or S atoms are not directly linked to one another, and wherein, in addition, one or more H atoms may be replaced by F, cl, CN or P 1-Sp1 -, particularly preferred are straight-chain or branched, optionally mono-or polyfluoro, alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy groups having 1 to 12C atoms, where alkenyl and alkynyl have at least two C atoms and branched groups have at least three C atoms, and where R aa does not represent or contain the radicals P 1、P2 or P 3,
R 0,R00 is H or alkyl having 1 to 12C atoms,
R y and R z are H, F, CH 3 or CF 3,
X 1,X2,X3 is-CO-O-, -O-CO-or a single bond,
Z M1 is-O-, -CO-; -C (R yRz) -or-CF 2CF2 -,
Z M2,ZM3 is-CO-O- -O-CO- -CH 2O-、-OCH2-、-CF2O-、-OCF2 -or- (CH 2)n -, wherein n is 2,3 or 4,
L is F, cl, CN or a linear or branched, optionally mono-or polyfluoro, alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 12C atoms,
L ', L' is H, F or Cl,
K is 0 or 1, and the number of the groups is,
R is 0, 1,2, 3 or 4,
S is 0, 1,2 or 3,
T is 0, 1 or 2,
X is 0 or 1.
Very particular preference is given to compounds of the formulae M2 and M13, in particular to the double-reactive compounds which contain exactly two polymerizable groups P 1 and P 2.
Further preferred are compounds selected from the group consisting of the formulae M17 to M32, in particular the formulae M20, M22, M24, M27, M30 and M32, in particular the three reactive compounds which happen to contain three polymerizable groups P 1、P2 and P 3.
Of the compounds of the formulae M1 to M31
Preferably/>
Wherein L has, identically or differently for each occurrence, one of the meanings given in the context, and preferably F、Cl、CN、NO2、CH3、C2H5、C(CH3)3、CH(CH3)2、CH2CH(CH3)C2H5、OCH3、OC2H5、COCH3、COC2H5、COOCH3、COOC2H5、CF3、OCF3、OCHF2、OC2F5 or P-Sp-, very preferably F, cl, CN, CH 3、C2H5、OCH3、COCH3、OCF3 or P-Sp-, more preferably F, cl, CH 3、OCH3、COCH3 or OCF 3, most preferably F or OCH 3.
Preferred compounds of the formulae M1 to M32 are those in which P 1、P2 and P 3 represent acrylate, methacrylate, oxetane or epoxy groups, very preferably acrylate or methacrylate groups, most preferably methacrylate groups.
Further preferred compounds of the formulae M1 to M32 are those in which Sp 1、Sp2 and Sp 3 are single bonds.
Further preferred compounds of formulae M1 to M32 are those in which one of Sp 1、Sp2 and Sp 3 is a single bond and the other of Sp 1、Sp2 and Sp 3 is different from the single bond.
Other preferred compounds of the formulae M1 to M32 are those in which Sp 1、Sp2 and Sp 3 are different from the single bond representing- (CH 2)s1 -X "", wherein s1 is an integer from 1 to 6, preferably 2,3,4 or 5, and X' is a bond to a benzene ring, and is-O-, -O-CO-, -CO-O-O-CO-O-or a single bond.
Other preferred compounds of the formulae M1 to M32 are selected from table D below, in particular from those below: formulas RM-1、RM-4、RM-8、RM-17、RM-19、RM-35、RM-37、RM-39、RM-40、RM-41、RM-48、RM-52、RM-54、RM-57、RM-58、RM-64、RM-74、RM-76、RM-88、RM-91、RM-102、RM-103、RM-109、RM-116、RM-117、RM-120、RM-121、RM-122、RM-139、RM-140、RM-142、RM-143、RM-145、RM-146、RM-147、RM-149、RM-156to RM-163、RM-169、RM-170 and RM-171 to RM-183.
Particularly preferred is an LC medium comprising: in addition to the compounds of the formula I, there are one, two or three polymerizable compounds of the formulae M1 to M32.
Further preferred is an LC medium comprising: in addition to the compounds of the formula I, one or more di-reactive polymerizable compounds selected from the formulae M1 to M16, very preferably from the formulae M2 and M13.
Further preferred is an LC medium comprising: in addition to the compounds of the formula I, one or more double-reactive polymerizable compounds selected from the formulae M1 to M16, very preferably from the formulae M2 and M13, and/or one or more triple-reactive polymerizable compounds selected from the formulae M17 to M32, very preferably from the formulae M20, M22, M24, M27, M30 and M32.
Further preferred is an LC medium comprising: in addition to the compounds of formula I, there are one or more polymerizable compounds of formula M1-M32 wherein at least one r is other than 0, or at least one s and t are other than 0, very preferably selected from the formulae M2, M13, M22, M24, M27, M30 and M32, and wherein L is selected from the preferred groups indicated above, most preferably selected from F and OCH 3.
Further preferred are polymerizable compounds exhibiting absorption in the wavelength range from 320 to 380nm, preferably selected from formulae M1 to M32, more preferably selected from formulae in table D above, most preferably selected from ：RM-1、RM-4、RM-8、RM-17、RM-19、RM-35、RM-37、RM-39、RM-40、RM-41、RM-48、RM-52、RM-54、RM-57、RM-58、RM-64、RM-74、RM-76、RM-88、RM-91、RM-102、RM-103、RM-109、RM-116、RM-117、RM-120、RM-121、RM-122、RM-139、RM-140、RM-142、RM-143、RM-145、RM-146、RM-147、RM-149、RM-156to RM-163、RM-169、RM-170 and RM-171 to RM-183 below.
Further preferred further polymerisable compounds are selected from the compounds used in the examples of mixtures below.
In another preferred embodiment, the LC medium comprises, in addition to the polymerizable compounds of formula I or its subformulae, one or more polymerizable compounds selected from the group consisting of CM having two polymerizable groups
Wherein each group, independently of the other and identically or differently for each occurrence, has the following meanings:
p, sp is one of the meanings given in formula I or its subformulae or one of their preferred meanings as given above and below,
L is F, cl, CN or a straight-chain or branched chain having 1 to 12C atoms, optionally mono-or polyfluoro-substituted alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy,
R1, r2 is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, very preferably 0 or 1.
Preferred compounds of formula CM are selected from the following subformulae:
Wherein P and Sp, L, r1 and r2 independently of each other have one of the meanings given in formula CM, or one of their preferred meanings as given above and below, and Sp' has one of the meanings given for Sp other than a single bond.
Preferably at least one of r1 and r2 is other than 0.
P is preferably an acrylate group or a methacrylate group, very preferably a methacrylate group. Preferably, all groups P in the formulae CM, CM-1 and CM-2 have the same meaning and very preferably represent methacrylate groups. Sp' is preferably selected from -(CH2)2-、-(CH2)3-、-(CH2)4-、-O-(CH2)2-、-O-(CH2)3-、-O-CO-(CH2)2 and-CO-O- (CH) 2 -in which the O atom or CO group is attached to the benzene ring.
L is preferably selected from F, CH 3、OCH3、OC2H5、C2H5、CH＝CH2 and C (CH 3)＝CH2, very preferably F.
Very preferred are compounds of formula CM-1.
More preferred compounds of formula CM are selected from the following subformulae
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Wherein P, sp' and L have one of the meanings given in the formulae CM-1 and CM-2. P is preferably an acrylate group or a methacrylate group, very preferably a methacrylate group. Preferably, all groups P in the formulae CM-1-1 to CM-2-9 have the same meaning and very preferably represent methacrylate groups. Sp' is preferably selected from -(CH2)2-、-(CH2)3-、-(CH2)4-、-O-(CH2)2-、-O-(CH2)3-、-O-CO-(CH2)2 and-CO-O- (CH) 2 -in which the O atom or CO group is attached to the benzene ring. L is preferably selected from F, CH 3、OCH3、OC2H5、C2H5、CH＝CH2 and C (CH 3)＝CH2, very preferably from F and OCH 3).
Very preferred are the compounds of the formulae CM-1-1, CM-1-2, CM-1-3, CM-1-4, CM-1-5, CM-1-6 and their subformulae. Most preferred are compounds of formula CM-1-1.
Highly preferred compounds of formula CM are selected from the following subformulae:
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Very preferred are compounds of the formulae CM-1-1a, CM-1-2a and CM-1-3 a. Most preferred are compounds of formula CM-1-1 a.
Further preferred are compounds of the formulae CM-1-1a to CM-2-9a in which one or two methacrylate groups are replaced by acrylate groups, and compounds of the formulae CM-1-1a to CM-2-9a in which all methacrylate groups are replaced by acrylate groups.
Further preferred compounds of formula CM are selected from the following Table D, very preferably from RM-1, RM-2, RM-3 and RM-7 to RM-49, very preferably from RM-1, RM-4, RM-8, RM-17, RM-19, RM-35, RM-37, RM-39, RM-40, RM-41 and RM-48.
In another preferred embodiment, the LC medium comprises the following: in addition to the polymerizable compounds of the formula I or its subformulae, there are one or more polymerizable compounds selected from the group consisting of the formula MT having three polymerizable groups
Wherein P, sp, L, r and r2 independently of one another have one of their preferred meanings given in the formula CM or in the context, k is 0 or 1 and r3 is 0, 1,2 or 3, preferably 0, 1 or 2, very preferably 0 or 1.
Preferred compounds of formula MT are selected from the following subformulae
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Wherein P, sp, L, r, r2 and r3 independently of one another have one of the meanings given in the formula MT or one of their preferred meanings given in the context, as described above.
Preferably, at least one of r1, r2 and r3 is other than 0.
P is preferably an acrylate or methacrylate group, very preferably a methacrylate group.
L is preferably selected from F, CH 3、OCH3、OC2H5、C2H5、CH＝CH2 and C (CH 3)＝CH2, very preferably from F.
Preferably, all groups P in formulae MT and MT-1 to MT-6 have the same meaning and very preferably represent methacrylate groups.
Very particular preference is given to compounds of the formulae MT-1, MT-4 and MT-5.
More preferred compounds of formula MT are selected from the following subformulae
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Wherein P, sp and L have one of the meanings given in formula MT and Sp' has one of the meanings given for Sp other than a single bond. P is preferably an acrylate group or a methacrylate group, very preferably a methacrylate group. Preferably, all groups P in the formulae MT-1-1 to MT-6-12 have the same meaning and very preferably represent methacrylate groups. Sp' is preferably selected from -(CH2)2-、-(CH2)3-、-(CH2)4-、-O-(CH2)2-、-O-(CH2)3-、-O-CO-(CH2)2 and-CO-O- (CH) 2 -in which the O atom or CO group is attached to the benzene ring. L is preferably selected from F, CH 3,OCH3,OC2H5,C2H5,CH＝CH2 and C (CH 3)＝CH2, very preferably from F and OCH 3).
Very particular preference is given to compounds of the formulae MT-1-1, MT-1-6, MT-5-1 and their subformulae.
Highly preferred compounds of formula MT are selected from the following subformulae:
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of the compounds of the formulae MT-1 to MT-3, very particular preference is given to compounds of the formulae MT-1-1a, MT-1-2b, MT-2-1a, MT-2-2b, MT-3-1a, MT-3-2a and MT-3-2 b. Most preferred are compounds of the formulae MT-1-1a, MT-1-2b, MT-2-1a, MT-2-2a and MT-2-2 b.
Of the compounds of the formulae MT-4 to MT-6, very particular preference is given to the compounds of the formulae MT-4-1a、MT-4-2a、MT-4-3a、MT-4-4a、MT-4-5a、MT-4-6a、MT-4-7a、MT-4-7b、MT-4-8a、MT-4-9a、MT-4-10a、MT-4-11a、MT-4-12a、MT-5-1a、MT-5-2a、MT-5-4a、MT-5-5a、MT-5-6a、MT-5-7a、MT-5-7b、MT-5-8a、MT-5-9a、MT-5-10a、MT-5-11a and MT-5-12 a. Most preferred are compounds of the formulae MT-4-1a, MT-4-7b, MT-5-1a, MT-5-7a and MT-5-7 b.
Further preferred are compounds of the formulae MT-1-1a to MT-6-11a, in which one or two methacrylate groups are replaced by acrylate groups. Further preferred are compounds of the formulae MT-1-1a to MT-6-11a, in which all methacrylate groups are replaced by acrylate groups.
Further preferred compounds of formula MT are selected from Table D below, preferably from formulae RM-120 to RM-144.
The total proportion of further polymerisable compounds of the formulae M1 to M32, CM and MT in the LC medium according to the invention is preferably from 0.01 to 1.0%, more preferably from 0.1 to 0.8%, very preferably from 0.1 to 0.5%.
The polymerizable compounds of the formulae I and M1 to M32 can be prepared analogously to methods known to the person skilled in the art and described in the standard works of organic chemistry, for example in Houben-Weyl, methoden der Organischen Chemie [ Methods of Organic Chemistry ], thieme-Verlag, stuttgart.
For example, acrylates or methacrylates can be prepared by esterifying the corresponding alcohols with acid derivatives, such as (meth) acryloyl chloride or (meth) acrylic anhydride, in the presence of a base such as pyridine or triethylamine, and 4- (N, N-dimethylamino) pyridine (DMAP). Alternatively, the esters may be prepared by esterification of an alcohol with (meth) acrylic acid in the presence of a dehydrating agent, such as Dicyclohexylcarbodiimide (DCC), N- (3-dimethylaminopropyl) -N '-Ethylcarbodiimide (EDC), or N- (3-dimethylaminopropyl) -N' -ethylcarbodiimide hydrochloride according to stelich, and DMAP.
The invention further relates to an LC medium or LC display as described above, wherein the polymerisable compound is present in polymerized form.
The LC display is preferably a PS-VA, PS-IPS, PS-FFS or SA-VA display.
In order to produce PSA or polymer stabilized SA displays, the polymerisable compounds contained in the LC medium are polymerised by in-situ polymerisation in the LC medium between the LC display substrates, preferably with simultaneous application of a voltage to the electrodes.
As described in the prior art cited in the opening paragraph, the structure of the inventive display corresponds to the usual geometry of PSA displays. Preferably, geometries without protrusions, especially those in which the electrodes on the color filter side are unstructured and only the electrodes on the TFT side have slots. Particularly suitable and preferred electrode structures for PS-VA displays are described, for example, in US2006/0066793 A1.
A preferred PSA-type LC display of the invention comprises:
a first substrate comprising pixel electrodes defining pixel areas, said pixel electrodes being connected to switching elements arranged in each pixel area and optionally comprising a micro-slit pattern, and optionally a first alignment layer arranged on said pixel electrodes,
A second substrate comprising a common electrode layer, which may be disposed on an entire portion of the second substrate facing the first substrate, and optionally a second alignment layer,
An LC layer arranged between the first substrate and the second substrate and comprising an LC medium as described above and below, wherein the polymerisable compound may also be present in polymerized form.
The first and/or second alignment layers control the alignment direction of LC molecules of the LC layer. For example, in a PS-VA display, the alignment layer is selected such that it imparts homeotropic (or vertical) alignment (i.e., perpendicular to the surface) or tilt alignment to the LC molecules. Such an alignment layer may for example comprise polyimide, which may also be rubbed, or may be prepared by a photoalignment method.
The LC layer with LC medium can be deposited between the substrates of the display by methods conventionally used by display manufacturers, such as the so-called one-drop-fill (ODF) method. The polymerisable component of the LC medium is then polymerised, for example by UV photopolymerization. The polymerization may be carried out in one step or in two or more steps.
PSA displays may include other elements such as color filters, black matrices, passivation layers, optical retardation layers, transistor elements for addressing individual pixels, etc., all of which are well known to those skilled in the art and may be used without the inventive skill.
The electrode structure may be designed by the skilled person in accordance with the respective display type. For example, for a PS-VA display, the multi-domain orientation of LC molecules may be induced by providing electrodes with slits and/or protrusions or protuberances to create two, four or more different tilted alignment directions.
After polymerization, the polymerizable compound forms a copolymer, resulting in LC molecules in the LC medium having a tilt angle. Without wishing to be bound by a particular theory, it is believed that at least a portion of the crosslinked polymer formed from the polymerizable compound will phase separate or precipitate from the LC medium and form a polymer layer on the substrate or electrode, or an alignment layer is disposed thereon. Microscopic measurement data (e.g., SEM and AFM) have confirmed that at least a portion of the formed polymer accumulates at the LC/substrate interface.
The polymerization can be carried out in one step. It is also possible to first carry out the polymerization in a first step to produce a tilt angle, optionally with the application of a voltage, and then to polymerize or crosslink the compounds unreacted from the first step in a second polymerization step in the absence of an applied voltage ("final cure").
Suitable and preferred polymerization methods are, for example, thermal polymerization or photopolymerization, preferably photopolymerization, in particular UV-induced photopolymerization, which can be achieved by exposing the polymerizable compound to UV radiation.
Preferred methods of making PSA displays include one or more of the following features:
Exposing the polymerizable medium to UV light in a display in a two-step process comprising a first UV exposure step ("UV 1 step"), applying a voltage to create a tilt angle, and a second UV exposure step ("UV 2 step"), applying no voltage to complete the polymerization,
Preferably at least in the UV2 step, more preferably in the UV1 and UV2 steps, the polymerizable medium is exposed to UV light generated by the UV-LED lamp in the display.
In displays the polymerizable medium is exposed to UV light generated by UV lamps whose irradiation spectrum is shifted to longer wavelengths, preferably ≡340nm, more preferably 350 to <370nm, very preferably 355-368nm, to avoid short UV light exposure in PS-VA processes.
Using lower intensities and shifting UV to longer wavelengths can protect the organic layers from damage that may be caused by UV light.
Preferred embodiments of the present invention relate to a method of manufacturing a PSA display as described above and below, the method comprising one or more of the following features:
In a two-step process, in which the polymerizable LC medium is irradiated with UV light, the process comprises a first UV exposure step ("UV 1 step"), applying a voltage to produce a tilt angle, and a second UV exposure step ("UV 2 step"), not applying a voltage to complete the polymerization,
Preferably in a UV2 step and optionally also in a UV1 step, irradiating the polymerizable LC medium with UV light generated by a UV lamp having an intensity of 0.5mW/cm 2 to 10mW/cm 2,
Irradiating the polymerizable LC medium with UV light having a wavelength of 340 and 420nm or more, preferably >350nm, preferably in the range of 340-400nm, more preferably in the range of 350-390nm, very preferably in the range of 360-380nm, most preferably in the range of 360-368nm,
Irradiating the polymerizable LC medium with UV light while applying a voltage to the electrodes of the display,
UV light irradiation using a UV-LED lamp.
For example, the preferred method may be carried out by using a desired UV lamp or by using bandpass and/or cutoff filters that are substantially transmissive to UV light having each desired wavelength and substantially blocking light for each undesired wavelength. For example, when it is desired to irradiate with UV light having a wavelength λ of 300-400nm, UV exposure may be performed using a broadband filter that is substantially transmissive to wavelengths 300nm < λ <400 nm. When it is desired to irradiate with UV light having a wavelength lambda greater than 340nm, UV irradiation may be performed using a cut-off filter that is substantially transmissive to wavelengths lambda >340 nm.
Preferably, UV irradiation is performed using a UV-LED lamp.
In the PSA process, the use of UV-LED lamps having only one narrow emission peak provides various advantages, such as a more efficient transfer of light energy to the polymerizable compound in the LC medium, depending on the selection of a suitable polymerizable compound that exhibits absorption at the LED lamp emission wavelength. This allows a reduction in UV intensity and/or UV irradiation time, thereby enabling a shortening of takt time and saving of energy and production costs. Another advantage is that the emission spectrum of the lamp is narrow and that the appropriate wavelength can be more easily selected for photopolymerization.
Very preferably, the UV light source is a UV-LED lamp with an emission wavelength in the range of 340-400nm, more preferably in the range of 350-390nm, very preferably in the range of 360-380 nm, most preferably in the range of 360-368 nm. Particularly preferred are UV-LED lamps which emit UV light with a wavelength of 365 nm.
Preferably, the UV-LED lamp emits light having an emission peak with a Full Width Half Maximum (FWHM) of 30nm or less.
UV-LED lamps are commercially available, for example, from Dr. Hoenle AG, germany or PRIMELITE GMBH, germany or from IST Metz GmbH, germany, with emission wavelengths of, for example, 365, 385, 395 and 405nm.
This preferred method enables the manufacture of displays by using longer UV wavelengths, thereby reducing or even avoiding the damaging and damaging effects of short UV light components.
The UV irradiation energy is generally 6-100J, depending on the production process conditions.
Preferably, the total amount of all polymerizable compounds in the LC medium is 0.02-1.5%, more preferably 0.05-1.2%, most preferably 0.15-1.0%.
In a first preferred embodiment, the LC medium according to the invention contains one or more polymerizable compounds of formula I or subformulae thereof in a concentration of 0.01 to 0.12%, more preferably 0.01 to 0.1%, very preferably 0.025 to 0.075%, and also contains one or more polymerizable compounds of formula I other than compounds of formula I in a concentration of 0.15 to 0.7%, preferably selected from the group consisting of formulae M1 to M32 or subformulae thereof, very preferably selected from the group consisting of formulae CM and MT or subformulae thereof, more preferably 0.15 to 0.5%, very preferably 0.2 to 0.4%, and the concentration of the polymerizable compounds of formula I is less than the concentration of the polymerizable compounds other than compounds of formula I.
The LC medium according to this first preferred embodiment is particularly suitable and preferred for use in PSA displays or PSA display manufacturing processes, wherein the polymerization is performed using a fluorescent UV lamp, preferably a fluorescent UV C lamp in UV1 step and a fluorescent B UV lamp in UV2 step, as described above.
In a second preferred embodiment, the LC medium according to the invention contains one or more polymerizable compounds of formula I or subformulae thereof in a concentration of 0.2 to 1.0%, more preferably 0.2 to 1.0%, very preferably 0.3 to 0.8%, and one or more polymerizable compounds different from the compounds of formula I, preferably selected from the formulae M1 to M32, very preferably selected from the formulae CM and MT or subformulae thereof in a concentration of 0.1 to 0.5%, more preferably 0.15 to 0.5%, very preferably 0.2 to 0.4%, and preferably in these LC media the concentration of the polymerizable compounds of formula I is at least equal to, and very preferably higher than, the polymerizable compounds different from the compounds of formula I.
In a third preferred embodiment, the LC medium of the invention contains two or more polymerisable compounds of formula I or sub-formulae thereof in a total concentration of 0.2 to 1.5%, more preferably 0.3 to 1.2%, very preferably 0.4 to 1.0%.
The LC medium according to these second and third preferred embodiments is particularly suitable and preferred for use in PSA displays or PSA display manufacturing processes, wherein the polymerization is performed using UV LED lamps as described above, preferably using UV LED lamps in the UV1 step and UV LED lamps in the UV2 step, preferably having a wavelength in the preferred range as described above, most preferably 365nm.
The LC medium according to the present invention may additionally comprise one or more other components or additives, preferably selected from the list comprising but not limited to comonomers, chiral dopants, polymerization initiators, inhibitors, stabilizers, surfactants, wetting agents, lubricants, dispersants, hydrophobing agents, binders, flow improvers, defoamers, deaerators, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments and nanoparticles.
The LC medium preferably has a phase-aligned LC phase.
In a preferred embodiment, the LC medium contains one or more polymerization initiators. Suitable polymerization conditions, as well as suitable initiator types and amounts, are known to those skilled in the art and are described in the literature. Suitable for free-radical polymerization are, for example, commercially available photoinitiatorsOr/>(Ciba AG). If a polymerization initiator is used, the proportion thereof is preferably from 0.001 to 5% by weight, particularly preferably from 0.001 to 1% by weight.
The polymerizable compounds according to the invention are also suitable for polymerization without initiator, which has considerable advantages, for example lower material costs, in particular less contamination of the LC medium with possible residual amounts of initiator or degradation products thereof.
Therefore, polymerization can be performed without adding an initiator. Thus, in another preferred embodiment, the LC medium does not contain a polymerization initiator.
In another preferred embodiment, the LC medium additionally comprises one or more stabilizers to prevent undesired spontaneous polymerization of the RM, for example during storage or transport. Suitable types and amounts of stabilizers are known to the person skilled in the art and are described in the literature. It is particularly suitable that the first and second components are, for example,Series (Ciba AG) of commercially available stabilizers, e.g1076. If stabilizers are used, their proportion is preferably from 10 to 50,000ppm, particularly preferably from 50 to 5,000ppm, based on the total amount of RM or polymerizable components (component A).
In a preferred embodiment, the LC medium contains one or more chiral dopants, preferably in a concentration of 0.01 to 1wt%, very preferably 0.05 to 0.5wt%. The chiral dopant is preferably selected from the compounds of the following Table B, very preferably R-or S-1011, R-or S-2011, R-or S-3011, R-or S-4011 and R-or S-5011.
In another preferred embodiment, the LC medium contains racemates of one or more chiral dopants, which are preferably selected from the chiral dopants mentioned in the previous paragraph.
In a further preferred embodiment of the invention, the LC medium contains one or more further stabilizers, preferably selected from the following formulae
Wherein each group, independently of the other and identically or differently for each occurrence, has the following meanings:
r a-d is a straight or branched alkyl group having 1 to 10, preferably 1 to 6, very preferably 1 to 4C atoms, most preferably methyl,
X S is H, CH 3, OH or O ●,
A S is a straight-chain, branched or cyclic alkylene radical having 1 to 20C atoms, which is optionally substituted,
N is an integer from 1 to 6, preferably 3.
Preferred stabilizers of formula S3 are selected from the group consisting of formula S3A
Wherein n2 is an integer from 1 to 12, and wherein one or more H atoms in the group (CH 2)n2) are optionally replaced by methyl, ethyl, propyl, butyl, pentyl or hexyl.
Very preferred stabilizers are selected from the following formulae
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In a preferred embodiment, the LC medium comprises one or more stabilizers selected from the group consisting of formulas S1-1, S2-1, S3-1 and S3-3.
In a preferred embodiment, the LC medium comprises one or more stabilizers selected from table C below.
The proportion of stabilizers (such as those of the formulae S1 to S3) in the LC medium is preferably from 10 to 500ppm, very preferably from 20 to 100ppm.
In another preferred embodiment, the LC medium of the present invention contains a self-alignment (SA) additive, preferably in a concentration of 0.1-2.5%.
In another preferred embodiment, the LC medium of the present invention contains a self-alignment (SA) additive, preferably in a concentration of 0.1-2.5%.
In a preferred embodiment, the SA-VA display of the invention does not contain a polyimide alignment layer. In another preferred embodiment, the SA-VA display according to the preferred embodiment contains a polyimide alignment layer.
Preferred SA additives for this preferred embodiment are selected from compounds comprising mesogenic groups and linear or branched alkyl side chains terminated by one or more polar anchoring groups selected from hydroxyl, carboxyl, amino or thiol groups.
Further preferred SA additives contain one or more polymerizable groups, optionally linked to the mesogenic groups via spacer groups. These polymerizable SA additives can be polymerized in the LC medium under similar conditions as used for RM in the PSA process.
Suitable SA additives for inducing homeotropic alignment, in particular for SA-VA mode displays, are disclosed, for example, in US2013/0182202 A1, US 2014/0838581A1, US2015/0166890 A1 and US2015/0252265 A1.
In another preferred embodiment, the LC medium or polymer stabilized SA-VA display according to the invention contains one or more self-aligning additives selected from table E below.
In another preferred embodiment, the LC medium according to the invention contains one or more SA additives, preferably of formula II or subformulae thereof or selected from table E, in a concentration of 0.1-5%, very preferably 0.2-3%, most preferably 0.2-1.5%.
In addition to the polymerizable compounds and additives described above, the LC medium for LC displays according to the invention also comprises an LC mixture ("host mixture") comprising one or more, preferably two or more LC compounds selected from the group of non-polymerizable low molecular weight compounds, at least one of which is a compound of formula II. These LC compounds are selected such that they are stable and/or non-reactive to the polymerization reaction under the polymerization conditions applied to the polymerizable compounds.
Particularly preferred embodiments of such LC media are shown below.
Preferably, the LC medium contains one or more compounds of formula II selected from the group consisting of compounds of formulas IIA, IIB, IIC and IID
Wherein the method comprises the steps of
R 2A and R 2B each independently of one another represent H, alkyl or alkenyl having up to 15C atoms, which is unsubstituted, monosubstituted by CN or CF 3 or at least monosubstituted by halogen, wherein, in addition, one or more CH 2 groups of these radicals may be such that O atoms are not directly connected to one another by-O-, -S-, a radical of formula I, -C.ident.C-, -CF 2O-、-OCF2 -, -OC-O-or-O-CO-substitution,
L 1-L4 each independently of the other represents F, cl, CF 3 or CHF 2,
Y represents H, F, cl, CF 3、CHF2 or CH 3, preferably H or CH 3, particularly preferably H,
Z 2,Z2B and Z 2D each independently of the other represent a single bond 、-CH2CH2-、-CH＝CH-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C2F4-、-CF＝CF-、-CH＝CHCH2O-,
P represents 0, 1 or 2, and
Q represents, identically or differently, for each occurrence, 0 or 1.
Preferred compounds of formulae IIA, IIB, IIC and IID are those in which R 2B represents alkyl or alkoxy having up to 15C atoms, and very preferably (O) C vH2v+1, where (O) is an oxygen atom or a single bond and v is 1,2, 3, 4, 5 or 6.
Further preferred compounds of formulae IIA, IIB, IIC and IID are those wherein R 2A or R 2B represent or contain cycloalkyl or cycloalkoxy groups, preferably selected from Wherein S 1 is C 1-5 -alkylene or C 2-5 -alkenylene and S 2 is H, C 1-7 -alkyl or C 2-7 -alkenyl, and is very preferably selected from/>
Further preferred compounds of formulas IIA, IIB, IIC and IID are shown below:
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Wherein the parameter a represents 1 or 2, the alkyl and the alkyl * each represent, independently of one another, a linear alkyl group having 1 to 6C atoms, and the alkinyl represents a linear alkenyl group having 2 to 6C atoms, and (O) represents an oxygen atom or a single bond. The alkinyl preferably represents CH2＝CH-、CH2＝CHCH2CH2-、CH3-CH＝CH-、CH3-CH2-CH＝CH-、CH3-(CH2)2-CH＝CH-、CH3-(CH2)3-CH＝CH- or CH 3-CH＝CH-(CH2)2 -.
Particularly preferred LC media of the present invention comprise one or more compounds of formulas IIA-2, IIA-8, IIA-10, IIA-16, II-18, IIA-40, IIA-41, IIA-42, IIA-43, IIB-2, IIB-10, IIB-16, IIC-1 and IID-4.
The proportion of the compounds of the formulae IIA and/or IIB in the overall mixture is preferably at least 20% by weight.
In another preferred embodiment, the LC medium comprises one or more compounds of formula III
Wherein the method comprises the steps of
R 11 and R 12 each independently of one another represent H, alkyl having 1 to 15C atoms or alkoxy, where one or more CH 2 groups of these groups can each independently of one another be linked in such a way that O atoms are not directly linked to one another -C≡C-, -CF 2O-、-OCF2 -, -CH=CH-, replaced by-O-, -CO-O-or-O-CO-, and wherein in addition, one or more H atoms may be replaced by halogen,
A 3 each occurrence independently of one another
A) 1, 4-cyclohexenylene or 1, 4-cyclohexylene, in which one or two non-adjacent CH 2 groups may be replaced by-O-or-S-,
B) 1, 4-phenylene in which one or two CH groups may be replaced by N, or
C) A group selected from the group consisting of spiro [3.3] heptane-2, 6-diyl, 1, 4-bicyclo [2.2.2] octylene, naphthalene-2, 6-diyl, decalin-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, phenanthrene-2, 7-diyl and fluorene-2, 7-diyl,
Wherein the radicals a), b) and c) may be mono-or polysubstituted by halogen atoms,
N represents 0, 1 or 2, preferably 0 or 1,
Z 1, independently of one another, represents -CO-O-、-O-CO-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、-CH2-、-CH2CH2-、-(CH2)4-、-CH＝CH-CH2O-、-C2F4-、-CH2CF2-、-CF2CH2-、-CF＝CF-、-CH＝CF-、-CF＝CH-、-CH＝CH-、-C≡C- or a single bond, and
L 11 and L 12 each independently of one another represent F, cl, CF 3 or CHF 2, preferably H or F, most preferably F, and
W represents O or S.
In a preferred embodiment of the invention, the LC medium comprises one or more compounds of the formulae III-1 and/or III-2
Wherein the radicals present have the same meanings as given under formula III above and are preferably
R 11 and R 12 each independently of the other have up to 15C atoms of alkyl, alkenyl or alkoxy groups, more preferably one or both of them represent alkoxy groups, and
L 11 and L 12 each preferably represent F.
In another preferred embodiment, the LC medium comprises one or more compounds of formula III-1 selected from the group consisting of formulas III-1-1 to III-1-10, preferably formula III-1-6,
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Wherein alkyl and alkyl * each independently of the other represent a linear alkyl group having 1 to 6C atoms, alkyl and alkinyl * each independently of the other represent a linear alkenyl group having 2 to 6C atoms, alkoxy and alkoxy * each independently of the other represent a linear alkoxy group having 1 to 6C atoms, and L 11 and L 12 each independently of the other represent F or Cl, preferably both F.
In another preferred embodiment, the LC medium comprises one or more compounds of formula III-2 selected from the group consisting of formulas III-2-1 to III-2-10, preferably formula III-2-6,
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Wherein alkyl and alkyl * each independently of the other represent a linear alkyl group having 1 to 6C atoms, alkyl and alkinyl * each independently of the other represent a linear alkenyl group having 2 to 6C atoms, alkoxy and alkoxy * each independently of the other represent a linear alkoxy group having 1 to 6C atoms, and L 11 and L 12 each independently of the other represent F or Cl, preferably both F.
In another preferred embodiment of the invention, the LC medium comprises one or more compounds of formula IIIA-1 and/or IIIA-2
Wherein L 11 and L 12 have the same meaning as given under formula III, (O) represents O or a single bond,
R IIIA represents an alkyl or alkenyl group having up to 7C atoms, or a group Cy-C mH2m+1 -,
M and n are identical or different and are 0, 1, 2, 3, 4, 5 or 6, preferably 1, 2 or 3, very preferably 1, and
Cy represents a cycloaliphatic radical having 3, 4 or 5 ring atoms, optionally substituted with alkyl or alkenyl groups each having up to 3C atoms, or with halogen or CN, and preferably represents cyclopropyl, cyclobutyl or cyclopentyl.
The compounds of formula IIIA-1 and/or IIIA-2 may be substituted for the compound of formula III or additionally contained in an LC medium, preferably additionally.
Highly preferred compounds of formulae IIIA-1 and IIIA-2 are as follows:
Wherein alkoxy represents a straight chain alkoxy group having 1 to 6C atoms.
In a preferred embodiment of the invention, the LC medium comprises one or more compounds of formula III-3
Wherein the method comprises the steps of
R 11,R12 identical or different represent H, alkyl having 1 to 15C atoms or alkoxy, wherein one or more CH 2 groups of these radicals are optionally, independently of one another, substituted by-C.ident.C-in such a way that the O atoms are not directly bonded to one another-CF 2O-、-OCF2 -, -ch=ch-,-O-, -CO-O-or-O-CO-substitution, and wherein, in addition, one or more H atoms may be replaced by halogen.
The compound of formula III-3 is preferably selected from the group consisting of formulas III-3-1 to III-3-10:
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Wherein R 12 represents an alkyl group having 1 to 7C atoms, preferably ethyl, n-propyl or n-butyl, or alternatively, cyclopropylmethyl, cyclobutylmethyl or cyclopentylmethyl.
In another preferred embodiment of the invention, the LC medium comprises one or more compounds of the formulae III-4 to III-6, preferably of the formula III-5,
Wherein the parameters have the meanings given above, R 11 preferably represents a straight-chain alkyl group and R 12 preferably represents an alkoxy group, each having 1 to 7C atoms.
In another preferred embodiment, the LC medium comprises one or more compounds of formula III selected from the group consisting of formulas III-7 to III-9, preferably formula III-8,
Wherein the parameters have the meanings given above, R 11 preferably represents a straight-chain alkyl group and R 12 preferably represents an alkoxy group, each having 1 to 7C atoms.
In a preferred embodiment, the medium comprises one or more compounds of formula IV,
Wherein the method comprises the steps of
R 41 represents unsubstituted alkyl having 1 to 7C atoms or unsubstituted alkenyl having 2 to 7C atoms, preferably n-alkyl, particularly preferably having 2, 3, 4 or 5C atoms, and
R 42 represents an unsubstituted alkyl group having 1 to 7C atoms or an unsubstituted alkoxy group having 1 to 6C atoms (each preferably having 2 to 5C atoms), an unsubstituted alkenyl group having 2 to 7C atoms, preferably having 2, 3 or 4C atoms, more preferably vinyl or 1-propenyl and especially vinyl.
The compound of formula IV is preferably selected from formulas IV-1 to IV-4,
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Wherein the method comprises the steps of
The alkyl and alkyl radicals' independently of one another represent alkyl radicals having from 1 to 7C atoms, preferably from 2 to 5C atoms,
Alkinyl represents an alkenyl group having 2 to 5C atoms, preferably having 2 to 4C atoms, particularly preferably 2C atoms,
Alkinyl' denotes alkenyl having 2 to 5C atoms, preferably having 2 to 4C atoms, particularly preferably having 2 to 3C atoms, and
Alkoxy denotes an alkoxy group having 1 to 5C atoms, preferably having 2 to 4C atoms.
Preferably, the LC medium comprises one or more compounds selected from the group consisting of compounds of formulas IV-1-1 to IV-1-6
Very preferably, the LC medium according to the invention comprises one or more compounds of the formulae IV-2-1 and/or IV-2-2
Very preferably, the LC medium according to the invention comprises a compound of formula IV-3, in particular a compound selected from the group consisting of formulae IV-3-1 to IV-3-4
Very preferably, the LC medium according to the invention comprises compounds of the formula IV-4, in particular compounds selected from the group consisting of the formulae IV-4-1 and IV-4-2
The LC medium preferably additionally comprises one or more compounds of the formula Iva,
Wherein the method comprises the steps of
R 41 and R 42 each independently of one another represent straight-chain alkyl, alkoxy, alkenyl, alkoxyalkyl or alkoxy having up to 12C atoms, and
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Z 4 represents a single bond, -CH 2CH2-、-CH＝CH-、-CF2O-、-OCF2-、-CH2 O-,
-OCH 2-、-COO-、-OCO-、-C2F4-、-C4H8 -or-cf=cf-.
Preferred compounds of formula IVa are shown below:
wherein alkyl and alkyl * each independently of the other represent a straight-chain alkyl group having 1 to 6C atoms.
The LC medium according to the invention preferably comprises at least one compound of the formula IVa-1 and/or IVa-2.
The proportion of the compound of formula IVa in the overall mixture is preferably at least 5% by weight.
Preferably, the LC medium comprises one or more compounds of formulae IVb-1 to IVb-3
Wherein the method comprises the steps of
The alkyl and alkyl * each independently of the other represent a straight-chain alkyl radical having 1 to 6C atoms, and
Each of alkinyl and alkinyl *, independently of the other, represents a straight-chain alkenyl group having 2 to 6C atoms.
The proportion of biphenyl of the formulae IV-1 to IV-3 in the entire mixture is preferably at least 3% by weight, in particular.gtoreq.5% by weight.
Of the compounds of formulae IVb-1 to IVb-3, the compounds of formula IVb-2 are particularly preferred.
Particularly preferred biphenyls are
Wherein alkyl * represents an alkyl group having 1 to 6C atoms and preferably represents an n-propyl group.
The LC medium according to the invention particularly preferably comprises one or more compounds of the formulae IVb-1-1 and/or IVb-2-3.
In a preferred embodiment, the LC medium comprises one or more compounds of formula V
Wherein the method comprises the steps of
R 51 and R 52 independently of one another have one of the meanings given for R 41 and R 42 and preferably represent alkyl having 1 to 7C atoms, preferably n-alkyl, particularly preferably n-alkyl having 1 to 5C atoms, alkoxy having 1 to 7C atoms, preferably n-alkoxy, particularly preferably n-alkoxy having 2 to 5C atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 7C atoms, preferably 2 to 4C atoms, preferably alkenyloxy,
The same or different expressions
Wherein the method comprises the steps of
Preferred representation/>
Z 51,Z52 each independently of the other represents-CH 2-CH2-、-CH2 -O-; -CH=CH-, -C≡C-, -COO-, or a single bond, preferably-CH 2-CH2-、-CH2 -O-or a single bond and particularly preferably a single bond, and
N is 1 or 2.
The compound of formula V is preferably selected from compounds of formulae V-1 to V-16:
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Wherein R 1 and R 2 have the meanings described above for R 2A.
R 1 and R 2 preferably each independently of one another represent a linear alkyl or alkenyl radical.
Preferred LC media comprise one or more compounds of the formulae V-1, V-3, V-4, V-6, V-7, V-10, V-11, V-12, V-14, V-15 and/or V-16.
The LC medium according to the invention very particularly preferably comprises compounds of the formulae V-10, V-12, V-16 and/or IV-1, in particular in an amount of from 5 to 30%.
Preferred compounds of formula V-10 are shown below:
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LC media according to the invention particularly preferably comprise a tricyclic compound of formula V-10a and/or formula V-10b in combination with one or more bicyclic compounds of formula IV-1. The total proportion of the compounds of the formula V-10a and/or V-10b in combination with one or more compounds selected from dicyclohexyl compounds of the formula IV-1 is from 5 to 40%, very particularly preferably from 15 to 35%.
Very particularly preferred LC media comprise the compounds V-10a and IV-1
The compounds V-10a and IV-1-1 are preferably present in the mixture in a concentration of 15 to 35%, particularly preferably 15 to 25% and particularly preferably 18 to 22%, based on the entire mixture.
Very particularly preferred LC media comprise the compounds V-10b and IV-1-1:
the compounds V-10b and IV-1-1 are preferably present in the mixture in a concentration of 15 to 35%, particularly preferably 15 to 25% and particularly preferably 18 to 22%, based on the entire mixture.
Very particularly preferred LC media comprise the following three compounds:
The compounds V-10a, V-10b and IV-1-1 are preferably present in the mixture in a concentration of 15 to 35%, particularly preferably 15 to 25%, and particularly preferably 18 to 22%, based on the entire mixture.
Preferred LC media comprise at least one compound selected from
Wherein R 41 and R 42, and R 51 and R 52 have the meanings as described above. Preferably, in compounds V-6, V-7 and IV-1, R 41 and R 51 represent alkyl or alkenyl groups having 1 to 6C atoms or 2 to 6C atoms, respectively, and R 42 and R 52 represent alkenyl groups having 2 to 6C atoms.
Preferred LC media comprise at least one compound of the formulae V-6a, V-6b, V-7a, V-7b, IV-4-1, IV-4-2, IV-3a and IV-3 b:
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Wherein alkyl represents an alkyl group having 1 to 6C atoms and alkinyl represents an alkenyl group having 2 to 6C atoms.
The compounds of the formulae V-6a, V-6b, V-7a, V-7b, IV-4-1, IV-4-2, IV-3a and IV-3b are preferably present in the LC medium according to the invention in an amount of from 1 to 40% by weight, preferably from 5 to 35% by weight and very particularly preferably from 10 to 30% by weight.
In a preferred embodiment of the invention, the LC medium additionally comprises one or more compounds of the formulae VI-1 to VI-9
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Wherein the method comprises the steps of
R 7 each independently of the other has one of the meanings described for R 2A in formula IIA, and w and x each independently of the other represent 1 to 6.
It is particularly preferred that the LC medium comprises at least one compound of formula V-9.
In a preferred embodiment of the invention, the LC medium additionally comprises one or more compounds of the formulae VII-1 to VII-25,
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Wherein the method comprises the steps of
R represents a linear alkyl or alkoxy group having 1 to 6C atoms, (O) represents-O-or a single bond, X represents F, cl, OCF 3 or OCHF 2,Lx represents H or F, m is 0,1, 2, 3, 4, 5 or 6 and n is 0,1, 2, 3 or 4.
R preferably represents methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentoxy.
X preferably represents F or OCH 3, very preferably F.
The LC medium according to the invention preferably comprises terphenyl of the formulae VII-1 to VII-25, in particular 5 to 20% by weight, in an amount of 2 to 30% by weight.
Particular preference is given to compounds of the formulae VII-1, VII-2, VII-4, VII-20, VII-21 and VII-22 in which X denotes F. In these compounds, R preferably represents alkyl, as well as alkoxy, each having 1 to 5C atoms. In the compounds of the formulae VII to 20, R preferably represents alkyl or alkenyl, in particular alkyl. In the compounds of the formulae VII-21, R preferably represents alkyl. In the compounds of the formulae VII-22 to VII-25, X preferably denotes F.
If the Δn value of the mixture is ≡0.1, terphenyl of the formulae VII-1 to VII-25 is preferably used in the LC medium according to the invention. Preferred LC media contain 2-20wt% of one or more terphenyl compounds selected from the group consisting of compounds of formulas VII-1 through VII-25.
Further preferred embodiments are listed below:
a) The LC medium comprises at least one compound of the formulae Z-1 to Z-7,
Wherein R, (O) and alkyl have the meanings as described above for formula III.
B) Preferred LC media of the invention comprise one or more substances containing tetrahydronaphthyl or naphthyl units, for example compounds of the formulae N-1 to N-5,
Wherein R 1N and R 2N each independently of the other have the meaning described above for R 2A, preferably represent a linear alkyl, linear alkoxy or linear alkenyl group, and
Z 1 and Z 2 each independently of one another represent -C2H4-、-CH＝CH-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-CH＝CHCH2CH2-、-CH2CH2CH＝CH-、-CH2O-、-OCH2-、-COO-、-OCO-、-C2F4-、-CF＝CF-、-CF＝CH-、-CH＝CF-、-CF2O-、-OCF2-、-CH2- or a single bond.
C) Preferred LC media comprise one or more compounds selected from the group consisting of difluorodibenzochromans of formula BC, CR chromans, and fluorophenanthrene compounds of formulae PH-1 and PH-2,
Wherein the method comprises the steps of
R B1,RB2,RCR1,RCR2,R1,R2 each independently of one another have the meaning of R 2A. c is 0,1 or 2.R 1 and R 2 preferably represent, independently of one another, alkyl or alkoxy having 1 to 6C atoms.
The LC medium according to the invention preferably comprises compounds of the formulae BC, CR, PH-1, PH-2 in an amount of 3 to 20% by weight, in particular 3 to 15% by weight.
Particularly preferred compounds of the formulae BC and CR are the compounds BC-1 to BC-7 and CR-1 to CR-5,
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Wherein the method comprises the steps of
The alkyl and alkyl * each independently of the other represent a straight-chain alkyl radical having 1 to 6C atoms, and
Alkinyl, and
Each of alkenyl * independently of the others represents a straight-chain alkenyl group having 2 to 6C atoms.
Very particular preference is given to LC media comprising one, two or three compounds of the formulae BC-2, BF-1 and/or BF-2.
D) Preferred LC media contain one or more indane compounds of formula In,
Wherein the method comprises the steps of
R11,R12,
R 13 each independently of the other represents a straight-chain alkyl, alkoxy, alkoxyalkyl or alkenyl radical having 1 to 6C atoms.
R 12 and R 13 additionally represent halogen, preferably F,
Representation/>
I represents 0, 1 or 2.
Preferred compounds of formula In are those of formulae In-1 to In-16 described below:
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Particularly preferred are compounds of the formulae In-1, in-2, in-3 and In-4.
The compounds of the formulae In and the sub-formulae In-1 to In-16 are preferably used In the LC medium according to the invention In a concentration of.gtoreq.5 wt.%, in particular 5 to 30 wt.% and very particularly preferably 5 to 25 wt.%.
E) Preferred LC media additionally comprise one or more compounds of the formulae L-1 to L-5,
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Wherein the method comprises the steps of
R and R 1 each independently of one another have the meaning described above for R 2A in formula IIA, and alkyl represents alkyl having 1 to 6C atoms. The parameter s represents 1 or 2.
The compounds of the formulae L-1 to L-5 are preferably used in concentrations of 5 to 50% by weight, in particular 5 to 40% by weight, and very particularly preferably 10 to 40% by weight.
F) Preferred LC media additionally comprise one or more compounds of formula IIA-Y
Wherein R 11 and R 12 have one of the meanings given above for R 2A in formula IIA, and L 1 and L 2, identically or differently, represent F or Cl.
Preferred compounds of formula IIA-Y are selected from the following subformulae
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Wherein, alkyl and Alkyl * each independently represent a linear Alkyl group having 1 to 6C atoms, alkoxy represents a linear alkoxy group having 1 to 6C atoms, alkenyl and Alkenyl * each independently represent a linear alkenyl group having 2 to 6C atoms, and O represents an oxygen atom or a single bond. Alkenyl and Alkenyl * preferably represent CH2＝CH-、CH2＝CHCH2CH2-、CH3-CH＝CH-、CH3-CH2-CH＝CH-、CH3-(CH2)2-CH＝CH-、CH3-(CH2)3-CH＝CH- or CH 3-CH＝CH-(CH2)2 -.
Particularly preferred compounds of the formula IIA-Y are selected from the following subformulae:
Wherein Alkoxy and Alkoxy * have the meanings defined above and preferably represent methoxy, ethoxy, n-propoxy, n-butoxy or n-pentoxy.
G) An LC medium additionally comprising one or more tetrabenamine compounds selected from the following formulae:
Wherein the method comprises the steps of
R Q is alkyl, alkoxy, oxaalkyl or alkoxyalkyl having 1 to 9C atoms or alkenyl or alkenyloxy having 2 to 9C atoms, all of which are optionally fluorinated,
X Q is F, cl, haloalkyl or alkoxy having 1 to 6C atoms or haloalkenyl or alkenyloxy having 2 to 6C atoms,
Each L Q1-LQ6 is independently H or F, wherein at least one of L Q1-LQ6 is F.
Preferred compounds of formula Q are those in which R Q represents a straight-chain alkyl radical having 2 to 6C-atoms, very preferably ethyl, n-propyl or n-butyl.
Preferred compounds of formula Q are those wherein L Q3 and L Q4 are F. Further preferred compounds of formula Q are those wherein L Q3、LQ4 and one or both of L Q1 and L Q2 are F.
Preferred compounds of formula Q are those wherein X Q represents F or OCF 3, very preferably F.
The compound of formula Q is preferably selected from the following subformulae
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Wherein R Q has one of the meanings of the formula Q or one of its preferred meanings given in the context, and preferably ethyl, n-propyl or n-butyl.
Particular preference is given to compounds of the formula Q1, in particular those in which R Q is n-propyl.
Preferably, the proportion of the compound of formula Q in the LC host mixture is from >0 to < 5 wt.%, very preferably from 0.05 to 2 wt.%, more preferably from 0.1 to 1 wt.%, most preferably from 0.1 to 0.8 wt.%.
Preferably the LC medium contains 1 to 5, preferably 1 or 2 compounds of formula Q.
The addition of the formula Q tetrabenane compound to the LC host mixture can reduce ODF inhomogeneities while maintaining high UV absorption, achieve rapid and complete polymerization, produce strong and rapid tilt angles, and improve UV stability of the LC medium.
Furthermore, the addition of the compound of formula Q having positive dielectric anisotropy to LC medium having negative dielectric anisotropy can better control the values of dielectric constants epsilon || and epsilon ⊥, and in particular can achieve a high dielectric constant epsilon || and keep the dielectric anisotropy delta epsilon constant, thereby reducing the kickback voltage and reducing image sticking.
The LC medium according to the invention preferably comprises
One or more compounds of the formula I, preferably of the formula I1, very preferably of the formulae I1-1 to I1-10, preferably in a total concentration of 0.01% to 2.0%, more preferably of 0.1% to 1.0%, most preferably of 0.2% to 0.8%,
And/or
-One or more compounds of formula IIA, preferably in a total concentration of 5% to 30%, more preferably 7% to 25%, particularly preferably 10% to 20%;
and/or
-One or more compounds of formulae IIA and IIB, preferably in a total concentration of 30% to 45%;
and/or
-One or more compounds of formula IV, preferably in a total concentration of 35% to 70%, more preferably 40% to 65%, particularly preferably 45% to 60%;
and/or
-One or more compounds of formula IV-3, preferably in a total concentration of 35% to 60%, more preferably 40% to 55%, particularly preferably 45% to 50%;
and/or
One or more compounds of the formula III-2, preferably of the formula III-2-6, preferably in a total concentration of 2% to 25%, more preferably 5% to 15%, particularly preferably 5% to 12%.
In particular, the medium comprises
-One or more compounds CY-n-Om, in particular CY-3-O4, CY-5-O4 and/or CY-3-O2, preferably in a total concentration of 5% to 30%, preferably 10% to 20%;
and/or
-One or more compounds PY-n-Om, in particular PY-3-O2 and/or PY-1-O2, preferably in a total concentration of 5% to 30%, preferably 5% to 20%;
and/or
CPY-n-Om, in particular CPY-2-O2, CPY-3-O2 and/or CPY-5-O2, preferably in a total concentration of >5%, in particular 7% to 20%, based on the whole mixture,
And/or
-One or more compounds CCY-n-Om, preferably CCY-4-O2, CCY-3-O3, CCY-3-O1 and/or CCY-5-O2, preferably in a total concentration of >3%, in particular 5-15%, based on the whole mixture;
and/or
-One or more compounds CPY-n-Om, preferably CPY-2-O2 and/or CPY-3-O2, preferably in a total concentration of >3%, in particular 5-15%, based on the whole mixture;
and/or
-CLY-n-Om, preferably CLY-2-O4, CLY-3-O2 and/or CLY-3-O3, preferably in a total concentration >5%, in particular 10-30%, very preferably 15-20%, based on the whole mixture;
and/or
CPY-n-Om and CY-n-Om, preferably in a total concentration of 10-80%, based on the whole mixture,
And/or
CPY-n-Om and PY-n-Om, preferably CPY-2-O2 and/or CPY-3-O2 and PY-3-O2 or PY-1-O2, preferably in a total concentration of 5 to 20%, more preferably 10 to 15%, based on the whole mixture,
And/or
-CC-3-V, preferably in a total concentration of 5-50% based on the whole mixture.
And/or
The total concentration of the compounds of the formula CC-3-V1 is from 5 to 40%, more preferably from 15% to 35%, particularly preferably from 20% to 30%,
And/or
One or more compounds of the formula B-nO-Om and/or B (S) -nO-Om, in particular compounds B (S) -2O-O4 and/or B (S) -2O-O5, preferably in a concentration of 2 to 12%.
And/or
-0.1% -3% Of compound PPGU-3-F.
The invention further relates to an electro-optic display with active matrix addressing, characterized in that it contains an LC medium according to claim 1 as dielectric, and wherein the display is a VA, SA-VA, IPS, U-IPS, FFS, UB-FFS, SA-FFS, PS-VA, PS-OCB, PS-IPS, PS-FFS, PS-UB-FFS, PS-posi-VA, PS-TN, polymer stabilized SA-VA or polymer stabilized SA-FFS display.
It is advantageous for the LC medium according to the invention to have preferably a nematic phase of from.ltoreq.20℃to.gtoreq.70℃and particularly preferably from.ltoreq.30℃to.gtoreq.80℃and very particularly preferably from.ltoreq.40℃to.gtoreq.90℃.
The media of the present invention have a clearing temperature of 70 ℃ or higher, preferably 74 ℃ or higher.
The expression "having a nematic phase" here means on the one hand that no smectic phase and no crystallization are observed at the respective temperatures at low temperatures and on the other hand that the heating from the nematic phase does not yet clear. The low temperature study was performed in a flow viscometer at the corresponding temperature and examined by storage in a test box having a layer thickness corresponding to the electro-optic application for at least 100 hours. If the storage stability in the corresponding test cartridge is 1000 hours or more at a temperature of-20 ℃, the medium is said to be stable at that temperature. At temperatures of-30℃and-40℃the corresponding times were 500 hours and 250 hours, respectively. At elevated temperature, the clearing point is measured in a capillary tube by conventional methods.
The liquid-crystalline mixture preferably has a nematic phase range of at least 60K and a flow viscosity v 20 of at most 30mm 2·s-1 at 20 ℃.
The mixture is nematic at a temperature of-20 ℃ or less, preferably-30 ℃ or less, and very preferably-40 ℃ or less.
The birefringence delta n in the liquid-crystalline mixture is generally from 0.07 to 0.16, preferably from 0.08 to 0.15, very preferably from 0.09 to 0.14.
In a preferred embodiment of the invention, the medium has a birefringence of from 0.090 to 0.110, preferably from 0.095 to 0.105, in particular from 0.100 to 0.105.
In another preferred embodiment, the medium of the present invention has a birefringence of 0.120 or higher, preferably 0.125-0.145, more preferably 0.130-0.140.
The liquid-crystalline mixtures according to the invention have a dielectric anisotropy Δεof from-1.5 to-8.0, preferably from-2.0 to-4.0, in particular from-2.5 to-3.5,
The rotational viscosity γ 1 is preferably not more than 120 mPas, in particular not more than 100 mPas, at 20 ℃.
In a preferred embodiment, the rotational viscosity gamma 1 at 20℃is.ltoreq.100 mPas, in particular.ltoreq.95 mPas.
The liquid-crystalline medium according to the invention has a relatively low threshold voltage (V 0). They are preferably in the range from 1.7V to 3.0V, particularly preferably 2.7V and very particularly preferably 2.5V.
For the purposes of the present invention, the term "threshold voltage" refers to a capacitive threshold (V 0), also known as Freedericks threshold, unless explicitly indicated otherwise.
Furthermore, the inventive liquid-crystalline media have high voltage retention values in the liquid-crystalline cell.
In general, liquid crystal media with low addressing voltages or threshold voltages exhibit lower voltage retention than those LC media with higher addressing voltages or threshold voltages, and vice versa.
For the purposes of the present invention, the term "dielectrically positive compounds" means compounds having a Δε >1.5, the term "dielectrically neutral compounds" means those having a Δε of-1.5.ltoreq.Δε.ltoreq.1.5 and the term "dielectrically negative compounds" means those having a Δε < -1.5. Here, the dielectric anisotropy of the compounds is determined by dissolving 10% of the compounds in the LC body in at least one test cell and measuring the capacitance of the resulting mixture, the test cell in each case having a layer thickness of 20 μm and having homeotropic and faceted surface alignment at 1 kHz. The measurement voltage is typically 0.5V-1.0V, but always below the capacitance threshold of the respective liquid crystal mixture under investigation.
All temperature values described in the present invention are in units of c.
The LC medium of the present invention is suitable for all VA-TFT (vertically aligned thin film transistor) applications, such as VAN (vertically aligned nematic), MVA (multi-domain VA), (S) -PVA (super patterned VA), ASV (advanced super view or axisymmetric VA), PSA (polymer stabilized VA) and PS-VA (polymer stabilized VA). Furthermore, they are also suitable for IPS (in-plane switching) and FFS (fringe field switching) applications with negative Δ∈.
The nematic LC medium in the display according to the invention generally comprises two components a and B, which themselves consist of one or more individual compounds.
The component A has remarkable negative dielectric anisotropy, and the dielectric anisotropy of the nematic phase is less than or equal to-0.5. In addition to one or more compounds of formula I, it preferably comprises a compound of formula IIA, IIB and/or IIC, and one or more compounds of formula IV-1.
The proportion of component A is preferably 45 to 100%, in particular 60 to 85%.
For component A, it is preferable to select one or more individual compounds having a.DELTA.ε value of.ltoreq.0.8. The smaller the proportion of A in the overall mixture, the more negative this value must be.
Component B has a pronounced nematic nature (nematogeneity) and a flow viscosity at 20℃of not more than 30mm 2·s-1, preferably not more than 25mm 2·s-1.
A variety of suitable materials are known to those skilled in the art from the literature. Particular preference is given to compounds of the formula O-17.
Particularly preferred individual compounds in component B are very low-viscosity nematic liquid crystals whose flow viscosity at 20℃is not more than 18mm 2·s-1, preferably not more than 12mm 2·s-1.
Component B is a mono-or reciprocal (monotropically, enantiotropically) nematic phase, has no smectic phase, and is capable of preventing the occurrence of smectic phases in LC media at very low temperatures. For example, if various high nematic materials are added to a smectic phase liquid crystal mixture, the nematic states of these materials can be compared by suppressing to the extent of smectic phase.
The mixture may also optionally comprise component C, which comprises compounds having a dielectric anisotropy of Δε. Gtoreq.1.5. These so-called positive compounds are generally present in the mixture of negative dielectric anisotropy in an amount of.ltoreq.20 wt.%, based on the whole mixture.
In addition to one or more compounds of the formulae I1, I2 and optionally I3, the medium preferably comprises 4 to 15, in particular 5 to 12, and particularly preferably <10 compounds of the formulae IIA, IIB and/or IIC and optionally one or more compounds of the formula IV-1.
In addition to the compounds of the formulae I1, I2 and optionally I3 and the compounds of the formulae IIA, IIB and/or IIC and optionally IV-1, further constituents may also be present in amounts of up to 45%, but preferably up to 35%, in particular up to 10%, of the entire mixture.
The other component is preferably selected from nematic or nematic (nematogenic) substances, in particular from the following classes of known substances: azobenzene, benzylidene aniline, biphenyl, phenyl benzoate or cyclohexyl benzoate, phenyl or cyclohexyl cyclohexanecarboxylate, phenylcyclohexane, cyclohexylbiphenyl, cyclohexylcyclohexane, cyclohexylnaphthalene, 1, 4-dicyclohexylbiphenyl or cyclohexylpyrimidine, phenyldioxane or cyclohexyldioxane, optionally halogenated stilbene, benzyl phenyl ether, diphenylacetylene and substituted cinnamic acid esters.
The most important compounds suitable as components of this type of liquid crystal phase can be characterized by the following formula OC
R20-L-G-E-R21 OC
Wherein L and E each refer to a carbocyclic or heterocyclic ring system from the group formed by: 1, 4-disubstituted benzene rings and cyclohexane rings, 4' -disubstituted biphenyls, phenylcyclohexane and cyclohexylcyclohexane systems, 2, 5-disubstituted pyrimidines and 1, 3-dioxane rings, 2, 6-disubstituted naphthalenes, dihydronaphthalenes and tetrahydronaphthalenes, quinazolines and tetrahydroquinazolines,
G represents-CH=CH-N (O) =N-
-CH＝CQ- -CH＝N(O)-
-C≡C- -CH2-CH2-
-CO-O- -CH2-O-
-CO-S- -CH2-S-
-CH＝N- -COO-Phe-COO-
-CF2O- -CF＝CF-
-OCF2- -OCH2-
-(CH2)4- -(CH2)3O-
Or a c—c single bond, Q represents halogen, preferably chlorine or-CN, and R 20 and R 21 each represent alkyl, alkenyl, alkoxy, alkoxyalkyl or alkoxycarbonyloxy having up to 18, preferably up to 8 carbon atoms, or one of these groups refers to CN, NC, NO 2、NCS、CF3、SF5、OCF3, F, cl or Br.
In most of these compounds, R 20 and R 21 are different from each other, and one of these groups is typically an alkyl or alkoxy group. Other variations of the proposed substituents are also common. Many such materials or mixtures thereof are also commercially available. All these substances can be prepared by methods known from the literature.
It will be apparent to those skilled in the art that VA, IPS or FFS mixtures according to the invention may also comprise compounds in which, for example, H, N, O, cl and F are replaced by the corresponding isotopes.
The combination of the compounds of the preferred embodiments mentioned above with the above-mentioned polymeric compounds results in a low threshold voltage, a low rotational viscosity and a very good low temperature stability in the LC medium of the invention, while continuing a high clearing point and a high HR value and allowing a particularly low tilt angle (i.e. a large tilt) to be established rapidly in PSA displays. In particular, the LC media exhibit significantly reduced response times, particularly gray scale response times, in PSA displays as compared to LC media from the prior art.
The LC medium according to the invention may also contain other additives known to the person skilled in the art and described in the literature, such as polymerization initiators, inhibitors, stabilizers, surface-active substances or chiral dopants. These may be polymerizable or non-polymerizable. The polymerizable additives are correspondingly assigned to the polymerizable component or component a). Accordingly, the non-polymerizable additives are attributed to the non-polymerizable component or component B).
Furthermore, it is possible to add, for example, 0 to 15% by weight of a polychromatic dye to the LC medium, in addition to nanoparticles, conductive salts, preferably complex salts of ethyldimethyldodecyl4-hexyloxybenzoic acid ammonium, tetrabutyltetraphenylammonium borate or crown ether (see, for example, haller et al mol. Cryst. Liq. Cryst.24, 249-258 (1973)) for improving the conductivity, or substances for modifying the dielectric anisotropy, viscosity and/or alignment of the nematic phase. Such substances are described, for example, in DE-A22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430 and 28 53 728.
The individual components of the above-listed preferred embodiments of the LC medium according to the invention are known or the process for preparing them can be derived from the prior art by the person skilled in the relevant art, since they are based on standard processes described in the literature. The corresponding compounds of the formula CY are described, for example, in EP-A-0 364 538. The corresponding compounds of the formula ZK are described, for example, in DE-A-26 36 684 and DE-A-33 21 373.
The LC media which can be used according to the invention are prepared in a manner which is conventional per se, for example by mixing one or more of the compounds mentioned above with one or more polymerisable compounds as defined above and optionally with further liquid-crystalline compounds and/or additives. In general, the desired amount of the components used in minor amounts is dissolved in the components constituting the main ingredient, which is advantageously carried out at elevated temperatures. It is also possible to mix the solution of the components in an organic solvent, for example acetone, chloroform or methanol, and to remove the solvent again, for example by distillation after thorough mixing. The invention also relates to a method for the preparation of an LC medium according to the invention.
It is obvious to a person skilled in the art that the LC medium according to the invention may also comprise compounds, for example, in which H, N, O, cl, F is replaced by a corresponding isotope, for example deuterium.
The following examples illustrate the invention but do not limit it. However, they present the person skilled in the art with the preferred mixture concept, and the compounds preferably used and their respective concentrations, and their combinations with one another. Furthermore, the examples illustrate which properties and combinations of properties are available.
Preferred mixture components are shown in Table A below.
Table A
In Table A, m and n are each independently an integer from 1 to 12, preferably 1,2,3, 4, 5 or 6,k is 0, 1,2,3, 4, 5 or 6, and (O) C mH2m+1 represents C mH2m+1 or OC mH2m+1.
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In a preferred embodiment of the invention, the LC medium according to the invention comprises one or more compounds selected from the compounds of table a.
Table B
Table B shows chiral dopants that may be added to LC media of the present invention.
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The LC medium preferably contains 0 to 10% by weight, in particular 0.01 to 5% by weight, particularly preferably 0.1 to 3% by weight, of dopants. The LC medium preferably comprises one or more dopants selected from the group of compounds of table B.
Table C
Table C shows possible stabilizers that may be added to the LC medium of the present invention. Where n represents an integer from 1 to 12, preferably 1,2, 3,4,5,6, 7 or 8, and the terminal methyl group is not shown.
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The LC medium preferably contains 0 to 10% by weight, in particular 1ppm to 5% by weight, particularly preferably 1ppm to 1% by weight, of stabilizers. The LC medium preferably comprises one or more stabilizers selected from the group of compounds of table C.
Table D
Table D shows exemplary reactive mesogenic compounds that may be used in the LC media of the present invention.
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In a preferred embodiment, the mixture according to the invention comprises one or more polymerizable compounds, preferably selected from the group of polymerizable compounds of the formulae RM-1 to RM-183. Of these, compounds RM-1、RM-4、RM-8、RM-17、RM-19、RM-35、RM-37、RM-39、RM-40、RM-41、RM-48、RM-52、RM-54、RM-57、RM-58、RM-64、RM-74、RM-76、RM-88、RM-91、RM-102、RM-103、RM-109、RM-116、RM-117、RM-120、RM-121、RM-122、RM-139、RM-140、RM-142、RM-143、RM-145、RM-146、RM-147、RM-149、RM-156 to RM-163, RM-169, RM-170, and RM-171 to RM-183 are particularly preferable.
Table E
Table E shows self-aligning additives for vertical alignment which can be used with the polymerizable compounds of formula I in LC media for SA-VA and SA-FFS displays according to the invention:
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In a preferred embodiment, the LC medium of the SA-VA and SA-FFS displays according to the invention comprises one or more SA additives selected from the group of formulae SA-1 to SA-48 (preferably from the group of formulae SA-14 to SA-48, very preferably from the group of formulae SA-20 to SA-34 and SA-44) and one or more RMs of formula I.
Examples
The following examples illustrate the invention without limiting it. However, it shows to the person skilled in the art the concept of a preferred mixture with the compounds preferably used and their corresponding concentrations and combinations with each other. In addition, the embodiments illustrate the characteristics and combinations of characteristics that can be obtained.
In addition, the following abbreviations and symbols are used:
v 0 represents the threshold voltage at 20 c, the capacitance V,
N e represents the extraordinary refractive index at 20℃and 589nm,
N o represents the ordinary refractive index at 20℃and 589nm,
Δn represents optical anisotropy at 20℃and 589nm,
Epsilon ⊥ represents the dielectric constant perpendicular to the director at 20 c and 1kHz,
Epsilon || represents the dielectric constant parallel to the director at 20 c and 1kHz,
Delta epsilon represents the dielectric anisotropy at 20 deg.c and 1kHz,
Cl.p., T (N, I) represents a clear light spot [. Degree.C ],
Gamma 1 represents the rotational viscosity at 20 c [ mpa·s ],
K 1 denotes the elastic constant at 20 ℃, the "splay" deformation [ pN ],
K 2 represents the elastic constant at 20 ℃, the "twist" deformation [ pN ],
K 3 represents the elastic constant at 20℃and the "bending" deformation [ pN ].
Unless explicitly indicated otherwise, all concentrations in the present application are given in weight percent and relate to the corresponding whole mixture, which contains all solid or liquid crystalline components (without solvent).
All temperature values indicated in the present application, e.g. melting point T (C, N), transition from smectic phase (S) to nematic phase (N) T (S, N) and clearing point T (N, I) are expressed in degrees celsius (°c), unless otherwise indicated. M.p. represents melting point, cl.p. =clearing point. Furthermore, c=liquid crystalline phase, n=nematic phase, s=smectic phase and i=isotropic phase. The data between these symbols represents the transition temperature.
All physical properties are and have been determined according to "Merck Liquid Crystals, physical Properties of Liquid Crystals" Status 1997, 11 months, MERCK KGAA, germany and are suitable for temperatures of 20 ℃, and Δn is determined at 589nm and Δε is determined at 1kHz, unless explicitly stated otherwise in each case.
The term "threshold voltage" as used in the present invention relates to a capacitive threshold (V 0), which is also referred to as Freedericks threshold unless otherwise indicated. In an embodiment, the optical threshold is also given as usual for a relative contrast of 10% (V 10).
Unless otherwise indicated, the process of polymerizing the polymerizable compound in a PSA display as described above and below is carried out at a temperature at which the LC medium exhibits a liquid crystal phase, preferably a nematic phase, and most preferably at room temperature.
Unless otherwise indicated, the methods of preparing the test cartridges and measuring their electro-optic and other properties are performed by the methods described below or similar methods.
Displays for measuring capacitive threshold voltages are typically composed of two plane-parallel glass plates 25 μm apart, each plate having an electrode layer on the inside and an unwarped polyimide alignment layer on top, which results in vertical edge alignment of the liquid crystal molecules.
The PSVA display or PSVA test cell for measuring tilt angle is typically composed of two plane parallel glass outer plates separated by 4 μm, each of which has an electrode layer and a polyimide alignment layer on top on the inside, where the two polyimide layers rub anti-parallel to each other and cause homeotropic edge alignment of the liquid crystal molecules, unless otherwise indicated. SAVA the display or test cartridge has the same structure, but with one or both polyimide layers omitted.
The polymerizable compound is typically polymerized in the display or the test cartridge by irradiating with UV light of a defined intensity for a predetermined time while applying a voltage (typically 10V-30V ac, 1 kHz) to the display.
The intensity was measured using a standard instrument (Hoenle UV-high end with UV sensor).
Tilt angle is typically determined using the Mueller Matrix Polarimeter "AxoScan" of Axometrics. A small value (i.e. a large deviation from the 90 ° angle) corresponds here to a large inclination.
Unless otherwise indicated, the term "tilt angle" means the angle between the LC director and the substrate, and "LC director" means the preferred orientation direction of the optically principal axes of LC molecules in a layer of LC molecules having a uniform orientation, corresponding to their molecular long axes in the case of rod-like, uniaxial positive birefringent LC molecules.
Example 1
Nematic LC host mixture N1 was formulated as follows
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The polymerizable mixture P1 according to the invention is prepared by adding 0.05% of the polymerizable compound 1 of the formula I and 0.3% of the polymerizable compound RM-1 to the nematic LC host mixture N1.
For comparison purposes, the polymerizable mixture C1 was prepared by adding only 0.3% of the polymerizable compound RM-1 to the nematic LC host mixture N1.
The absorption wavelength λ of the polymerisable compounds RM-1 and 1 at an extinction coefficient e=0.5 was measured in a solution in DCM at a concentration of 3 g/L. The results are shown in Table 1.
TABLE 1 UV absorption
As can be seen from Table 1, compound 1 of formula I has a longer absorption wavelength than compound RM-1. Thus, compound 1 is more suitable for UV photopolymerization at longer wavelengths.
Based on the UV-Vis absorption data shown in table 1 above, it is expected that compound RM-1 will not exhibit good polymerization when exposed to a UV-LED lamp having an emission centered at 365nm, because its absorption spectrum lacks overlap with the UV-LED emission spectrum of the UV-LED lamp.
Thus, unless otherwise indicated in the experiments below, mixtures containing only compound RM-1 were polymerized using a C-type fluorescent lamp having an emission peak at 313nm, while mixtures containing only compound of formula I were polymerized using a UV-LED lamp emitting centered at 365nm, and mixtures containing compound of formula I and compound RM-1 were polymerized using a C-type lamp in the UV1 step and a B-type lamp in the UV2 step.
For polymerizing the polymerizable compound 1, the test cartridge containing the polymerizable mixture P1 is exposed to UV light in a two-step process, the first step (UV 1) for generating an oblique angle, and the second step (UV 2) for polymerizing any residual monomers not polymerized in the first step. In the UV1 step, a voltage (20 Vpp square wave, 200 Hz) is applied. In the UV2 step, no voltage is applied. Unless otherwise indicated, other conditions are as follows:
UV1 (C lamp): 4.5mW/cm 2, at room temperature, 30-200 seconds
UV2 (type B lamp): 2.5mW/cm 2 at room temperature for 120 min
For polymerizing the polymerizable compound RM-1, a test cartridge containing the polymerizable mixture C1 is irradiated with a conventional lamp to polymerize the compound in two steps as described above. The conditions are as follows.
UV1 (C-type fluorescent lamp): 4.5mW/cm 2, at room temperature, 30-300 seconds
UV2 (C-type fluorescent lamp): 0.5mW/cm 2 at room temperature for 120min
Tilt angle generation
The tilt angle generated in the test cartridge after the above UV1 step was measured using an Otsuka t_rets-10 system. The time required to produce an 88 tilt angle is shown in table 2 below.
TABLE 2 Tilt Angle Generation
| Mixture of | UV1 time (seconds) |
| C1 | 150-160 |
| P1 | 50-60 |
As can be seen from table 2, the polymerizable mixture P1 according to the invention shows a significantly faster tilt angle generation than the reference mixture C1.
Tilt stability
The tilt stability, i.e. the change of tilt angle after repeated electrical stress, is a criterion for assessing the risk of image sticking. A low value of the change in tilt angle represents a high tilt stability and a low potential risk of image sticking.
To determine the tilt stability, the test cartridges polymerized as described above were electrically stressed with a square wave of 60V PP at 60Hz for 72 hours. After a relaxation time of 5-10 minutes, the tilt angle was measured using an Otsuka T_RETS-10 system.
Determining the change in tilt angle, Δtilt, according to equation (1)
tilt After stress tilt After tilting is generated ＝Δtilt (1)
And is shown in table 3 below.
The lower the value of delta tilt, the higher the tilt stability.
TABLE 3 Tilt stability
| Mixture of | Δtilt/° |
| C1 | 0.49 |
| P1 | 0.37 |
As can be seen from table 3, the polymerizable mixture P1 according to the invention shows a significantly better tilt stability than the reference mixture C1.
Voltage Holding Ratio (VHR)
The VHR of the polymerizable LC medium was measured at 60℃and a voltage of 1V/0.6Hz was applied initially and after UV exposure. Optical stress generally results in a decrease in VHR in the LC mixture, so the smaller the absolute decrease in VHR value after stress, the better the display application performance.
The results are shown in Table 4.
TABLE 4 VHR
As can be seen from table 4, the VHR of the polymerizable mixture P1 according to the invention is significantly higher than the VHR of the polymerizable mixture C1 after UV stress.
Overall, the above results show that the addition of small amounts of polymerizable compounds of formula I to polymerizable LC media comprising the polymerizable compounds RM-1 of the prior art results in a significant improvement of tilt angle generation, tilt stability and VHR after UV stress.
Examples 2&3
Nematic LC host mixture N2 was formulated as follows
The polymerisable mixtures P2 and P3 according to the invention are prepared by adding polymerisable compounds 1 of the formula I and polymerisable compounds RM-1 in different concentrations to a nematic LC host mixture N2.
For comparison purposes, the polymerizable reference mixture C2 was prepared by adding only the polymerizable compound RM-1 to the nematic LC host mixture N2.
The composition of the polymerizable mixture is shown in table 5 below.
TABLE 5 composition of polymerizable mixture
The mixture was polymerized as described in example 1, using a type C lamp in the UV1 step and a type B lamp in the UV2 step.
Inclination angle
The tilt angle produced in the test cartridge after UV1 step was determined as described in example 1. The time required to produce an 88 tilt angle is shown in table 6 below.
TABLE 6 Tilt Angle
| Mixture of | UV1 time (seconds) |
| C2 | 150-160 |
| P2 | 70-80 |
| P3 | 50-60 |
As can be seen from Table 6, the polymerizable mixtures P2 and P3 according to the invention showed significantly faster tilt angle development than mixture C2.
Tilt stability
The change in tilt angle Δtilt was determined as described in example 1, as shown in table 7 below.
TABLE 7 Tilt stability
| Mixture of | Δtilt/° |
| C2 | 0.17 |
| P2 | 0.18 |
| P3 | 0.18 |
As can be seen from table 7, the polymerizable mixtures P2 and P3 according to the invention show good tilt stability similar to the mixture C2.
The above results show that the addition of only small amounts of polymerizable compounds of formula I makes the LC medium suitable for PSA displays prepared by polymerization using longer UV wavelengths (e.g. by using UV type B lamps in the UV2 step).
Examples 4 to 9
The polymerizable mixtures P4 to P9 according to the invention are prepared by adding polymerizable compounds 1 or 2 and polymerizable compound RM-1 in different concentrations to nematic LC host mixture N1.
The composition of the polymerizable mixture is shown in table 8 below.
TABLE 8 composition of polymerizable mixture
The absorption wavelength λ of compound 2 at extinction coefficient e=0.5 was measured as 361nm in a solution in DCM at a concentration of 3 g/L.
Thus, compound 2 of formula I, like compound 1, has a longer absorption wavelength than compound RM-1. Thus, compound 2 is more suitable for UV photopolymerization at longer wavelengths.
Since the polymerizable mixture contains a higher amount of the compound of formula I than compound RM-1, a UV LED lamp having a high emission wavelength can be used for the polymerization of the UV1 and UV2 steps.
For polymerization cartridges containing polymerizable mixtures P4-P9, exposure to UV light was performed in a two-step process, the first step (UV 1) was used to create a tilt angle, and the second step (UV 2) was used to polymerize any residual monomers that were not polymerized in the first step. In the UV1 step, a voltage (20 Vpp square wave, 200 Hz) is applied. In the UV2 step, no voltage is applied. Unless otherwise indicated, other conditions are as follows:
UV1 (LED lamp): 20mW/cm 2, at room temperature, 30-300 seconds
UV2 (LED lamp): 20mW/cm 2 at room temperature for 90 min
Tilt stability
The change in tilt angle Δtilt was determined as described in example 1 and is shown in table 9 below in comparison to mixture C1.
TABLE 9 tilt stability
| Mixture of | Δtilt/° |
| C1 | 0.49 |
| P5 | 0.34 |
| P6 | 0.34 |
| P7 | 0.33 |
| P8 | 0.39 |
| P9 | 0.35 |
As can be seen from Table 9, the polymerizable mixtures P5 to P9 according to the invention exhibit significantly better tilt stability than the reference mixture C1.
Voltage Holding Ratio (VHR)
The VHR of the polymerizable LC medium was measured at 60℃and a voltage of 1V/0.6Hz was applied initially and after UV exposure. Optical stress generally results in a decrease in VHR in the LC mixture, so the smaller the absolute decrease in VHR value after stress, the better the display application performance.
The results are shown in Table 10.
TABLE 10 VHR
As can be seen from table 10, the VHR of the polymerizable mixtures P4 to P9 according to the invention after UV stress was significantly higher than that of the reference mixture C1.
The above results show that LC media containing the polymerizable compounds of formula I are very suitable for PSA displays prepared by polymerization processes using long UV wavelengths > 350nm, in particular using UV-LED lamps.
Examples 10&11
The polymerizable mixtures P10 and P11 according to the invention are prepared by adding the polymerizable compounds 1,2 and RM-139 in various concentrations to the nematic LC host mixture N1.
The compound RM-139 has an absorption wavelength λ of 360nm in DCM solution at a concentration of 3g/L at an extinction coefficient of e=0.5, and is therefore suitable for UV photopolymerization at long wavelengths.
The composition of the polymerizable mixture is shown in table 11 below.
TABLE 11 composition of polymerizable mixture
Tilt stability
The change in tilt angle Δtilt was determined as described in example 1 and shown in table 12 below.
TABLE 12 tilt stability
| Mixture of | Δtilt/° |
| P10 | 0.39 |
| P11 | 0.36 |
As can be seen from table 12, the polymerizable mixtures P10 and P11 according to the invention show good tilt stability.
Voltage Holding Ratio (VHR)
The VHR of the polymerizable LC medium was measured at 60℃and a voltage of 1V/0.6Hz was applied initially and after UV exposure. Optical stress generally results in a decrease in VHR in the LC mixture, so the smaller the absolute decrease in VHR value after stress, the better the display application performance.
The results are shown in Table 13.
TABLE 13 VHR
As can be seen from table 13, the VHR of the polymerizable mixtures P10 and P11 according to the invention was high even after UV exposure.
The above results show that LC media containing two polymerisable compounds, at least one of which is of formula I, are very suitable for PSA displays prepared by polymerisation processes using long UV wavelengths > 350nm, in particular using UV-LED lamps.
Example 12
Nematic LC host mixture N3 was formulated as follows
The polymerizable mixture P12 was prepared by adding 0.45% of polymerizable compound 1, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N3.
Example 13
The polymerizable mixture P13 was prepared by adding 0.45% of polymerizable compound 2, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N3.
Example 14
Nematic LC host mixture N4 was formulated as follows
The polymerisable mixture P14 was prepared by adding 0.45% polymerisable compound 1 and 0.2% polymerisable compound RM-1 to the nematic LC host mixture N4.
Example 15
The polymerizable mixture P15 was prepared by adding 0.45% of polymerizable compound 2, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N4.
Example 16
Nematic LC host mixture N5 was formulated as follows
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The polymerizable mixture P16 was prepared by adding 0.4% of polymerizable compound 1, 0.3% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N5.
Example 17
The polymerizable mixture P17 was prepared by adding 0.45% of polymerizable compound 2, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N5.
Example 18
Nematic LC host mixture N6 was formulated as follows
The polymerizable mixture P18 was prepared by adding 0.45% of polymerizable compound 1, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N6.
Example 19
Nematic LC host mixture N7 was formulated as follows
The polymerizable mixture P19 was prepared by adding 0.4% of polymerizable compound 1, 0.1% of polymerizable compound RM-1 and 50ppm of stabilizer S2-1 to the nematic LC host mixture N7.
Example 20
Nematic LC host mixture N8 was formulated as follows
The polymerizable mixture P20 was prepared by adding 0.3% of polymerizable compound 1, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N8.
Example 21
Nematic LC host mixture N9 was formulated as follows
The polymerizable mixture P21 was prepared by adding 0.45% of polymerizable compound 1, 0.3% of polymerizable compound RM-1 and 0.6% of SA additive SA23 to nematic LC host mixture N9.
Example 22
Nematic LC host mixture N10 was formulated as follows
The polymerizable mixture P22 was prepared by adding 0.4% of polymerizable compound 2, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N10.
Example 23
Nematic LC host mixture N11 was formulated as follows
The polymerizable mixture P23 was prepared by adding 0.4% of polymerizable compound 1, 0.1% of polymerizable compound RM-1 and 50ppm of stabilizer S2-1 to the nematic LC host mixture N11.
Example 24
Nematic LC host mixture N12 was formulated as follows
The polymerizable mixture P24 was prepared by adding 0.4% of polymerizable compound 1, 0.15% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N12.
Example 25
Nematic LC host mixture N13 was formulated as follows
The polymerizable mixture P25 was prepared by adding 0.4% of polymerizable compound 2, 0.1% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N13.
Example 26
Nematic LC host mixture N14 was formulated as follows
The polymerizable mixture P26 was prepared by adding 0.4% of polymerizable compound 1, 0.1% of polymerizable compound RM-1 and 50ppm of stabilizer S2-1 to the nematic LC host mixture N14.
Example 27
Nematic LC host mixture N15 was formulated as follows
The polymerizable mixture P27 was prepared by adding 0.3% of polymerizable compound 2, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S3-1 to the nematic LC host mixture N15.
Example 28
Nematic LC host mixture N16 was formulated as follows
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The polymerizable mixture P28 was prepared by adding 0.45% of polymerizable compound 1, 0.1% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N16.
Example 29
Nematic LC host mixture N17 was formulated as follows
The polymerisable mixture P29 was prepared by adding 0.45% polymerisable compound 1, 0.4% polymerisable compound 2 and 50ppm stabiliser S3-2 to the nematic LC host mixture N17.
Example 30
Nematic LC host mixture N18 was formulated as follows
The polymerizable mixture P30 was prepared by adding 0.3% of polymerizable compound 1, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N18.
Example 31
Nematic LC host mixture N19 was formulated as follows
The polymerizable mixture P31 was prepared by adding 0.45% of polymerizable compound 2, 0.1% of polymerizable compound RM-1 and 100ppm of stabilizer S1-1 to the nematic LC host mixture N19.
Example 32
Nematic LC host mixture N20 was formulated as follows
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The polymerizable mixture P32 was prepared by adding 0.45% of polymerizable compound 1, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N20.
Example 33
Nematic LC host mixture N21 was formulated as follows
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PY-3-O2 10.50％
The polymerizable mixture P33 was prepared by adding 0.4% of polymerizable compound 1, 0.1% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N21.
Example 34
Nematic LC host mixture N22 was formulated as follows
The polymerizable mixture P34 was prepared by adding 0.8% of polymerizable compound 1, 0.2% of polymerizable mixture RM-1 and 0.6% of SA additive SA32 to nematic LC host mixture N22.
Example 35
Nematic LC host mixture N23 was formulated as follows
The polymerizable mixture P35 was prepared by adding 0.45% of polymerizable compound 2, 0.1% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N23.
Example 36
Nematic LC host mixture N24 was formulated as follows
The polymerizable mixture P36 was prepared by adding 0.45% of polymerizable compound 1, 0.1% of polymerizable compound RM-1 and 100ppm of stabilizer S2-1 to the nematic LC host mixture N24.
Example 37
Nematic LC host mixture N25 was formulated as follows
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The polymerizable mixture P37 was prepared by adding 0.3% of polymerizable compound 2, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N25.
Example 38
Nematic LC host mixture N26 was formulated as follows
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The polymerizable mixture P38 was prepared by adding 0.3% of polymerizable compound 2, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S3-1 to the nematic LC host mixture N26.
Example 39
Nematic LC host mixture N27 was formulated as follows
The polymerizable mixture P39 was prepared by adding 0.3% of polymerizable compound 1, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S3-3 to the nematic LC host mixture N27.
Example 40
Nematic LC host mixture N28 was formulated as follows
The polymerizable mixture P40 was prepared by adding 0.3% of polymerizable compound 1, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S2-1 to the nematic LC host mixture N28.
Example 41
Nematic LC host mixture N29 was formulated as follows
The polymerizable mixture P41 was prepared by adding 0.4% of polymerizable compound 2, 0.1% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N29.
Example 42
Nematic LC host mixture N30 was formulated as follows
The polymerizable mixture P42 was prepared by adding 0.3% of polymerizable compound 1, 0.2% of polymerizable compound RM-1 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N30.
Example 43
Nematic LC host mixture N31 was formulated as follows
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The polymerizable mixture P43 was prepared by adding 0.7% of polymerizable compound 2, 0.3% of polymerizable mixture RM-1 and 0.6% of SA additive SA23 to nematic LC host mixture N31.
Example 44
Nematic LC host mixture N32 was formulated as follows
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The polymerizable mixture P44 was prepared by adding 0.9% of polymerizable compound 1, 0.1% of polymerizable compound RM-1, 0.6% of SA additive SA23 and 50ppm of stabilizer S3-3 to the nematic LC host mixture N32.
Example 45
Nematic LC host mixture N33 was formulated as follows
The polymerizable mixture P45 was prepared by adding 1.0% of polymerizable compound 1, 0.1% of polymerizable compound RM-1, 0.6% of SA additive SA32 and 50ppm of stabilizer S3-1 to the nematic LC host mixture N33.
Example 46
Nematic LC host mixture N34 was formulated as follows
The polymerizable mixture P46 was prepared by adding 1.0% of polymerizable compound 2, 0.1% of polymerizable compound RM-1, 0.6% of SA additive SA32 and 50ppm of stabilizer S3-2 to the nematic LC host mixture N34.
Example 47
Nematic LC host mixture N35 was formulated as follows
The polymerizable mixture P47 was prepared by adding 0.8% of polymerizable compound 2, 0.2% of polymerizable compound RM-1, 0.6% of SA additive SA23 and 50ppm of stabilizer S3-3 to the nematic LC host mixture N35.
Example 48
Nematic LC host mixture N36 was formulated as follows
The polymerizable mixture P48 was prepared by adding 0.8% of polymerizable compound 1, 0.2% of polymerizable compound RM-1, 0.6% of SA additive SA23 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N36.
Example 49
Nematic LC host mixture N37 was formulated as follows
The polymerizable mixture P49 was prepared by adding 0.7% of polymerizable compound 2, 0.3% of polymerizable compound RM-1, 0.6% of SA additive SA23 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N37.
Example 50
Nematic LC host mixture N38 was formulated as follows
The polymerizable mixture P50 was prepared by adding 0.8% of polymerizable compound 1, 0.2% of polymerizable compound RM-1, 0.6% of SA additive SA32 and 50ppm of stabilizer S3-3 to the nematic LC host mixture N38.
Example 51
Nematic LC host mixture N39 was formulated as follows
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The polymerizable mixture P51 was prepared by adding 0.9% of polymerizable compound 1, 0.2% of polymerizable compound RM-1, 0.6% of SA additive SA23 and 50ppm of stabilizer S3-2 to the nematic LC host mixture N39.
Example 52
Nematic LC host mixture N40 was formulated as follows
The polymerizable mixture P52 was prepared by adding 1.0% of polymerizable compound 1, 0.1% of polymerizable compound RM-1, 0.6% of SA additive SA32 and 50ppm of stabilizer S3-3 to the nematic LC host mixture N40.
Example 53
Nematic LC host mixture N41 was formulated as follows
The polymerizable mixture P53 was prepared by adding 0.9% of polymerizable compound 1, 0.2% of polymerizable compound RM-1, 0.6% of SA additive SA32 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N41.
Example 54
Nematic LC host mixture N42 was formulated as follows
The polymerizable mixture P54 was prepared by adding 1.0% of polymerizable compound 2, 0.1% of polymerizable compound RM-1, 0.6% of SA additive SA32 and 50ppm of stabilizer S2-1 to the nematic LC host mixture N42.
Example 55
Nematic LC host mixture N43 was formulated as follows
The polymerizable mixture P55 was prepared by adding 0.7% of polymerizable compound 2, 0.3% of polymerizable compound RM-1, 0.6% of SA additive SA23 and 50ppm of stabilizer S3-2 to the nematic LC host mixture N43.
Example 56
Nematic LC host mixture N44 was formulated as follows
The polymerizable mixture P56 was prepared by adding 0.9% of polymerizable compound 1, 0.1% of polymerizable compound RM-1, 0.6% of SA additive SA23 and 50ppm of stabilizer S3-3 to the nematic LC host mixture N44.
Example 57
Nematic LC host mixture N45 was formulated as follows
The polymerizable mixture P57 was prepared by adding 0.8% of polymerizable compound 1, 0.1% of polymerizable compound RM-1, 0.6% of SA additive SA32 and 50ppm of stabilizer S3-1 to the nematic LC host mixture N45.
Example 58
Nematic LC host mixture N46 was formulated as follows
The polymerizable mixture P58 was prepared by adding 0.7% of polymerizable compound 2, 0.2% of polymerizable compound RM-1, 0.6% of SA additive SA32 and 50ppm of stabilizer S2-1 to the nematic LC host mixture N46.
Example 59
Nematic LC host mixture N47 was formulated as follows
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The polymerizable mixture P59 was prepared by adding 1.0% of polymerizable compound 1, 0.1% of polymerizable compound RM-1, 0.6% of SA additive SA32 and 50ppm of stabilizer S3-3 to nematic LC host mixture N47.
Example 60
Nematic LC host mixture N48 was formulated as follows
The polymerizable mixture P60 was prepared by adding 0.4% of polymerizable compound 1 and 0.1% of polymerizable compound RM-1 to the nematic LC host mixture N48.
Example 61
The polymerisable mixture P61 was prepared by adding 0.45% polymerisable compound 1 and 0.2% polymerisable compound RM-35 to the nematic LC host mixture N1.
Example 62
The polymerisable mixture P62 was prepared by adding 0.45% polymerisable compound 2 and 0.2% polymerisable compound RM-37 to the nematic LC host mixture N2.
Example 63
The polymerisable mixture P63 was prepared by adding 0.45% polymerisable compound 1 and 0.2% polymerisable compound RM-17 to the nematic LC host mixture N1.
Example 64
The polymerisable mixture P64 was prepared by adding 0.45% polymerisable compound 2 and 0.2% polymerisable compound RM-19 to the nematic LC host mixture N2.
Example 65
The polymerisable mixture P65 was prepared by adding 0.45% polymerisable compound 1 and 0.2% polymerisable compound RM-120 to the nematic LC host mixture N1.
Example 66
The polymerizable mixture P66 was prepared by adding 0.45% of polymerizable compound 2, 0.3% of polymerizable compound RM-139 and 50ppm of stabilizer S1-1 to the nematic LC host mixture N1.
Example 67
The polymerisable mixture P67 was prepared by adding 0.45% polymerisable compound 1 and 0.2% polymerisable compound RM-142 to the nematic LC host mixture N2.
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Claims (21)
- An lc medium comprising two or more polymerizable compounds, wherein at least one polymerizable compound is selected from formula I:wherein each group, independently of the other and identically or differently for each occurrence, has the following meanings:R a,Rb is P-Sp-or R, wherein at least one of R a and R b represents P-Sp-,A a,Ab is phenylene-1, 4-diyl or naphthalene-2, 6-diyl, which is optionally substituted by one or more radicals L,Z a,Zb is-CH=CH-, -CF=CF-, C.ident.C-or a single bond,P is a polymerizable group and is preferably a polymerizable group,Sp is a spacer group optionally substituted by one or more groups P, or a single bond,R is a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, wherein one or more non-adjacent CH 2 groups are optionally substituted by-O-, in such a way that the O-and/or S-atoms are not directly linked to each other-S-, -CO-O-, -O-CO-O-, CR 0＝CR00 -, -C≡C-, and,Substituted, and wherein one or more H atoms are each optionally replaced by F or Cl,L is F, cl, br, -CN or a linear, branched or cyclic alkyl having 1 to 25C atoms, wherein one or more non-adjacent CH 2 groups are optionally substituted by-O-, in such a way that the O-and/or S-atoms are not directly linked to each other-S-, -CO-O-, -O-CO-O-, -N (R 0)-、-Si(R0R00) -, -CH=CH-, or-C≡C-substitution, and wherein one or more H atoms are each optionally replaced by F or Cl,R 0,R00 is H or alkyl having 1 to 12 carbon atoms, preferably H,A, b is 0, 1 or 2, preferably 0 or 1,R4 is 0,1, 2, 3 or 4, preferably 0,1 or 2.
- 2. The LC medium of claim 1, wherein the compound of formula I is selected from formula I1:Wherein P, sp, L and r4 independently of each other have one of the meanings given in claim 1.
- 3. LC medium according to claim 1, wherein the compound of formula I is selected from the following subformulae:
- 4. LC medium according to one or more of claims 1 to 3, characterized in that it comprises one or more compounds of formula I as defined in claims 1 to 3, and one or more polymerizable compounds different from formula I.
- 5. LC medium according to one or more of claims 1 to 4, characterized in that it comprises one or more polymerizable compounds selected from the following formulae:wherein each group, independently of the other and identically or differently for each occurrence, has the following meanings:P 1、P2、P3 is a polymerizable group, preferably selected from the group consisting of ethyleneoxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetanyl and epoxy,Sp 1,Sp2,Sp3 is a single bond or a spacer group, wherein, in addition, one or more of the groups P 1-Sp1-、P2-Sp2 -and P 3-Sp3 -may represent R aa, provided that at least one of P 1-Sp1-、P2-Sp2 -and P 3-Sp3 -is present other than R aa, preferably- (CH 2)p1-,-(CH2)p1-O-,-(CH2)p1 -CO-O-or- (CH 2)p1 -O-CO-O-, wherein P1 is an integer of 1 to 12,R aa is H, F, cl, CN or a linear or branched alkyl radical having 1 to 25C atoms, where in addition, one or more non-adjacent CH 2 groups can each be replaced by-C (R 0)＝C(R00)-、-C≡C-、-N(R0) -, -O-, -S-, -CO-O-, -O-CO-O-in such a way that O and/or S atoms are not directly linked to one another, and wherein, in addition, one or more H atoms may be replaced by F, cl, CN or P 1-Sp1 -, particularly preferred are straight-chain or branched, optionally mono-or polyfluoro, alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy groups having 1 to 12C atoms, where alkenyl and alkynyl have at least two C atoms and branched groups have at least three C atoms, and where R aa does not represent or contain the radicals P 1、P2 or P 3,R 0,R00 is H or alkyl having 1 to 12C atoms,R y and R z are H, F, CH 3 or CF 3,X 1,X2,X3 is-CO-O-, -O-CO-or a single bond,Z M1 is-O-, -CO-; -C (R yRz) -or-CF 2CF2 -,Z M2,ZM3 is-CO-O- -O-CO- -CH 2O-、-OCH2-、-CF2O-、-OCF2 -or- (CH 2)n -, wherein n is 2,3 or 4,L is F, cl, CN or a linear or branched, optionally mono-or polyfluoro, alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 12C atoms,L ', L' is H, F or Cl,K is 0 or 1, and the number of the groups is,R is 0,1, 2, 3 or 4,S is 0, 1, 2 or 3,T is 0,1 or 2,X is 0 or 1.
- 6. LC medium according to one or more of claims 1 to 5, characterized in that it comprises one or more polymerizable compounds selected from the group of formula CM:wherein each group, independently of the other and identically or differently for each occurrence, has the following meanings:P, sp is one of the meanings given in formula I or its subformulae, or one of their preferred meanings as given above and below,L is F, cl, CN or a linear or branched, optionally mono-or polyfluoro, alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group having 1 to 12C atoms,R1, r2 is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, very preferably 0 or 1.
- 7. LC medium according to one or more of claims 1 to 6, characterized in that it comprises one or more polymerizable compounds selected from the group consisting of the formulae MT:Wherein P, sp, L, r and r2 independently of one another have the meanings given in claim 6, k is 0 or 1 and r3 is 0, 1,2 or 3, preferably 0, 1 or 2, very preferably 0 or 1.
- 8. LC medium according to one or more of claims 1 to 7, characterized in that it comprises one or more compounds of formula II:wherein each group, independently of the other and identically or differently for each occurrence, has the following meanings:r 1 and R 2 are straight-chain, branched or cyclic alkyl having 1to 25C atoms, wherein one or more non-adjacent CH 2 groups are optionally interrupted by-O-, in such a way that the O-and/or S-atoms are not directly linked to each other-S-, -CO-O-, -O-CO-O-, CR 0＝CR00 -, -C≡C-, and, Substituted, and wherein one or more H atoms are each optionally replaced by F or Cl, preferably alkyl or alkoxy having 1 to 6C atoms,R 0,R00 is H or alkyl having 1 to 12C atoms,A 1 and a 2 are groups selected from the following formulae:wherein each group, independently of the other and identically or differently for each occurrence, has the following meanings:Z 1 and Z 2 are -CH2CH2-、-CH＝CH-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、-CO-O-、-O-CO-、-C2F4-、-CF＝CF-、-CH＝CH-CH2O- or a single bond, preferably a single bond,L 1,L2,L3 and L 4 are F, cl, OCF 3、CF3、CH3、CH2 F or CHF 2, preferably F or Cl, very preferably F,Y is H, F, cl, CF 3、CHF2 or CH 3, preferably H or CH 3, very preferably H,L C is CH 3 or OCH 3, preferably CH 3,A1 is 1 or 2 and is preferably selected from the group consisting of,A2 is 0 or 1.
- 9. LC medium according to one or more of claims 1 to 8, characterized in that it contains one or more compounds of formula II selected from the compounds of formulae IIA, IIB, IIC and IID:Wherein the method comprises the steps ofR 2A and R 2B each independently of one another represent H, alkyl or alkenyl having up to 15C atoms, which is unsubstituted, monosubstituted by CN or CF 3 or at least monosubstituted by halogen, where, in addition, one or more CH 2 groups of these radicals may be such that the O atoms are not directly connected to one another by-O-, -S- -C.ident.C-, -CF 2O-、-OCF2 -, -OC-O-or-O-CO-substitution,L 1-L4 each independently of the other represents F, cl, CF 3 or CHF 2,Y represents H, F, cl, CF 3、CHF2 or CH 3, preferably H or CH 3, particularly preferably H,Z 2,Z2B and Z 2D each independently of the other represent a single bond 、-CH2CH2-、-CH＝CH-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、-COO-、-OCO-、-C2F4-、-CF＝CF-、-CH＝CHCH2O-,P represents 0, 1 or 2, andQ represents, identically or differently, for each occurrence, 0 or 1.
- 10. LC medium according to one or more of claims 1 to 9, characterized in that it comprises one or more compounds of formula III:Wherein the method comprises the steps ofR 11 and R 12 each independently of one another represent H, alkyl having 1 to 15C atoms or alkoxy, where one or more CH 2 groups of these groups can each independently of one another be linked in such a way that O atoms are not directly linked to one another -C≡C-, -CF 2O-、-OCF2 -, -CH=CH-, replaced by-O-, -CO-O-or-O-CO-, and wherein, in addition, one or more H atoms may be replaced by halogen,A 3 each occurrence independently of one anotherA) 1, 4-cyclohexenylene or 1, 4-cyclohexylene, in which one or two non-adjacent CH 2 groups may be replaced by-O-or-S-,B) 1, 4-phenylene in which one or two CH groups may be replaced by N, orC) A group selected from the group consisting of spiro [3.3] heptane-2, 6-diyl, 1, 4-bicyclo [2.2.2] octylene, naphthalene-2, 6-diyl, decalin-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, phenanthrene-2, 7-diyl and fluorene-2, 7-diyl,Wherein the radicals a), b) and c) may be mono-or polysubstituted by halogen atoms,N represents 0, 1 or 2, preferably 0 or 1,Z 1, independently of one another, represents -CO-O-、-O-CO-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、-CH2-、-CH2CH2-、-(CH2)4-、-CH＝CH-CH2O-、-C2F4-、-CH2CF2-、-CF2CH2-、-CF＝CF-、-CH＝CF-、-CF＝CH-、-CH＝CH-、-C≡C- or a single bond, andL 11 and L 12 each independently of one another represent F, cl, CF 3 or CHF 2, preferably H or F, most preferably F, andW represents O or S.
- 11. LC medium according to one or more of claims 1 to 10, characterized in that it comprises one or more compounds of formula IV:Wherein the method comprises the steps ofR 41 represents unsubstituted alkyl having 1 to 7C atoms or unsubstituted alkenyl having 2 to 7C atoms, preferably n-alkyl, particularly preferably having 2, 3, 4 or 5C atoms, andR 42 represents an unsubstituted alkyl group having 1 to 7C atoms or an unsubstituted alkoxy group having 1 to 6C atoms (each preferably having 2 to 5C atoms), an unsubstituted alkenyl group having 2 to 7C atoms, preferably having 2, 3 or 4C atoms, more preferably vinyl or 1-propenyl, especially vinyl.
- 12. LC medium according to one or more of claims 1 to 11, characterized in that it comprises one or more compounds of formula V:Wherein the method comprises the steps ofR 51 and R 52 independently of one another have one of the meanings given for R 41 and R 42 and preferably represent alkyl having 1 to 7C atoms, preferably n-alkyl, particularly preferably n-alkyl having 1 to 5C atoms, alkoxy having 1 to 7C atoms, preferably n-alkoxy, particularly preferably n-alkoxy having 2 to 5C atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 7C atoms, preferably 2 to 4C atoms, preferably alkenyloxy,The same or different expressionsWherein, Preferred representationZ 51,Z52 each independently of the other represents-CH 2-CH2-、-CH2 -O-; -CH=CH-, -C≡C-, -COO-, or a single bond, preferably-CH 2-CH2-、-CH2 -O-or a single bond and particularly preferably a single bond, andN is 1 or 2.
- 13. LC medium according to one or more of claims 1 to 12, characterized in that it additionally comprises one or more additives selected from the group consisting of stabilizers, chiral dopants, polymerization initiators and self-aligning additives.
- 14. A method of preparing an LC medium according to one or more of claims 1 to 13, comprising the steps of: mixing one or more polymerizable compounds as defined in one or more of claims 1 to 7 with one or more compounds of formulae II, III, IV and/or V as defined in one or more of claims 8 to 12 and optionally with further liquid-crystalline compounds and/or additives, and optionally polymerizing the polymerizable compounds.
- LC display comprising an LC medium as defined in one or more of claims 1 to 13.
- 16. The LC display of claim 15, which is a PS-VA, PS-IPS, PS-FFS, or SA-VA display.
- 17. LC display according to claim 15 or 16, characterized in that it comprises two substrates, at least one of which is transparent to light, one electrode being provided on each substrate or two electrodes being provided on only one of the substrates, and between the substrates is a layer of LC medium according to one or more of claims 1 to 13, wherein the polymerizable compound is polymerized between the substrates of the display by UV photopolymerization.
- 18. The method of producing an LC display as claimed in claim 17, comprising the steps of: LC medium according to one or more of claims 1 to 13 is provided between the substrates of the display and the polymerizable compound is polymerized by irradiation with UV light, preferably while applying a voltage to the display electrodes.
- 19. Method according to claim 18, characterized in that the wavelength of the UV light is >360nm.
- 20. The method according to claim 18 or 19, characterized in that UV light irradiation is performed using UV-LED lamps.
- 21. Energy saving method for producing LC displays, characterized by being as defined in any one of claims 18 to 20.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| EP21203658.6 | 2021-10-20 | ||
| EP21205963 | 2021-11-02 | ||
| EP21205963.8 | 2021-11-02 | ||
| PCT/EP2022/079014 WO2023066953A1 (en) | 2021-10-20 | 2022-10-19 | Liquid-crystal medium comprising polymerizable compounds |
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| CN118139946A true CN118139946A (en) | 2024-06-04 |
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