TW201940676A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same Download PDFInfo
- Publication number
- TW201940676A TW201940676A TW108102129A TW108102129A TW201940676A TW 201940676 A TW201940676 A TW 201940676A TW 108102129 A TW108102129 A TW 108102129A TW 108102129 A TW108102129 A TW 108102129A TW 201940676 A TW201940676 A TW 201940676A
- Authority
- TW
- Taiwan
- Prior art keywords
- liquid crystal
- group
- crystal alignment
- carbon atoms
- alignment agent
- Prior art date
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 159
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 60
- 229920001721 polyimide Polymers 0.000 claims abstract description 35
- 239000004642 Polyimide Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 54
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 125000000962 organic group Chemical group 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000000304 alkynyl group Chemical group 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 150000002466 imines Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920002098 polyfluorene Polymers 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims 1
- 239000010408 film Substances 0.000 description 71
- 239000000758 substrate Substances 0.000 description 50
- 238000000034 method Methods 0.000 description 31
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 210000002858 crystal cell Anatomy 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000000565 sealant Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 150000004985 diamines Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- -1 1,3-butadienyl Chemical group 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- 229910052581 Si3N4 Inorganic materials 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 229920005575 poly(amic acid) Polymers 0.000 description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000008033 biological extinction Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000007857 hydrazones Chemical class 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229960004592 isopropanol Drugs 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical group [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229940057867 methyl lactate Drugs 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- MTVLEKBQSDTQGO-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol Chemical compound CCOC(C)COC(C)CO MTVLEKBQSDTQGO-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 description 1
- CRORGGSWAKIXSA-UHFFFAOYSA-N 3-methylbutyl 2-hydroxypropanoate Chemical compound CC(C)CCOC(=O)C(C)O CRORGGSWAKIXSA-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HHDFKOSSEXYTJN-UHFFFAOYSA-N 4-[2-(4-aminophenoxy)ethoxy]aniline Chemical compound C1=CC(N)=CC=C1OCCOC1=CC=C(N)C=C1 HHDFKOSSEXYTJN-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- VWHKXXDIPOXHMQ-UHFFFAOYSA-N C[Sm]C Chemical compound C[Sm]C VWHKXXDIPOXHMQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- 108010088842 Fibrinolysin Proteins 0.000 description 1
- 244000126211 Hericium coralloides Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical compound [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 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
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 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
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([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
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229940001501 fibrinolysin Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 238000007866 imination reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
一種液晶配向劑，其含有下述(A)成分、(B)成分及有機溶劑。
(A)成分：選自由具有下述式(1)之構造單位之聚醯亞胺前驅物及該聚醯亞胺前驅物的醯亞胺化聚合物所成之群之至少一種聚合物，
(B)成分：具有2個以上下述式(2)之構造的化合物，
式中符號定義如說明書所記載。A liquid crystal alignment agent containing the following (A) component, (B) component, and an organic solvent.
(A) component: at least one polymer selected from the group consisting of a polyimide precursor having a structural unit of the following formula (1) and a polyimide polymer of the polyimide precursor,
(B) component: a compound having two or more structures of the following formula (2),
The definition of symbols in the formula is as described in the description.
Description
本發明有關液晶配向劑、自液晶配向劑所得之液晶配向膜及使用液晶配向膜之液晶顯示元件。The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from a liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film.
液晶電視、液晶顯示器等所用之液晶顯示元件通常係於元件內設置用以控制液晶排列狀態之液晶配向膜。Liquid crystal display elements used in liquid crystal televisions, liquid crystal displays, and the like are generally provided with a liquid crystal alignment film in the element for controlling the liquid crystal alignment state.
目前，工業上最普及之液晶配向膜係藉由以棉、尼龍、聚酯等布朝一定方向摩擦於電極基板上形成之由聚醯胺酸及/或使之醯亞胺化後之聚醯亞胺所成之膜之表面之所謂摩擦處理而製作。At present, the most popular liquid crystal alignment film in the industry is a polymer made of polyamic acid and / or imidized by rubbing cotton, nylon, polyester, and other cloths on the electrode substrate in a certain direction. The surface of the film formed by imine is made by so-called rubbing treatment.
摩擦處理係簡便且生產性優異之工業上有用之方法。然而，隨著液晶顯示元件之高性能化、高精細化、大型化，而有因摩擦處理產生之配向膜表面之刮傷、發塵、因機械力或靜電之影響，進而，有配向處理面內之不均一性等之各種問題。The rubbing treatment is an industrially useful method that is simple and excellent in productivity. However, as liquid crystal display elements have become more high-performance, higher-definition, and larger, there are scratches on the surface of the alignment film due to friction treatment, dust generation, and the influence of mechanical force or static electricity. Furthermore, there is an alignment treatment surface. Various problems such as internal heterogeneity.
作為替代摩擦處理之方法，已知有藉由照射經偏光之放射線，而賦予液晶配向能之光配向法。利用光配向法之液晶配向處理已提案有利用光異構化反應者，利用光交聯反應者，利用光分解反應者(參照非專利文獻1)。As a method for replacing the rubbing treatment, a light alignment method that imparts alignment energy to a liquid crystal by irradiating polarized radiation is known. Liquid crystal alignment processing using a photo-alignment method has been proposed to use a photo-isomerization reaction, a photo-cross-linking reaction, and a photo-decomposition reaction (see Non-Patent Document 1).
專利文獻1中，提案有將於主鏈具有環丁烷環等之脂環構造之聚醯亞胺膜用於光配向法。
如上述之光配向法，作為無摩擦配向處理方法，不僅可以工業上簡便地製造製程進行生產，於IPS驅動方式或邊緣場開關(Fringe-Field Switching)(以下稱為FFS)驅動方式之液晶顯示元件中，與藉摩擦處理法所得之液晶配向膜相比，由於可期待液晶顯示元件之對比度或視野角特性之提高，故作為渴望之液晶配向處理方法備受矚目。
[先前技術文獻]
[專利文獻]In Patent Document 1, a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain is proposed for a photo-alignment method.
As the above-mentioned light alignment method, as a frictionless alignment processing method, it can not only be produced in an industrially simple manufacturing process, but also used in IPS drive mode or Fringe-Field Switching (hereinafter referred to as FFS) liquid crystal display. Compared with the liquid crystal alignment film obtained by the rubbing treatment method, the improvement of the contrast or viewing angle characteristics of the liquid crystal display device is expected in the device, and therefore it has attracted attention as a desired liquid crystal alignment treatment method.
[Prior technical literature]
[Patent Literature]
[專利文獻1]：日本特開平9-297313號公報
[非專利文獻][Patent Document 1]: Japanese Patent Application Laid-Open No. 9-297313
[Non-patent literature]
非專利文獻1：「液晶光配向膜」 木戶脇，市村，機能材料，1997年11月號，Vol. 17 No.11 13-22頁
Non-Patent Document 1: "Liquid Crystal Alignment Film" Kito Waki, Ichimura, Functional Materials, November 1997, Vol. 17 No. 11 pages 13-22
[發明欲解決之課題][Questions to be Solved by the Invention]
作為智慧型手機或行動電話等之移動用途及車載用顯示器用途之液晶顯示元件之信賴性試驗，有實施面板之振動試驗。該振動試驗中，要求不發生亮點等之缺陷。為了獲得於振動試驗後不發生缺陷之液晶顯示元件，而有必要提高液晶配向膜之機械強度。作為改善液晶配向膜之機械強度尤其是硬度之方法，舉例有於液晶配向劑中添加交聯劑之方法。然而，本發明人等之檢討中，添加交聯劑時，雖改善了所得液晶配向膜之膜硬度，但有源自液晶顯示元件之黑亮度惡化的對比度惡化或因長期交流驅動所致之殘像惡化之虞。
因此，本發明之目的在於提供用以獲得膜硬度高、可抑制IPS驅動方式或FFS驅動方式之液晶顯示元件所發生之因長期交流驅動所致之殘像、且液晶顯示元件之對比度良好之液晶顯示元件的液晶配向劑、由該液晶配向劑所得之液晶配向膜、具有該液晶配向膜之液晶顯示元件。
[用以解決課題之手段]As a reliability test of liquid crystal display elements used in mobile applications such as smartphones and mobile phones, and automotive display applications, panel vibration tests are performed. In this vibration test, it is required that no defects such as bright spots occur. In order to obtain a liquid crystal display device in which no defect occurs after a vibration test, it is necessary to increase the mechanical strength of the liquid crystal alignment film. As a method for improving the mechanical strength, especially the hardness, of the liquid crystal alignment film, a method of adding a cross-linking agent to the liquid crystal alignment agent is exemplified. However, in the review by the present inventors, although the cross-linking agent was added, although the film hardness of the obtained liquid crystal alignment film was improved, the contrast caused by the black brightness deterioration of the liquid crystal display element was deteriorated or it was disabled due to long-term AC drive. Like deterioration.
Therefore, an object of the present invention is to provide a liquid crystal with high film hardness, which can suppress the afterimage caused by long-term AC driving of a liquid crystal display element with a high film hardness, and can suppress the IPS driving method or the FFS driving method, and the liquid crystal display element has a good contrast. A liquid crystal alignment agent for a display element, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.
[Means to solve the problem]
本發明人等為解決上述課題而進行積極檢討之結果，因而完成本發明。亦即，本發明之主旨係如以下所示。
1. 一種液晶配向劑，其含有下述(A)成分、(B)成分及有機溶劑：
(A)成分：選自由具有下述式(1)之構造單位之聚醯亞胺前驅物及該聚醯亞胺前驅物的醯亞胺化聚合物所成之群之至少一種聚合物，
(B)成分：具有2個以上下述式(2)之構造的化合物，As a result of an active review by the inventors to solve the above-mentioned problems, the present invention has been completed. That is, the gist of this invention is as follows.
1. A liquid crystal alignment agent comprising the following components (A), (B) and an organic solvent:
(A) component: at least one polymer selected from the group consisting of a polyimide precursor having a structural unit of the following formula (1) and a polyimide polymer of the polyimide precursor,
(B) component: a compound having two or more structures of the following formula (2),
X1 為4價有機基，Y1 為2價有機基，R1 為氫原子、或碳數1~5之烷基，A1 ~A2 分別獨立為氫原子或碳數1~10之烷基、碳數2~10之烯基或碳數2~10之炔基，X 1 is a tetravalent organic group, Y 1 is a divalent organic group, R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A 1 to A 2 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms Group, alkenyl group with 2 to 10 carbon atoms or alkynyl group with 2 to 10 carbon atoms,
Z1
為碳數1~6之烷基、碳數2~6之烯基或碳數2~6之炔基，Z2
為氫原子或碳數1~4之烷基、碳數2~6之烯基或碳數2~6之炔基，「＊」表示鍵結鍵。
[發明效果]Z 1 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms, Z 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and 2 to 6 carbon atoms "Alkenyl" or alkynyl having 2 to 6 carbon atoms, "*" indicates a bond.
[Inventive effect]
藉由使用本發明之液晶配向劑，可獲得膜硬度高的液晶配向膜。又，藉由使用本發明之液晶配向膜，儘管導入有交聯劑，亦可獲得對比度良好之液晶顯示元件。進而，藉由使用本發明之液晶配向劑，可不使液晶配向性或電特性降低而可達成上述課題。By using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having high film hardness can be obtained. In addition, by using the liquid crystal alignment film of the present invention, a liquid crystal display element with good contrast can be obtained despite the introduction of a crosslinking agent. Furthermore, by using the liquid crystal alignment agent of the present invention, the aforementioned problems can be achieved without lowering the liquid crystal alignment or electrical characteristics.
本發明之液晶配向劑之特徵係其含有下述(A)成分、(B)成分及有機溶劑。
(A)成分：選自由具有下述式(1)之構造單位之聚醯亞胺前驅物及該聚醯亞胺前驅物的醯亞胺化聚合物所成之群之至少一種聚合物，
(B)成分：具有2個以上下述式(2)之構造的化合物。
以下，針對各成分加以詳述。The liquid crystal alignment agent of the present invention is characterized in that it contains the following (A) component, (B) component, and an organic solvent.
(A) component: at least one polymer selected from the group consisting of a polyimide precursor having a structural unit of the following formula (1) and a polyimide polymer of the polyimide precursor,
(B) component: The compound which has a structure of two or more following formula (2).
Hereinafter, each component will be described in detail.
＜(A)成分＞
本發明之液晶配向劑所含之(A)成分係選自由具有下述式(1)之構造單位之聚醯亞胺前驅物及該聚醯亞胺前驅物的醯亞胺化聚合物所成之群之至少一種聚合物。作為聚醯亞胺前驅物若為聚醯胺酸、聚醯胺酸酯等之藉由加熱或利用觸媒之化學醯亞胺化，而形成醯亞胺環之聚醯亞胺前驅物，則未特別限制。基於容易進行加熱或化學醯亞胺化之觀點，作為聚醯亞胺前驅物，更好為聚醯胺酸或聚醯胺酸酯。＜ (A) component ＞
The component (A) contained in the liquid crystal alignment agent of the present invention is selected from the group consisting of a polyimide precursor having a structural unit of the following formula (1) and a polyimide polymer of the polyimide precursor. Group of at least one polymer. If the polyimide precursor is a polyimide precursor such as polyamic acid or polyimide, which is formed by heating or chemically imidizing with a catalyst, a polyimide ring is formed. Not particularly limited. From the viewpoint of easy heating or chemical imidization, the polyimide precursor is more preferably a polyamic acid or a polyamidate.
X1
為4價有機基，Y1
為2價有機基。R1
為氫原子、或碳數1~5之烷基，A1
~A2
分別獨立為氫原子或碳數1~10之烷基、碳數2~10之烯基或碳數2~10之炔基。
作為R1
中之上述烷基之具體例列舉為甲基、乙基、丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基等。基於易藉加熱而醯亞胺化之觀點，R1
較好為氫原子或甲基。
A1
及A2
分別獨立為氫原子或碳數1~10之烷基、可具有取代基之碳數2~10之烯基、可具有取代基之碳數2~10之炔基。
作為上述烷基之具體例，列舉為甲基、乙基、丙基、丁基、第三丁基、己基、辛基、癸基、環戊基、環己基、雙環己基等。作為烯基，列舉為將上述烷基中存在之1個以上之CH-CH構造置換成C=C構造者，更具體列舉為乙烯基、烯丙基、1-丙烯基、異丙烯基、2-丁烯基、1,3-丁二烯基、2-戊烯基、2-己烯基、環丙烯基、環戊烯基、環己烯基等。作為炔基列舉為將上述烷基中存在之1個以上之CH2
-CH2
構造置換成C≡C構造者，更體列舉為乙炔基、1-丙炔基、2-丙炔基等。
一般，若導入體積大的構造，則有降低胺基之反應性或液晶配向劑之可能性，故作為A1
及A2
，更好為氫原子或碳數1~5之烷基，特佳為氫原子、甲基或乙基。
以下，針對成為聚合物之原料的各成分加以詳述。X 1 is a tetravalent organic group, and Y 1 is a divalent organic group. R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and A 1 to A 2 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or 2 to 10 carbon atoms Of alkynyl.
Specific examples of the alkyl group in R 1 include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, and n-pentyl. From the viewpoint of being easily imidized by heating, R 1 is preferably a hydrogen atom or a methyl group.
A 1 and A 2 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, and an alkynyl group having 2 to 10 carbon atoms which may have a substituent.
Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, third butyl, hexyl, octyl, decyl, cyclopentyl, cyclohexyl, and dicyclohexyl. Examples of the alkenyl group include those in which one or more CH-CH structures existing in the alkyl group are replaced with a C = C structure, and more specifically, vinyl, allyl, 1-propenyl, isopropenyl, and 2 -Butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl, cyclopropenyl, cyclopentenyl, cyclohexenyl, and the like. Examples of the alkynyl group include those in which one or more CH 2 -CH 2 structures existing in the alkyl group are replaced with a C≡C structure, and more specifically, ethynyl, 1-propynyl, and 2-propynyl.
Generally, if a large volume structure is introduced, the reactivity of the amine group or the liquid crystal alignment agent may be reduced. Therefore, as A 1 and A 2 , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is more preferred. Is a hydrogen atom, methyl or ethyl.
Hereinafter, each component which becomes a raw material of a polymer is explained in full detail.
＜二胺＞
本發明之液晶配向劑所用之二胺成分其構造並未特別限制。
具有上述式(1)之構造的聚合物之聚合所用之二胺可藉以下之式(3)而通式化。若例示Y1
之構造，則如以下之(Y-1)~(Y-184)。＜ Diamine ＞
The structure of the diamine component used in the liquid crystal alignment agent of the present invention is not particularly limited.
The diamine used for polymerizing the polymer having the structure of the formula (1) can be generalized by the following formula (3). The structure of Y 1 is exemplified as (Y-1) to (Y-184) below.
上述式(3)之A1 及A2 ，亦包含較佳例在內，上述式(1)之A1 及A2 相同定義。A 1 and A 2 in the above formula (3) also include preferred examples, and A 1 and A 2 in the above formula (1) have the same definition.
又，基於液晶配向性之觀點，作為Y1 之構造，較好為直線性高的構造，舉例為下述式(4)及下述式(5)表示之構造。From the viewpoint of liquid crystal alignment, the structure of Y 1 is preferably a structure having a high linearity, and examples are structures represented by the following formula (4) and the following formula (5).
式(4)及式(5)中，A1 為單鍵、酯鍵、醯胺鍵、硫酯鍵或碳數2~20之2價有機基，A3 為氫原子、鹵原子、羥基、胺基、硫醇基、硝基、磷酸基或碳數1~20之1價有機基，a為1~4之整數，a為2以上時，A1 之構造可相同亦可不同。b及c分別獨立為1~2之整數。In formulas (4) and (5), A 1 is a single bond, an ester bond, a amine bond, a thioester bond, or a divalent organic group having 2 to 20 carbon atoms, and A 3 is a hydrogen atom, a halogen atom, a hydroxyl group, Amine group, thiol group, nitro group, phosphate group or monovalent organic group having 1 to 20 carbon atoms, a is an integer of 1 to 4, and when a is 2 or more, the structure of A 1 may be the same or different. b and c are each independently an integer of 1 ~ 2.
作為上述式(4)及式(5)表示之構造之具體例，較好為Y-7、Y-25、Y-26、Y-27、Y-43、Y-44、Y-45、Y-46、Y-48、Y-71、Y-72、Y-73、Y-74、Y-75、Y-76、Y-82、Y-87、Y-88、Y-89、Y-90、Y-92、Y-93、Y-94、Y-95、Y-96、Y-100、Y-101、Y-102、Y-103、Y-104、Y-105、Y-106、Y-110、Y-111、Y-112、Y-113、Y-115、Y-116、Y-121、Y-122、Y-126、Y-127、Y-128、Y-129、Y-132、Y-134、Y-153、Y-156、Y-157、Y-158、Y-159、Y-160、Y-161、Y-162、Y-163、Y-164、Y-165、Y-166、Y-167、Y-168、Y-169及Y-170。As specific examples of the structures represented by the above formulas (4) and (5), Y-7, Y-25, Y-26, Y-27, Y-43, Y-44, Y-45, and Y are preferable. -46, Y-48, Y-71, Y-72, Y-73, Y-74, Y-75, Y-76, Y-82, Y-87, Y-88, Y-89, Y-90 , Y-92, Y-93, Y-94, Y-95, Y-96, Y-100, Y-101, Y-102, Y-103, Y-104, Y-105, Y-106, Y -110, Y-111, Y-112, Y-113, Y-115, Y-116, Y-121, Y-122, Y-126, Y-127, Y-128, Y-129, Y-132 , Y-134, Y-153, Y-156, Y-157, Y-158, Y-159, Y-160, Y-161, Y-162, Y-163, Y-164, Y-165, Y -166, Y-167, Y-168, Y-169, and Y-170.
上述式(4)及式(5)表示之二胺含量，相對於總二胺成分1莫耳，較好為50%以上，更好為70莫耳%以上。
基於提高聚合物溶解性之觀點，Y1
構造中，較好包含下述式(6)表示之構造。The content of the diamine represented by the above formulas (4) and (5) is preferably 50% or more, and more preferably 70% or more by mole relative to 1 mole of the total diamine component.
From the viewpoint of improving the solubility of the polymer, the Y 1 structure preferably includes a structure represented by the following formula (6).
上述式(6)中，D為可藉由加熱而取代為氫原子之取代基，若為習知構造，則其構造未限定。基於熱脫離性之觀點，較好為第三丁氧羰基。包含上述式(6)表示之構造之Y1
之具體例，舉例為Y-158、Y-159、Y-160、Y-161、Y-162、Y-163。
包含上述式(6)表示之構造之二胺含量，相對於總二胺成分1莫耳，較好為0~50莫耳%，更好為5~30莫耳%。In the above formula (6), D is a substituent that can be replaced with a hydrogen atom by heating, and the structure is not limited as long as it is a conventional structure. From the viewpoint of thermal release, a third butoxycarbonyl group is preferred. Specific examples of Y 1 including the structure represented by the above formula (6) include Y-158, Y-159, Y-160, Y-161, Y-162, and Y-163.
The content of the diamine containing the structure represented by the above formula (6) is preferably from 0 to 50 mol%, more preferably from 5 to 30 mol% relative to 1 mole of the total diamine component.
又，作為Y1 之構造，於(Y-1)~(Y-184)中，特佳係如以下。In addition, as the structure of Y 1 , among (Y-1) to (Y-184), particularly preferable ones are as follows.
＜四羧酸衍生物＞
作為用以製作本發明之液晶配向劑中含有之具有上述式(1)之構造單位之聚合物的四羧酸衍生物成分，不僅可使用四羧酸二酐，亦可使用其四羧酸衍生物的四羧酸、四羧酸二鹵化合物、四羧酸二烷基酯化合物或四羧酸二烷基酯二鹵化合物。<Tetracarboxylic acid derivative>
As a tetracarboxylic acid derivative component for producing a polymer having the structural unit of the above formula (1) contained in the liquid crystal alignment agent of the present invention, not only tetracarboxylic dianhydride but also tetracarboxylic acid derivative thereof may be used. Tetracarboxylic acid, tetracarboxylic dihalide compound, tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid dialkyl ester dihalogen compound.
作為四羧酸二酐或其衍生物，較好為具有光反應性之四羧酸二酐或其衍生物，其中，更好使用選自下述式(7)表示之四羧酸二酐之至少一者。The tetracarboxylic dianhydride or a derivative thereof is preferably a tetracarboxylic dianhydride or a derivative thereof having a photoreactivity, and among them, a tetracarboxylic dianhydride selected from the following formula (7) is more preferably used. At least one.
X1 為具有脂環式構造之4價有機基，作為具體例，舉例為下述式(X1-1)~(X1-10)。X 1 is a tetravalent organic group having an alicyclic structure, and specific examples include the following formulae (X1-1) to (X1-10).
R3 至R23 分別獨立為氫原子、鹵原子、碳數1~6之烷基、碳數2~6之烯基、碳數2~6之炔基、含有氟原子之碳數1~6之1價有機基、或苯基，可為相同亦可不同。基於液晶配向性之觀點，R3 至R23 較好為氫原子、鹵原子、甲基或乙基，更好為氫原子或甲基。作為式(X1-1)之具體構造，舉例為以下述式(X1-11)~(X1-16)表示之構造。基於液晶配向性及光反應之感度的觀點，特佳為(X1-12)。R 3 to R 23 are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and a carbon number 1 to 6 containing fluorine atom The monovalent organic group or phenyl group may be the same or different. From the viewpoint of liquid crystal alignment, R 3 to R 23 are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group. As a specific structure of the formula (X1-1), a structure represented by the following formulae (X1-11) to (X1-16) is exemplified. From the viewpoint of liquid crystal alignment and sensitivity of photoreaction, particularly preferred is (X1-12).
本發明所用之四羧酸二酐，除上述式(7)以外，亦可使用下述式(8)表示之四羧酸二酐及其衍生物。As the tetracarboxylic dianhydride used in the present invention, in addition to the above formula (7), a tetracarboxylic dianhydride represented by the following formula (8) and a derivative thereof can also be used.
X2 為4價有機基，其構造未特別限制。若舉具體例，則舉例為下述式(X-9)~(X-42)之構造。基於化合物之取得性之觀點，X之構造舉例為X-17、X-25、X-26、X-27、X-28、X-32、X-35、X-37及X-39。又，基於獲得快速緩和因直流電壓而累積之殘留電荷之液晶配向膜之觀點，較好使用具有芳香族環構造之四羧酸二酐，作為X之構造，更好為X-26、X-27、X-28、X-32、X-35及X-37。X 2 is a tetravalent organic group, and its structure is not particularly limited. To give a specific example, the structure of the following formulae (X-9) to (X-42) is exemplified. From the viewpoint of the availability of compounds, examples of the structure of X are X-17, X-25, X-26, X-27, X-28, X-32, X-35, X-37, and X-39. In addition, from the viewpoint of obtaining a liquid crystal alignment film that rapidly relieves residual charges accumulated by a DC voltage, it is preferable to use a tetracarboxylic dianhydride having an aromatic ring structure as the structure of X, and more preferably X-26, X- 27, X-28, X-32, X-35 and X-37.
作為本發明中記載之聚醯亞胺前驅物及聚醯亞胺原料的四羧酸二酐及其衍生物，相對於全部四羧酸二酐及其衍生物1莫耳，以上述式(3)表示之四羧酸二酐及其衍生物較好含60~100莫耳%。為了獲得具有良好液晶配向性之液晶配向膜，更好為80莫耳%~100莫耳%，又更好為90莫耳%~100莫耳%。
＜(B)成分＞
本發明之液晶配向劑中含有之(B)成分係具有2個以上下述式(2)之構造的化合物。
(B)成分若含有2個以上下述式(2)表示之構造，則其構造未特別限制。分子量若過高，則由於對液晶配向性造成影響，故較好分子量2,000以下，更好1,000以下。The tetracarboxylic dianhydride and its derivative as the polyimide precursor and the polyimide raw material described in the present invention are represented by the above formula (3) with respect to 1 mole of all the tetracarboxylic dianhydride and its derivative. The tetracarboxylic dianhydride and its derivative represented by) preferably contain 60 to 100 mole%. In order to obtain a liquid crystal alignment film with good liquid crystal alignment, it is more preferably 80 mol% to 100 mol%, and still more preferably 90 mol% to 100 mol%.
＜ (B) component ＞
The component (B) contained in the liquid crystal alignment agent of the present invention is a compound having a structure of two or more formulas (2) below.
The component (B) is not particularly limited as long as it contains two or more structures represented by the following formula (2). If the molecular weight is too high, it affects the alignment of the liquid crystal. Therefore, the molecular weight is preferably 2,000 or less, and more preferably 1,000 or less.
Z1
係碳數1~6之烷基、碳數2~6之烯基或碳數2~6之炔基。基於液晶配性向之觀點，Z1
較好為甲基、乙基，更好為甲基。
Z2
係氫原子或碳數1~4之烷基、碳數2~6之烯基或碳數2~6之炔基。基於交聯反應性之觀點，更好為氫原子。「＊」表示鍵結鍵。
作為(B)成分，較好為具有2個以上之上述式(2)表示之構造的化合物，更好具有3個以上之上述式(2)表示之構造的化合物。
又，作為(B)成分，較好為具有2個以上之下述式(B1-1)表示之構造的化合物。Z 1 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms. From the viewpoint of liquid crystal alignment, Z 1 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
Z 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms. From the viewpoint of crosslinking reactivity, a hydrogen atom is more preferred. "*" Indicates a bond key.
The component (B) is preferably a compound having two or more structures represented by the formula (2), and more preferably a compound having three or more structures represented by the formula (2).
The component (B) is preferably a compound having a structure represented by the following formula (B1-1).
Z1 ，亦包含較佳具體例，係使式(2)同樣之定義。作為(B)成分之具體例舉例為下述式(B-1)~(B-18)之化合物。Z 1 also includes a preferred specific example, and is the same definition as in formula (2). Specific examples of the component (B) include compounds of the following formulae (B-1) to (B-18).
上述(B)成分若過多時，對液晶配向性或預傾角造成影響，過少時，無法獲得本發明效果。因此，(B)成分之添加量，相對於(A)成分之聚合物，較好為0.1~30質量%，更好為0.1~20質量%，又更好為1~15質量%。
＜聚醯胺酸酯、聚醯胺酸及聚醯亞胺之製造方法＞
本發明所用之聚醯亞胺前驅物之聚醯胺酸酯、聚醯胺酸及聚醯亞胺可藉如例如國際公開公報WO2013/157586中記載之習知方法合成。When the (B) component is too much, it affects the liquid crystal alignment or pretilt angle, and when it is too small, the effect of the present invention cannot be obtained. Therefore, the addition amount of the component (B) is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 1 to 15% by mass relative to the polymer of the component (A).
<Manufacturing method of polyamidate, polyamidate, and polyimide>
The polyamidate precursor, polyamidate, and polyimide of the polyamidate precursor used in the present invention can be synthesized by a conventional method described in, for example, International Publication WO2013 / 157586.
＜液晶配向劑＞
本發明所用之液晶配向劑具有將前述之(A)成分的選自由聚醯亞胺前驅物及該聚醯亞胺前驅物的醯亞胺化聚合物所成之群之至少一種聚合物(以下稱為特定構造之聚合物)及(B)成分的化合物溶解於有機溶劑中之溶液形態。特定構造聚合物之分子量，以重量平均分子量計較好為2,000~500,000，更好為5,000~ 300,000，又更好為10,000~100,000。又，數平均分子量較好為1,000~ 250,000，更好為2,500~150,000，又更好為5,000~50,000。＜ Liquid crystal alignment agent ＞
The liquid crystal alignment agent used in the present invention has at least one polymer selected from the group consisting of a polyimide precursor and a polyimide polymer of the polyimide precursor (the following (A) component (hereinafter A solution in which a compound of a specific structure) and (B) components are dissolved in an organic solvent. The molecular weight of the specific structural polymer is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000 in terms of weight average molecular weight. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
本發明所用之液晶配向劑之聚合物濃度，可藉由欲形成之塗膜厚度之設定而適當變更，但基於形成均一且無缺陷之塗膜之觀點，較好為1重量%以上，基於溶液之保存安定性之觀點，較好為10重量%以下。The polymer concentration of the liquid crystal alignment agent used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but from the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by weight or more based on the solution. From the viewpoint of storage stability, it is preferably 10% by weight or less.
本發明所用之液晶配向劑中含有之有機溶劑若為可均一溶解聚合物成分者，則未特別限制。若舉例其具體例，則可舉例為N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-甲基己內醯胺、2-吡咯啶酮、N-乙烯基-2-吡咯啶酮、二甲基亞碸、二甲基碸、γ-丁內酯、1,3-二甲基-咪唑啶酮、3-甲氧基-N,N-二甲基丙醯胺等。該等可使用1種或混合2種以上使用。又，即使為單獨無法均一溶解聚合物成分之聚合物，但於聚合物不析出之範圍內，則亦可混合於上述有機溶劑中。The organic solvent contained in the liquid crystal alignment agent used in the present invention is not particularly limited as long as it can uniformly dissolve the polymer component. For specific examples, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2- Pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfine, dimethyl Samarium, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. These can be used singly or in combination of two or more kinds. Moreover, even if it is a polymer which cannot dissolve a polymer component uniformly by itself, as long as a polymer does not precipitate, you may mix in the said organic solvent.
本發明所用之液晶配向劑中，除了用以溶解聚合物成分之有機溶劑以外，亦可含有用以提高對基板塗佈液晶配向劑時之塗膜均一性之溶劑。該溶劑一般係使用表面張力比上述有機溶劑低的溶劑。作為其具體例，舉例為乙基溶纖素、丁基溶纖素、乙基卡必醇、丁基卡必醇、乙基卡必醇乙酸酯、乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲醚-2-乙酸酯、丙二醇-1-單乙醚-2-乙酸酯、丁基溶纖素乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸正丁酯、乳酸異戊酯等。該等溶劑亦可併用2種以上。The liquid crystal alignment agent used in the present invention may contain, in addition to an organic solvent for dissolving a polymer component, a solvent for improving uniformity of a coating film when a liquid crystal alignment agent is applied to a substrate. The solvent is generally a solvent having a surface tension lower than that of the organic solvent. Specific examples thereof include ethylcellosolvin, butylcellosolvin, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, and 1-methoxy-2- Propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol- 1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, Methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents may be used in combination of two or more.
本發明所用之液晶配向劑中，除上述以外，若在不損及本發明效果之範圍內，亦可添加特定聚合物以外之聚合物、為改變液晶配向膜之介電率或導電性等之電特性之介電體或導電物質、為提高液晶配向膜與基板之密著性之矽烷偶合劑、為提高作成液晶配向膜時之膜之硬度或緻密度之交聯性化合物、進而為了於塗膜燒成時使聚醯胺酸之醯亞胺化有效地進行之醯亞胺化促進劑等。
＜液晶配向膜＞
＜液晶配向膜之製造方法＞
本發明之液晶配向膜係將上述液晶配向劑塗佈於基板上，並乾燥、燒成所得之膜。作為塗佈本發明之液晶配向劑之基板若為透明性高之基板，則未特別限制，可使用玻璃基板、氮化矽基板、丙烯酸基板、聚碳酸酯基板等塑膠基板等，使用形成有用於液晶驅動之ITO電極等之基板時，基於製程簡單化之方面係較佳。且，反射型之液晶顯示元件中，亦可僅於單側之基板使用矽晶圓等不透明物，該情況下之電極亦可使用鋁等使光反射之材料。In the liquid crystal alignment agent used in the present invention, in addition to the above, as long as the effect of the present invention is not impaired, a polymer other than a specific polymer may be added to change the dielectric constant or conductivity of the liquid crystal alignment film. Electrical properties of a dielectric or conductive substance, a silane coupling agent to improve the adhesion between the liquid crystal alignment film and the substrate, a crosslinkable compound to increase the hardness or density of the film when forming a liquid crystal alignment film, and furthermore, for coating A polyimidization accelerator that efficiently performs polyimidation of polyimide at the time of film firing, and the like.
＜ Liquid crystal alignment film ＞
＜ Manufacturing method of liquid crystal alignment film ＞
The liquid crystal alignment film of the present invention is a film obtained by coating the liquid crystal alignment agent on a substrate, and drying and firing the substrate. The substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a substrate with high transparency. Plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates, and polycarbonate substrates can be used. In the case of a substrate such as an ITO electrode driven by a liquid crystal, it is preferable in terms of simplification of the manufacturing process. Moreover, in a reflective liquid crystal display element, an opaque object such as a silicon wafer may be used only on one side of the substrate, and in this case, an electrode such as aluminum may be used to reflect light.
作為本發明之液晶配向劑之塗佈方法列舉為旋塗法、印刷法、噴墨法等。塗佈本發明之液晶配向劑後之乾燥、燒成步驟可選擇任意溫度及時間。通常為了充分去除所含有之有機溶劑而於50~120℃下乾燥1~10分鐘，隨後在150~300℃下燒成5~120分鐘。燒成後之塗膜厚度雖無特別限制，但太薄時會有液晶顯示元件之信賴性下降之情況，故較好為5~300nm，更好為10~200nm。Examples of the application method of the liquid crystal alignment agent of the present invention include a spin coating method, a printing method, and an inkjet method. The drying and firing steps after applying the liquid crystal alignment agent of the present invention can be selected at any temperature and time. Usually, in order to fully remove the organic solvent contained, it is dried at 50 to 120 ° C for 1 to 10 minutes, and then fired at 150 to 300 ° C for 5 to 120 minutes. Although the thickness of the coating film after firing is not particularly limited, if it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 200 nm.
作為使所得液晶配向膜進行配向處理之方法，舉例為摩擦法、光配向處理法等。
摩擦處理可利用既有摩擦裝置進行。此時之摩擦布的材質舉例為棉、尼龍、縲縈等。作為摩擦處理條件一般使用旋轉速度300~ 2,000rpm、送給速度5~100mm/s、擠壓量0.1~1.0mm之條件。隨後，使用純水或醇利用超音波洗淨去除摩擦所產生之殘渣。Examples of a method for subjecting the obtained liquid crystal alignment film to an alignment treatment include a rubbing method and a photo-alignment treatment method.
The friction treatment can be performed using an existing friction device. Examples of the material of the friction cloth at this time are cotton, nylon, and rayon. As the friction treatment conditions, conditions of a rotation speed of 300 to 2,000 rpm, a feed speed of 5 to 100 mm / s, and an extrusion amount of 0.1 to 1.0 mm are generally used. Subsequently, ultrasonic cleaning is performed using pure water or alcohol to remove residues caused by friction.
作為光配向處理法之具體例，舉例為於前述塗膜表面照射於一定方向偏光之放射線，根據情況進而進行於150~250℃之溫度的加熱處理，而賦予液晶配向能之方法。作為放射線，可使用具有100nm~ 800nm波長之紫外線及可見光。其中，較好為具有100~400nm波長之紫外線，特佳為具有200~400nm波長之紫外線。又，為了改善液晶配向性，亦可邊將塗膜基板於50~250℃加熱，邊照射放射線。前述放射線之照射量，較好為1~10,000mJ/cm2 ，特佳為100~5,000mJ/cm2 。如上述製作之液晶配向膜可使液晶分子於一定方向安定地配向。As a specific example of the photo-alignment treatment method, a method in which the surface of the coating film is irradiated with polarized light in a certain direction and further subjected to a heating treatment at a temperature of 150 to 250 ° C. according to the situation to give the liquid crystal alignment energy. As the radiation, ultraviolet rays and visible light having a wavelength of 100 nm to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferred, and ultraviolet rays having a wavelength of 200 to 400 nm are particularly preferred. In addition, in order to improve the alignment of the liquid crystal, the coating film substrate may be irradiated with radiation while being heated at 50 to 250 ° C. The radiation dose is preferably 1 to 10,000 mJ / cm 2 , and particularly preferably 100 to 5,000 mJ / cm 2 . The liquid crystal alignment film produced as described above can stably align liquid crystal molecules in a certain direction.
經偏光之紫外線之消光比越高，越可賦予更高向異性，故而較佳。具體而言，於直線偏光之紫外線之消光比較好為10：1以上，更好為20：1以上。The higher the extinction ratio of polarized ultraviolet light, the more anisotropy can be imparted, so it is better. Specifically, the extinction of ultraviolet rays in linear polarized light is preferably 10: 1 or more, and more preferably 20: 1 or more.
如上述，經照射經偏光放射線之膜接著亦可以包含選自水及有機溶劑之至少一種溶劑進行接觸處理。As described above, the film irradiated with polarized radiation may then include at least one solvent selected from water and an organic solvent for contact treatment.
作為接觸處理所使用之溶劑，若為可溶解因光照射所生成之分解物，則未特別限制。作為具體例，舉例為水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮、1-甲氧基-2-丙醇、1-甲氧基-2-丙醇乙酸酯、丁基溶纖素、乳酸乙酯、乳酸甲酯、二丙酮醇、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸丙酯、乙酸丁酯及乙酸環己酯等。該等溶劑亦可併用2種以上。
基於廣泛利用性及安全性之觀點，更好為自水、2-丙醇、1-甲氧基-2-丙醇及乳酸乙酯所成之群選出之至少一種。特佳為水、2-丙醇、及水與2-丙醇之混合溶劑。The solvent used for the contact treatment is not particularly limited as long as it can dissolve the decomposed matter generated by light irradiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, Butylfibrinolysin, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. These solvents may be used in combination of two or more.
From the viewpoint of wide availability and safety, at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol, and ethyl lactate is more preferable. Particularly preferred are water, 2-propanol, and a mixed solvent of water and 2-propanol.
本發明中，經照射經偏光放射線之膜與包含有機溶劑之溶液之接觸處理，可藉浸漬處理、噴霧(spray)處理等之可使膜與液較好地充分接觸之處理。其中，較好為使膜於包含有機溶劑之溶液中較好浸漬處理10秒~1小時，更好1~30分鐘之方法。接觸處理可於常溫亦可於加溫下，但較好為10~80℃，更好於20~50℃實施。又，可根據需要實施超音波等之提高接觸之手段。In the present invention, the contact treatment of the film that is irradiated with polarized radiation and the solution containing an organic solvent can be a treatment that can sufficiently contact the film and the liquid by immersion treatment, spray treatment, and the like. Among them, a method of making the film in a solution containing an organic solvent is preferably immersed for 10 seconds to 1 hour, more preferably 1 to 30 minutes. The contact treatment may be performed at normal temperature or under heating, but it is preferably performed at 10 to 80 ° C, and more preferably at 20 to 50 ° C. Further, a means for increasing contact such as an ultrasonic wave can be implemented as necessary.
上述接觸處理後，基於去除使用之溶液中有機溶劑之目的，亦可進行利用水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮等之低沸點溶劑沖洗(清洗)或乾燥之任一者或兩者。
再者，進行利用上述之溶劑之接觸處理的膜，基於溶劑乾燥及膜中之分子鏈之再配向目的，亦可於150℃以上加熱。
作為加熱溫度，較好為150~300℃。溫度越高，越促進分子鏈之再配向，但溫度過高時，有伴隨分子鏈分解之虞。因此，作為加熱溫度，較好為180~250℃，更好為200~230℃。
加熱時間過短時，有無法獲得分子鏈再配向之效果之可能性，過長時，有分子鏈分解之可能性，故較好為10秒~30分鐘，更好為1分鐘~10分鐘。After the above contact treatment, for the purpose of removing the organic solvent in the used solution, it can also be washed (washed) or dried with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone and the like. Either or both.
Furthermore, the film subjected to the contact treatment with the above-mentioned solvent may be heated at 150 ° C. or higher for the purpose of solvent drying and realignment of molecular chains in the film.
The heating temperature is preferably 150 to 300 ° C. The higher the temperature, the more the realignment of the molecular chains is promoted. However, when the temperature is too high, the molecular chains may be decomposed. Therefore, the heating temperature is preferably 180 to 250 ° C, and more preferably 200 to 230 ° C.
When the heating time is too short, the effect of realignment of the molecular chain may not be obtained. When the heating time is too long, the molecular chain may be decomposed. Therefore, it is preferably 10 seconds to 30 minutes, more preferably 1 minute to 10 minutes.
＜液晶顯示元件＞
本發明之液晶顯示元件之特徵為具備藉由上述液晶配向膜之製造方法所得之液晶配向膜。
本發明之液晶顯示元件係自本發明之液晶配向劑利用前述液晶配向膜之製造方法獲得附液晶配向膜之基板後，藉習知方法製作液晶胞，使用其作成液晶顯示元件者。<Liquid crystal display element>
The liquid crystal display element of the present invention is characterized by including a liquid crystal alignment film obtained by the method for producing a liquid crystal alignment film.
The liquid crystal display element of the present invention is obtained from the liquid crystal alignment agent of the present invention by using the aforementioned liquid crystal alignment film manufacturing method to obtain a substrate with a liquid crystal alignment film, and a liquid crystal cell is prepared by a known method, and used to make a liquid crystal display element.
作為液晶胞製作方法之一例，舉例被動式矩陣(passive matrix)構造之液晶顯示元件加以說明。又，亦可為於構成圖像顯示之各像素部分設置TFT(Thin Film Transistor，薄膜電晶體)等之開關元件之主動矩陣構造之液晶顯示元件。As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. In addition, a liquid crystal display element having an active matrix structure in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting an image display.
首先，準備透明玻璃製之基板，於其一基板上設置共用電極，於另一基板上設置分段電極。該等電極可為例如ITO電極，且可以期望之圖像顯示之方式圖型化。接著，以被覆共用電極與分段電極之方式於各基板上設置絕緣膜。絕緣膜可為例如以溶凝膠法形成之由SiO2 -TiO2 所成之膜。First, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segmented electrode is provided on the other substrate. The electrodes may be, for example, ITO electrodes, and may be patterned in a manner that a desired image is displayed. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film may be, for example, a film made of SiO 2 -TiO 2 formed by a sol-gel method.
其次，於各基板上形成本發明之液晶配向膜。接著，以使配向膜面彼此對向之方式於其一基板上重疊另一基板，以密封劑接著周邊。密封劑中為了控制基板間隙，通常預先混入隔離材。且，於未設置密封劑之面內部分較好亦預先散佈基板間隙控制用之隔離材。於密封劑之一部分設置可自外部填充液晶之開口部。Next, a liquid crystal alignment film of the present invention is formed on each substrate. Next, another substrate is superposed on one of the substrates so that the alignment film surfaces face each other, and the periphery is sealed with a sealant. In order to control the substrate gap in the sealant, a spacer is usually mixed in advance. In addition, it is preferable to disperse a spacer for controlling the substrate gap in advance on the in-plane portion where the sealant is not provided. An opening portion capable of being filled with liquid crystal from outside is provided on a part of the sealant.
其次，通過設於密封劑之開口部，將液晶材料注入於以2片基板與密封劑包圍之空間內。隨後，以接著劑密封該開口部。注入可使用真空注入法，亦可使用在大氣中利用毛細管現象之方法。接著，進行偏光板之設置。具體而言，於2片基板之與液晶層相反側之面上貼合一對偏光板。經過以上步驟，而獲得本發明之液晶顯示元件。Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant through the opening provided in the sealant. Subsequently, the opening is sealed with an adhesive. The injection may be performed by a vacuum injection method or a method using a capillary phenomenon in the atmosphere. Next, the polarizing plate is set. Specifically, a pair of polarizing plates are bonded to the surface of the two substrates on the side opposite to the liquid crystal layer. Through the above steps, the liquid crystal display element of the present invention is obtained.
本發明中，作為密封劑舉例為例如具有環氧基、丙烯醯基、甲基丙烯醯基、羥基、烯丙基、乙醯基等之反應性基之藉由紫外線照射或加熱而硬化之樹脂。尤其，較好使用具有環氧基與(甲基)丙烯醯基兩者之反應性基之硬化樹脂系。In the present invention, as the sealant, for example, a resin having a reactive group such as an epoxy group, an acrylic fluorenyl group, a methacryl fluorenyl group, a hydroxyl group, an allyl group, an ethyl fluorenyl group, and the like is hardened by irradiation or heating with ultraviolet rays. . In particular, a hardening resin system having a reactive group having both an epoxy group and a (meth) acrylfluorenyl group is preferably used.
本發明之密封劑中，以提高接著性、耐濕性為目的，亦可調配無機填充劑。作為欲使用之無機填充劑，並未特別限定，但具體而言舉例為球狀氧化矽、熔融氧化矽、結晶氧化矽、氧化鈦、鈦黑、碳化矽、氮化矽、氮化硼、碳酸鈣、碳酸鎂、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氧化鎂、氧化鋯、氫氧化鋁、矽酸鈣、矽酸鋁、矽酸鋰鋁、矽酸鋯、鈦酸鋇、玻璃纖維、碳纖維、二硫化鉬、石綿等，較佳為球狀氧化矽、熔融氧化矽、結晶氧化矽、氧化鈦、鈦黑、氮化矽、氮化硼、碳酸鈣、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氫氧化鋁、矽酸鈣、矽酸鋁。前述之無機填充劑亦可混合2種以上使用。
[實施例]In the sealing agent of the present invention, an inorganic filler may be blended for the purpose of improving adhesion and moisture resistance. The inorganic filler to be used is not particularly limited, but specific examples include spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, silicon nitride, boron nitride, and carbonic acid. Calcium, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconia, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate , Glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon nitride, boron nitride, calcium carbonate, barium sulfate, sulfuric acid Calcium, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate. The foregoing inorganic fillers may be used in combination of two or more.
[Example]
以下列舉實施例更具體說明本發明，但本發明並不受限於此。以下之化合物的簡寫及各特性之測定方法如下。
NMP：N-甲基-2-吡咯啶酮
GBL：γ-丁內酯
BCS：丁基溶纖素
DA-1：1,2-雙(4-胺基苯氧基)乙烷
DA-2：N-第三丁氧羰基-N-(2-(4-胺基苯基)乙基)-N-(4-胺基苄基)胺
DA-3：對-苯二胺
DA-4：參考下述式(DA-4)
DA-5：4,4’-二胺基二苯基胺
DA-6：4,4’-二胺基二苯基甲烷
CA-1：參考下述式(CA-1)
CA-2：參考下述式(CA-2)
CA-3：參考下述式(CA-3)
AD-1：參考下述式(AD-1)
AD-2：參考下述式(AD-2)The following examples illustrate the invention more specifically, but the invention is not limited thereto. The following compounds are abbreviated and the methods for measuring each characteristic are as follows.
NMP: N-methyl-2-pyrrolidone
GBL: γ-butyrolactone
BCS: Butyl Fibrinolysin
DA-1: 1,2-bis (4-aminophenoxy) ethane
DA-2: N-third butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4-aminobenzyl) amine
DA-3: p-phenylenediamine
DA-4: Refer to the following formula (DA-4)
DA-5: 4,4'-diaminodiphenylamine
DA-6: 4,4'-diaminodiphenylmethane
CA-1: Refer to the following formula (CA-1)
CA-2: Refer to the following formula (CA-2)
CA-3: Refer to the following formula (CA-3)
AD-1: Refer to the following formula (AD-1)
AD-2: Refer to the following formula (AD-2)
[黏度]
溶液之黏度係使用E型黏度計TVE-22H(東機產業公司製)，樣品量1.1mL，錐形轉子TE-1(1°34’，R24)，在溫度25℃測定。[Viscosity]
The viscosity of the solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a tapered rotor TE-1 (1 ° 34 ', R24) at a temperature of 25 ° C.
[分子量]
分子量係藉由GPC(常溫凝膠滲透層析)裝置測定，以聚乙二醇、聚環氧乙烷換算值算出數平均分子量(Mn)與重量平均分子量(Mw)。[Molecular weight]
The molecular weight is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) are calculated in terms of polyethylene glycol and polyethylene oxide.
GPC裝置：Shodex公司製(GPC-101)，管柱：Shodex公司製(KD803、KD805串聯)，管柱溫度：50℃，溶離液：N,N-二甲基甲醯胺(作為添加劑為溴化鋰一水合物(LiBr・H2 O)為30mmol/L，磷酸・無水結晶(o-磷酸)為30mmol/L，四氫呋喃(THF)為10mL/L)，流速：1.0mL/min。GPC device: Shodex (GPC-101), column: Shodex (KD803, KD805 in series), column temperature: 50 ° C, eluent: N, N-dimethylformamide (as the additive is lithium bromide The monohydrate (LiBr · H 2 O) was 30 mmol / L, the phosphoric acid · anhydrous crystal (o-phosphoric acid) was 30 mmol / L, the tetrahydrofuran (THF) was 10 mL / L), and the flow rate was 1.0 mL / min.
製作校正線用標準樣品：TOSOH公司製TSK標準聚環氧乙烷(重量平均分子量(Mw)約900,000、150,000、100,000、30,000)及Polymer Laboratory公司製聚乙二醇(峰頂分子量(Mp)約12,000、4,000、1,000)。為了避免波峰重疊，測定係分別測定將900,000、100,000、12,000、1,000之4種混合成之樣品、及150,000、30,000、4,000之3種混合成之樣品的2種樣品。Preparation of standard samples for calibration lines: TSK standard polyethylene oxide (weight average molecular weight (Mw) approximately 900,000, 150,000, 100,000, 30,000) manufactured by TOSOH company and polyethylene glycol (peak molecular weight (Mp) approximately) manufactured by Polymer Laboratory 12,000, 4,000, 1,000). In order to avoid overlapping of the peaks, the measurement was performed by measuring two samples of a mixture of four types of 900,000, 100,000, 12,000, and 1,000, and three samples of 150,000, 30,000, and 4,000.
＜醯亞胺化率之測定＞
將聚醯亞胺粉末20mg放入NMR樣品管(NMR標準取樣管，ϕ5(草野科學公司製))，添加氘化二甲基亞碸(DMSO-d6，0.05%TMS(四甲基矽烷)混合物)(0.53mL)，施加超音波使完全溶解。該溶液以NMR測定機(JNW-ECA500)(日本電子DATUM公司製)，測定500MHz之質子NMR。醯亞胺化率係將源自醯亞胺化前後為變化之構造之質子作為基準質子而決定，使用該質子之波峰積分值與在9.5ppm~10.0 ppm附近出現之源自醯胺酸之NH基之質子波峰積分值由以下之式求出。＜ Determination of imidization ratio ＞
20 mg of polyfluorene imine powder was put into an NMR sample tube (NMR standard sampling tube, hydrazone 5 (manufactured by Kusano Science Co., Ltd.)), and deuterated dimethylsulfine (DMSO-d6, 0.05% TMS (tetramethylsilane)) ) (0.53 mL), and an ultrasonic wave was applied to completely dissolve. This solution was used to measure a proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500) (manufactured by Japan Electronics DATUM). The hydrazone imidization rate is determined by using protons derived from structures that change before and after hydrazone as the reference protons. The peak integral value of the protons and the NH derived from hydrazone are present around 9.5 ppm to 10.0 ppm. The proton wave integral value of the base is obtained by the following formula.
醯亞胺化率(%)=(1-α・x/y)×100
上述式中，x為源自醯胺酸之NH基之質子波峰積分值，y係基準質子之波峰積分值，α係聚醯胺酸(醯亞胺化率為0%)時之基準質子相對於醯胺酸之NH基1個質子的個數比例。醯 Imination ratio (%) = (1-α ・ x / y) × 100
In the above formula, x is the integral value of the proton peak derived from the NH group of amido acid, y is the integral value of the peak value of the reference proton, and the relative value of the reference proton at the time of α-type polyamido acid (the imidization ratio is 0%) Proportion of the number of 1 proton of the NH group in the amino acid.
[液晶胞之製作]
製作具備邊緣場開關(Fringe-Field Switching：FFS)模式液晶顯示元件之構成之液晶胞。[Manufacture of LCD cell]
A liquid crystal cell having a structure of a fringe field switching (FFS) mode liquid crystal display element is produced.
最初，準備附電極之基板。基板係30mm×50mm之大小，厚度為0.7mm之玻璃基板。於基板上形成作為第1層之構成對向電極之具備填滿狀圖型之ITO電極。於第1層之對向電極上形成作為第2層之藉由CVD法成膜之SiN(氮化矽)膜。第2層之SiN膜之膜厚為500nm，作為層間絕緣膜發揮功能。第2層之SiN膜上，配置作為第3層之將ITO膜圖型化而形成之梳齒狀像素電極，形成第1像素及第2像素之2個像素。各像素之尺寸為縱約10mm橫約5mm。此時，第1層之對向電極與第3層之像素電極係藉由第2層之SiN膜的作用而電性絕緣。Initially, a substrate with electrodes is prepared. The substrate is a glass substrate having a size of 30 mm × 50 mm and a thickness of 0.7 mm. An ITO electrode having a filled pattern is formed on the substrate as a first-layer counter electrode. A SiN (silicon nitride) film formed by a CVD method as a second layer is formed on the counter electrode of the first layer. The SiN film of the second layer has a thickness of 500 nm and functions as an interlayer insulating film. On the SiN film of the second layer, comb-shaped pixel electrodes formed by patterning the ITO film as the third layer are arranged to form two pixels of the first pixel and the second pixel. The size of each pixel is about 10 mm in length and about 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.
第3層之像素電極具有中央部分為彎曲く字形狀之電極要素複數排列而構成之梳齒狀形狀。各電極要素之短邊方向之寬度為3μm，電極要素間之間隔為6μm。形成各像素之像素電極由於係中央部分之彎曲く字形狀之電極要素複數排列而構成，故各像素之形狀不為長方形狀，與電極要素同樣為於中央部分彎曲之似粗字的く字形狀。因此，各像素以其中央之彎曲部分為界分割為上下，具有彎曲部分之上側之第1區域與下側之第2區域。The pixel electrode of the third layer has a comb-tooth shape formed by arranging a plurality of electrode elements in a curved く shape at the center. The width in the short-side direction of each electrode element is 3 μm, and the interval between the electrode elements is 6 μm. The pixel electrode forming each pixel is formed by plurally arranged electrode elements in a curved shape of the central portion. Therefore, the shape of each pixel is not rectangular, and like the electrode element, it is a thick letter-like shape curved in the central portion . Therefore, each pixel is divided into an upper part and a lower part by a curved portion in the center, and has a first region on the upper side and a second region on the lower side.
若比較各像素之第1區域與第2區域，則構成該等之像素電極之電極要素的形成方向不同。亦即，以後述之液晶配向膜的摩擦方向為基準時，於像素之第1區域，像素電極之電極要素形成為+10°之角度(順時針)，於像素之第2區域，像素電極之電極要素形成為-10°之角度(順時針)。亦即各像素之第1區域與第2區域中，構成為藉由於像素電極與對向電極之間之電壓施加而誘發之液晶於基板面內之旋轉動作(平面間切換)之方向互為相反方向。When the first region and the second region of each pixel are compared, the formation directions of the electrode elements constituting such pixel electrodes are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed at an angle of + 10 ° (clockwise) in the first region of the pixel, and in the second region of the pixel, the pixel electrode The electrode elements are formed at an angle (clockwise) of -10 °. That is, in the first region and the second region of each pixel, the directions of the rotation (switching between planes) of the liquid crystal in the substrate surface induced by the voltage application between the pixel electrode and the counter electrode are opposite to each other. direction.
其次，液晶配向劑以1.0μm之過濾器過濾後，藉由旋轉塗佈法塗佈於所準備之上述附電極之基板與於背面成膜有ITO膜之具有高4μm之柱狀間隔物之玻璃基板上。於80℃之加熱板上乾燥2分鐘，對塗膜面經由偏光板照射消光比10：1以上之經直線偏光之波長254nm之紫外線後，以230℃之熱風循環式烘箱進行20分鐘燒成，形成膜厚100nm之塗膜。將上述2片基板設為一組，於基板上印刷密封劑，使另一片基板以使液晶配向膜面對向且配向方向成為0°之方式貼合後，使密封劑硬化製作空胞。以減壓注入法將液晶MLC-3019(Merck公司製)注入於該空胞後，密封注入口，作成液晶胞。隨後，以110℃加熱所得之液晶胞1小時，放置一晚後使用於評價。Next, after the liquid crystal alignment agent is filtered through a 1.0 μm filter, the prepared substrate with the electrode and the glass having a columnar spacer with a height of 4 μm having an ITO film formed on the back surface are spin-coated. On the substrate. Dry on a hot plate at 80 ° C for 2 minutes, and irradiate the coating film surface with ultraviolet rays with a linear extinction wavelength of 254nm at an extinction ratio of 10: 1 or more through a polarizing plate, then fire in a hot air circulation oven at 230 ° C for 20 minutes A coating film having a thickness of 100 nm was formed. The above two substrates are set as a set, and a sealant is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction becomes 0 °, and then the sealant is hardened to produce air cells. Liquid crystal MLC-3019 (manufactured by Merck) was injected into the cell by a reduced pressure injection method, and then the injection port was sealed to form a liquid crystal cell. Subsequently, the obtained liquid crystal cells were heated at 110 ° C. for 1 hour, and left for one night for evaluation.
[黑亮度評價]
將上述液晶胞配置於以偏光軸正交之方式配置之2片偏光板之間，以使於未施加電壓之狀態將背光點亮時，透過光之亮度成為最小之方式調整液晶胞的配置角度。隨後，使用亮度計(TOPCON製SR-UL2)測定於未施加電壓之狀態之透過光之亮度(黑亮度)。[Evaluation of black brightness]
The above-mentioned liquid crystal cell is arranged between two polarizing plates arranged with orthogonal polarization axes, so that when the backlight is turned on without a voltage applied, the arrangement angle of the liquid crystal cell is adjusted to minimize the brightness of the transmitted light. . Subsequently, the luminance (black luminance) of the transmitted light in a state where no voltage was applied was measured using a luminance meter (SR-UL2 manufactured by TOPCON).
[鉛筆硬度之評價]
如以下般製作鉛筆硬度評價之樣品。於30mm×40mm之ITO基板上，藉由旋轉塗佈法塗佈液晶配向劑。於80℃之加熱板上乾燥2分鐘，於塗膜面經由偏光板照射消光比10：1以上之經直線偏光之波長254nm之紫外線後，以230℃之熱風循環式烘箱進行20分鐘燒成，獲得附液晶配向膜之基板。以鉛筆硬度試驗法(JIS K5400)測定該基板。[Evaluation of pencil hardness]
Samples for pencil hardness evaluation were prepared as follows. A liquid crystal alignment agent was applied on a 30 mm × 40 mm ITO substrate by a spin coating method. Dry on a hot plate at 80 ° C for 2 minutes, and irradiate a linearly polarized light with a wavelength of 254nm at an extinction ratio of 10: 1 or more on the coating film surface through a polarizing plate, and then fire in a hot air circulation oven at 230 ° C for 20 minutes. A substrate with a liquid crystal alignment film was obtained. This substrate was measured by a pencil hardness test method (JIS K5400).
＜合成例1＞
於附攪拌裝置及氮氣導入管之100mL之四頸燒瓶中，取入DA-1 3.91g(16.0mmol)、DA-2 2.19(6.41mmol)、DA-3 0.519g(4.80mmol)、DA-4 1.54g(4.81mmol)，添加NMP 46.2g，邊送入氮氣邊攪拌而溶解。邊攪拌該二胺溶液邊添加CA-1 5.70g(25.4mmol)、CA-2 1.20g(4.80mmol)，進而以使固形分濃度成為15質量%之方式添加NMP 39.1g，於40℃攪拌24小時，獲得聚醯胺酸溶液(A)(黏度：450mPa・s)。聚醯胺酸之分子量係Mn=11200，Mw=26900。<Synthesis example 1>
In a 100 mL four-neck flask with a stirring device and a nitrogen introduction tube, take DA-1 3.91g (16.0mmol), DA-2 2.19 (6.41mmol), DA-3 0.519g (4.80mmol), DA-4 1.54 g (4.81 mmol), 46.2 g of NMP was added, and dissolved while being stirred while being fed with nitrogen. While stirring this diamine solution, 5.70 g (25.4 mmol) of CA-1 and 1.20 g (4.80 mmol) of CA-2 were added, and further 39.1 g of NMP was added so that the solid content concentration became 15% by mass, and stirred at 40 ° C for 24 After 1 hour, a polyamic acid solution (A) was obtained (viscosity: 450 mPa · s). The molecular weight of polyamic acid is Mn = 11200 and Mw = 26900.
＜合成例2＞
於附攪拌裝置及氮氣導入管之100mL之四頸燒瓶中，取入DA-5 5.10g(25.6mmol)、DA-6 1.27(6.41mmol)，添加NMP 36.1g，邊送入氮氣邊攪拌而溶解。邊攪拌該二胺溶液邊添加CA-2 4.00g(16.0mmol)、CA-3 4.42g(15.0mmol)，進而以使固形分濃度成為15質量%之方式添加NMP 47.7g，於50℃攪拌24小時，獲得聚醯胺酸溶液(B)(黏度：904mPa・s)。聚醯胺酸之分子量係Mn=14600，Mw=37500。<Synthesis example 2>
In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, take 5.10 g (25.6 mmol) of DA-5 and 1.27 (6.41 mmol) of DA-6, add 36.1 g of NMP, and stir and dissolve while sending nitrogen. . Add 4.00 g (16.0 mmol) of CA-2 and 4.42 g (15.0 mmol) of CA-3 while stirring the diamine solution, and further add 47.7 g of NMP so that the solid content concentration becomes 15% by mass, and stir at 50 ° C for 24 After 1 hour, a polyamic acid solution (B) was obtained (viscosity: 904 mPa · s). The molecular weight of polyamic acid is Mn = 14600 and Mw = 37500.
＜合成例3＞
於附攪拌裝置及氮氣導入管之100mL之四頸燒瓶中，取入所得聚醯胺酸溶液(A) 30g，添加NMP 15.0g，攪拌30分鐘。於所得聚醯胺酸溶液中，添加乙酸酐4.89g、吡啶1.51g，於50℃加熱2小時30分鐘，進行化學醯亞胺化。所得反應液邊攪拌邊投入154mL甲醇中，濾取析出之沉澱物，接著，以154mL之甲醇洗淨3次。所得樹脂粉末於60℃乾燥12小時，獲得聚醯亞胺樹脂粉末(A)。該聚醯亞胺樹脂粉末之醯亞胺化率為64%，Mn=9900，Mw=20000。<Synthesis example 3>
In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 30 g of the obtained polyamic acid solution (A) was taken, 15.0 g of NMP was added, and the mixture was stirred for 30 minutes. To the obtained polyfluorenic acid solution, 4.89 g of acetic anhydride and 1.51 g of pyridine were added, and the mixture was heated at 50 ° C. for 2 hours and 30 minutes to carry out chemical fluorination. The obtained reaction solution was poured into 154 mL of methanol while stirring, and the precipitate was collected by filtration, and then washed three times with 154 mL of methanol. The obtained resin powder was dried at 60 ° C. for 12 hours to obtain a polyimide resin powder (A). The polyfluorene imine resin powder had a hydrazone imidation ratio of 64%, Mn = 9900, and Mw = 20,000.
＜合成例4＞
將合成例3所得之聚醯亞胺樹脂粉末(A) 3.00g取入100mL三角燒瓶中，以使固形分濃度成為12%之方式添加NMP 22.0g，於70℃攪拌24小時予以溶解，獲得聚醯亞胺溶液(A)。<Synthesis example 4>
3.00 g of the polyimide resin powder (A) obtained in Synthesis Example 3 was put into a 100 mL Erlenmeyer flask, 22.0 g of NMP was added so that the solid content concentration became 12%, and the mixture was stirred at 70 ° C for 24 hours to dissolve to obtain a polymer. Hydrazone solution (A).
＜實施例1＞
將合成例4所得之聚醯亞胺溶液(A) 3.80g與合成例2所得之聚醯胺酸溶液(B) 4.56g取入100mL三角燒瓶中，添加AD-1 0.114g、NMP 1.64g、GBL 6.00g、BCS 4.00g，於室溫攪拌3小時，獲得液晶配向劑(1)。於該液晶配向劑中，未見到混濁或析出等之異常，確認為均一溶液。<Example 1>
3.80 g of the polyimide solution (A) obtained in Synthesis Example 4 and 4.56 g of the polyimide solution (B) obtained in Synthesis Example 2 were put into a 100 mL Erlenmeyer flask, and 0.114 g of AD-1, 1.64 g of NMP, and GBL 6.00g, BCS 4.00g, and stirred at room temperature for 3 hours to obtain a liquid crystal alignment agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed to be a uniform solution.
＜比較例1＞
將合成例4所得之聚醯亞胺溶液(A) 3.80g與合成例2所得之聚醯胺酸溶液(B) 4.56g取入100mL三角燒瓶中，添加NMP 1.64g、GBL 6.00g、BCS 4.00g，於室溫攪拌3小時，獲得液晶配向劑(2)。於該液晶配向劑中，未見到混濁或析出等之異常，確認為均一溶液。〈Comparative example 1〉
3.80 g of the polyimide solution (A) obtained in Synthesis Example 4 and 4.56 g of the polyimide solution (B) obtained in Synthesis Example 2 were put into a 100 mL Erlenmeyer flask, and NMP 1.64 g, GBL 6.00 g, and BCS 4.00 were added. g, and stirred at room temperature for 3 hours to obtain a liquid crystal alignment agent (2). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed to be a uniform solution.
＜比較例2＞
將合成例4所得之聚醯亞胺溶液(A) 3.80g與合成例2所得之聚醯胺酸溶液(B) 4.56g取入100mL三角燒瓶中，添加AD-2 0.114g、NMP 1.64g、GBL 6.00g、BCS 4.00g，於室溫攪拌3小時，獲得液晶配向劑(1)。於該液晶配向劑中，未見到混濁或析出等之異常，確認為均一溶液。
＜實施例2＞
將實施例1所得之液晶配向劑(1)以1.0μm之過濾器過濾後，藉由旋轉塗佈法塗佈於所準備之上述附電極之基板與於背面成膜有ITO膜之具有高4μm之柱狀間隔物之玻璃基板上。於80℃之加熱板上乾燥2分鐘，對塗膜面經由偏光板照射消光比26：1之經直線偏光之波長254nm之紫外線0.25J/cm2
後，以230℃之熱風循環式烘箱進行20分鐘燒成，形成膜厚100nm之附液晶配向膜之基板。
將所得之上述2片基板設為一組，於基板上印刷密封劑，使另一片基板以使液晶配向膜面對向且配向方向成為0°之方式貼合後，使密封劑硬化製作空胞。以減壓注入法將液晶MLC-3019(Merck公司製)注入於該空胞後，密封注入口，獲得液晶胞。隨後，以110℃加熱所得之液晶胞1小時，放置一晚後實施黑亮度評價。該液晶胞之未施加電壓狀態之透過光的亮度為27cd/m2
。〈Comparative example 2〉
3.80 g of the polyimide solution (A) obtained in Synthesis Example 4 and 4.56 g of the polyimide solution (B) obtained in Synthesis Example 2 were put into a 100 mL Erlenmeyer flask, and 0.114 g of AD-2, 1.64 g of NMP, and GBL 6.00g, BCS 4.00g, and stirred at room temperature for 3 hours to obtain a liquid crystal alignment agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed to be a uniform solution.
<Example 2>
The liquid crystal alignment agent (1) obtained in Example 1 was filtered through a 1.0 μm filter, and then applied to the prepared substrate with electrodes and a ITO film formed on the back surface by a spin coating method to have a height of 4 μm. On a glass substrate. Dried on a hot plate of 80 deg.] C for 2 minutes, irradiated extinction ratio polarizers 26 pairs of the coated surface by: a wavelength of linearly polarized light by ultraviolet of 254nm of 0.25J / cm 2, 230 deg.] C with hot air circulation type oven of 20 It is fired in minutes to form a substrate with a liquid crystal alignment film with a thickness of 100 nm.
Set the two substrates obtained above as a set, print a sealant on the substrate, attach another substrate so that the liquid crystal alignment film faces and the alignment direction becomes 0 °, and then harden the sealant to produce air cells. . A liquid crystal MLC-3019 (manufactured by Merck) was injected into the air cell by a reduced pressure injection method, and then the injection port was sealed to obtain a liquid crystal cell. Subsequently, the obtained liquid crystal cell was heated at 110 ° C. for 1 hour, and left to perform evaluation of black brightness after being left overnight. The brightness of the transmitted light of the liquid crystal cell in a state where no voltage was applied was 27 cd / m 2 .
＜比較例3~4＞
取代液晶配向劑(1)，分別使用表1所示之液晶配向劑以外，以與實施例2同樣之方法製作液晶胞，實施黑亮度評價。各所得之液晶胞之未施加電壓狀態的透過光的亮度示於表1。<Comparative Examples 3 to 4>
Instead of the liquid crystal alignment agent (1), a liquid crystal cell was produced in the same manner as in Example 2 except that the liquid crystal alignment agent shown in Table 1 was used, and black luminance evaluation was performed. Table 1 shows the brightness of the transmitted light of each of the obtained liquid crystal cells when no voltage is applied.
＜實施例3＞
將實施例1所得之液晶配向劑(1)以1.0μm之過濾器過濾後，藉由旋轉塗佈法塗佈於所準備之上述附電極之基板與於背面成膜有ITO膜之具有高4μm之柱狀間隔物之玻璃基板上。於80℃之加熱板上乾燥2分鐘，對塗膜面經由偏光板照射消光比26：1之經直線偏光之波長254nm之紫外線0.25J/cm2
後，以230℃之熱風循環式烘箱進行20分鐘燒成，形成膜厚100nm之附液晶配向膜之基板。該基板以鉛筆硬度試驗法(JIS K5400)測定之結果為3H。<Example 3>
The liquid crystal alignment agent (1) obtained in Example 1 was filtered through a 1.0 μm filter, and then applied to the prepared substrate with electrodes and a ITO film formed on the back surface by a spin coating method to have a height of 4 μm. On a glass substrate. Dried on a hot plate of 80 deg.] C for 2 minutes, irradiated extinction ratio polarizers 26 pairs of the coated surface by: a wavelength of linearly polarized light by ultraviolet of 254nm of 0.25J / cm 2, 230 deg.] C with hot air circulation type oven of 20 It is fired in minutes to form a substrate with a liquid crystal alignment film with a thickness of 100 nm. The substrate was measured by a pencil hardness test method (JIS K5400) to be 3H.
＜比較例5~6＞
取代液晶配向劑(1)，分別使用表2所示之液晶配向劑以外，以與實施例3同樣之方法分別製作鉛筆硬度試驗用之樣品。各進行鉛筆硬度試驗之評價結果示於表2。<Comparative Examples 5 to 6>
Instead of the liquid crystal alignment agent (1), samples other than the liquid crystal alignment agent shown in Table 2 were used in the same manner as in Example 3 to prepare samples for pencil hardness testing. The evaluation results of each pencil hardness test are shown in Table 2.
Claims (19)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-007030 | 2018-01-19 | ||
| JP2018007030 | 2018-01-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201940676A true TW201940676A (en) | 2019-10-16 |
| TWI798337B TWI798337B (en) | 2023-04-11 |
Family
ID=67302288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW108102129A TWI798337B (en) | 2018-01-19 | 2019-01-19 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7193783B2 (en) |
| KR (1) | KR102759522B1 (en) |
| CN (1) | CN111602088B (en) |
| TW (1) | TWI798337B (en) |
| WO (1) | WO2019142927A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI874658B (en) * | 2021-05-18 | 2025-03-01 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025254022A1 (en) * | 2024-06-06 | 2025-12-11 | 日産化学株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3893659B2 (en) | 1996-03-05 | 2007-03-14 | 日産化学工業株式会社 | Liquid crystal alignment treatment method |
| DE19860170A1 (en) * | 1998-12-24 | 2000-06-29 | Basf Coatings Ag | Multi-layer systems with at least one layer based on mesomorphic polyelectrolyte complexes, process for their production and their use |
| KR101875240B1 (en) * | 2010-08-31 | 2018-07-05 | 닛산 가가쿠 고교 가부시키 가이샤 | Diamine, polyimide precursor, polyimide, liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element |
| TWI598668B (en) * | 2012-11-30 | 2017-09-11 | Nissan Chemical Ind Ltd | A method of manufacturing a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element |
| WO2015072554A1 (en) * | 2013-11-15 | 2015-05-21 | 日産化学工業株式会社 | Liquid crystal aligning agent, and liquid crystal display element using same |
| KR102346494B1 (en) * | 2014-04-03 | 2021-12-31 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal alignment agent containing polyamic acid ester-polyamic acid copolymer, and liquid crystal alignment film using same |
| KR102719144B1 (en) * | 2015-03-24 | 2024-10-18 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| TWI715629B (en) * | 2015-09-16 | 2021-01-11 | 日商日產化學工業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| JP6747452B2 (en) * | 2015-11-25 | 2020-08-26 | 日産化学株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device |
| KR102710874B1 (en) * | 2015-12-03 | 2024-09-26 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using the same |
| WO2017119461A1 (en) * | 2016-01-07 | 2017-07-13 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element using same |
-
2019
- 2019-01-18 JP JP2019566535A patent/JP7193783B2/en active Active
- 2019-01-18 KR KR1020207021374A patent/KR102759522B1/en active Active
- 2019-01-18 WO PCT/JP2019/001553 patent/WO2019142927A1/en not_active Ceased
- 2019-01-18 CN CN201980008740.0A patent/CN111602088B/en active Active
- 2019-01-19 TW TW108102129A patent/TWI798337B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI874658B (en) * | 2021-05-18 | 2025-03-01 | 奇美實業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102759522B1 (en) | 2025-01-23 |
| TWI798337B (en) | 2023-04-11 |
| JPWO2019142927A1 (en) | 2021-01-14 |
| KR20200110350A (en) | 2020-09-23 |
| WO2019142927A1 (en) | 2019-07-25 |
| CN111602088A (en) | 2020-08-28 |
| JP7193783B2 (en) | 2022-12-21 |
| CN111602088B (en) | 2023-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI820187B (en) | Liquid crystal alignment agent, manufacturing method thereof, liquid crystal alignment film and liquid crystal display element | |
| JP6187457B2 (en) | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element for photo-alignment method | |
| JP6627772B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device using the same | |
| JP4013052B2 (en) | Liquid crystal aligning agent and liquid crystal display element | |
| CN105593754A (en) | Liquid crystal aligning agent for lateral electric field driving method, liquid crystal aligning film, and liquid crystal display element using same | |
| KR20190082293A (en) | A liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element | |
| TWI820010B (en) | Manufacturing method of liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element | |
| TWI820011B (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| TWI798337B (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using same | |
| TW202321427A (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element production method, and liquid crystal display element | |
| CN121362586A (en) | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal element | |
| WO2014148596A1 (en) | Liquid crystal orientation agent, liquid crystal orientation membrane, and liquid crystal display element using same | |
| CN104704421B (en) | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells | |
| TWI826504B (en) | Liquid crystal alignment agent, manufacturing method thereof, liquid crystal alignment film and liquid crystal display element | |
| JP2019101196A (en) | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element | |
| TW201823436A (en) | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element | |
| JP2018040979A (en) | Production method of liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element | |
| TW202544125A (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| WO2025079519A1 (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element | |
| TW202536065A (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| JP2019101195A (en) | Production method of liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element |