CN113412449A - 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
- CN113412449A CN113412449A CN202080013164.1A CN202080013164A CN113412449A CN 113412449 A CN113412449 A CN 113412449A CN 202080013164 A CN202080013164 A CN 202080013164A CN 113412449 A CN113412449 A CN 113412449A
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- carbon atoms
- liquid crystal
- diamine
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 190
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 81
- 150000004985 diamines Chemical class 0.000 claims abstract description 166
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 70
- 229920001721 polyimide Polymers 0.000 claims abstract description 63
- 239000004642 Polyimide Substances 0.000 claims abstract description 62
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 33
- -1 siloxane skeleton Chemical group 0.000 claims abstract description 31
- 125000006239 protecting group Chemical group 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 118
- 125000000962 organic group Chemical group 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- 125000002947 alkylene group Chemical group 0.000 claims description 29
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000002345 steroid group Chemical group 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 68
- 239000000758 substrate Substances 0.000 description 55
- 239000002904 solvent Substances 0.000 description 50
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 38
- 238000011282 treatment Methods 0.000 description 36
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 29
- 238000000034 method Methods 0.000 description 24
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- 210000002858 crystal cell Anatomy 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920005575 poly(amic acid) Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000565 sealant Substances 0.000 description 7
- 150000003431 steroids Chemical class 0.000 description 7
- 101100328884 Caenorhabditis elegans sqt-3 gene Proteins 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-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
- 239000000843 powder Substances 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 238000001556 precipitation Methods 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 101100328886 Caenorhabditis elegans col-2 gene Proteins 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 235000012000 cholesterol Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-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 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- HQLKZWRSOHTERR-UHFFFAOYSA-N 2-Ethylbutyl acetate Chemical compound CCC(CC)COC(C)=O HQLKZWRSOHTERR-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 2
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 2
- GALUFHRFAYTRDG-UHFFFAOYSA-N 3-ethoxybutyl acetate Chemical compound CCOC(C)CCOC(C)=O GALUFHRFAYTRDG-UHFFFAOYSA-N 0.000 description 2
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 2
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 2
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 2
- MHBPZEDIFIPGSX-UHFFFAOYSA-N ethyl n-(3-trimethoxysilylpropyl)carbamate Chemical compound CCOC(=O)NCCC[Si](OC)(OC)OC MHBPZEDIFIPGSX-UHFFFAOYSA-N 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- RXTNIJMLAQNTEG-UHFFFAOYSA-N hexan-2-yl acetate Chemical compound CCCCC(C)OC(C)=O RXTNIJMLAQNTEG-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 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
- 238000000746 purification Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- HTVULPNMIHOVRU-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CC(C)OCC1CO1 HTVULPNMIHOVRU-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- ULAFJDYDLJSYLI-UHFFFAOYSA-N 1,3-diphenylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound C1(=CC=CC=C1)C1(C(C(C1C(=O)O)(C(=O)O)C1=CC=CC=C1)C(=O)O)C(=O)O ULAFJDYDLJSYLI-UHFFFAOYSA-N 0.000 description 1
- DQVRVXRIKVWXQH-UHFFFAOYSA-N 1,8-bis(oxiran-2-yl)-4,6-bis(oxiran-2-ylmethyl)octane-3,5-diol Chemical compound C1OC1CC(C(O)C(CCC1OC1)CC1OC1)C(O)CCC1CO1 DQVRVXRIKVWXQH-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- NPMRPDRLIHYOBW-UHFFFAOYSA-N 1-(2-butoxyethoxy)propan-2-ol Chemical compound CCCCOCCOCC(C)O NPMRPDRLIHYOBW-UHFFFAOYSA-N 0.000 description 1
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- HXJZEGBVQCRLOD-UHFFFAOYSA-N 1-triethoxysilylpropan-2-amine Chemical compound CCO[Si](CC(C)N)(OCC)OCC HXJZEGBVQCRLOD-UHFFFAOYSA-N 0.000 description 1
- KBRVQAUYZUFKAJ-UHFFFAOYSA-N 1-trimethoxysilylpropan-2-amine Chemical compound CO[Si](OC)(OC)CC(C)N KBRVQAUYZUFKAJ-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- FDKIPLUTIFGOQS-UHFFFAOYSA-N 2,6-dimethylheptan-4-ol Chemical compound CC(C)CC(CC(C)C)O.C(C(C)C)C(O)CC(C)C FDKIPLUTIFGOQS-UHFFFAOYSA-N 0.000 description 1
- ACUGAGLDFIVSBR-UHFFFAOYSA-N 2,6-dimethylheptan-4-one Chemical compound CC(C)CC(=O)CC(C)C.CC(C)CC(=O)CC(C)C ACUGAGLDFIVSBR-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- XGSQEQCOQAAOHE-UHFFFAOYSA-N 2-(2-butoxyethoxy)propan-1-ol Chemical compound CCCCOCCOC(C)CO XGSQEQCOQAAOHE-UHFFFAOYSA-N 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- 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
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- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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Abstract
本发明提供一种液晶取向剂，所述液晶取向剂能得到即使暴露于高温高湿后，也维持了电压保持率的液晶取向膜。本发明的液晶取向剂的特征在于，含有选自由聚酰亚胺前体和聚酰亚胺构成的组中的至少一种聚合物，该聚酰亚胺前体通过使下述二胺成分(1)和二胺成分(2)中的任意者与四羧酸成分进行聚合反应而得到，该聚酰亚胺将该聚酰亚胺前体酰亚胺化而得到。二胺成分(1)：含有具有通过热而被氢原子取代的保护基的二胺和具有硅氧烷骨架的二胺的二胺成分。二胺成分(2)：含有具有通过热而被氢原子取代的保护基和硅氧烷骨架的二胺的二胺成分。The present invention provides a liquid crystal aligning agent capable of obtaining a liquid crystal aligning film that maintains a voltage holding ratio even after being exposed to high temperature and high humidity. The liquid crystal aligning agent of this invention contains at least 1 type of polymer chosen from the group which consists of a polyimide precursor and a polyimide, It is characterized by making the following diamine component ( 1) and any of the diamine components (2) are obtained by a polymerization reaction with a tetracarboxylic acid component, and the polyimide is obtained by imidizing the polyimide precursor. Diamine component (1): A diamine component containing a diamine having a protective group substituted with a hydrogen atom by heat and a diamine having a siloxane skeleton. Diamine component (2): a diamine component containing a diamine having a protective group substituted with a hydrogen atom by heat and a siloxane skeleton.
Description
Technical Field
The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element using the liquid crystal alignment film.
Background
In a liquid crystal display element, a liquid crystal alignment film plays a role of aligning liquid crystals in a certain direction. As the liquid crystal alignment film, a polyimide-based liquid crystal alignment film has been mainly used, which is obtained by applying a liquid crystal alignment agent containing a polyimide precursor such as polyamic acid and a solution of a soluble polyimide as main components onto a glass substrate or the like and firing the applied liquid crystal alignment agent.
As the liquid crystal display device has been highly functionalized, the liquid crystal alignment film is required to have not only excellent liquid crystal alignment properties and a stable pretilt angle but also high voltage holding ratio, low residual charge when a dc voltage is applied, and/or characteristics such that the residual charge accumulated by the dc voltage is quickly relaxed.
In order to meet the above requirements, various proposals have been made. For example, patent document 1 proposes a liquid crystal aligning agent composed of an imidized polymer satisfying the following formula (1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2005-179429
Disclosure of Invention
Problems to be solved by the invention
With the recent enhancement of the performance of liquid crystal display elements, liquid crystal display elements are used for liquid crystal television vehicle-mounted applications with a large screen and high definition, for example, vehicle navigation systems, instrument panels, and the like. In such applications, in addition to the requirement for good initial characteristics, it is also required that the voltage holding ratio is not easily lowered even after a long-term exposure to high temperature and high humidity.
In addition, in general, when a liquid crystal aligning agent having a high imidization rate is used, a high voltage holding ratio is easily obtained, but there is a problem that when the solubility in a solvent is lowered and when printing is performed on a substrate, polyimide is precipitated due to moisture absorption, and a phenomenon that varnish is easily whitened occurs. Therefore, even when a liquid crystal aligning agent having a low imidization rate is used, it is required that the voltage holding ratio of the liquid crystal alignment film is not easily lowered.
However, patent document 1 does not disclose the voltage holding ratio after exposure to high temperature and high humidity. In addition, the examples of patent document 1 only disclose the case of using a liquid crystal aligning agent having a high imidization rate.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal aligning agent capable of providing a liquid crystal alignment film which maintains a voltage holding ratio even after exposure to high temperature and high humidity. Further, another object of the present invention is to provide a liquid crystal aligning agent which can provide a liquid crystal alignment film maintaining a voltage holding ratio even when the imidization ratio is low.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a liquid crystal aligning agent containing a specific polymer satisfies the above problems.
The present invention has been completed based on the above-described findings, and the following contents are the gist.
A liquid crystal aligning agent comprising at least one polymer selected from the group consisting of a polyimide precursor obtained by polymerizing a tetracarboxylic acid component with either of a diamine component (1) and a diamine component (2) described below and a polyimide obtained by imidizing the polyimide precursor.
Diamine component (1): a diamine component containing a diamine having a protecting group substituted with a hydrogen atom by heat and a diamine having a siloxane skeleton.
Diamine component (2): a diamine component containing a diamine having a protecting group substituted with a hydrogen atom by heat and a siloxane skeleton.
Effects of the invention
According to the liquid crystal aligning agent of the present invention, a liquid crystal alignment film maintaining a voltage holding ratio even after exposure to high temperature and high humidity can be obtained. Further, according to the liquid crystal aligning agent of the present invention, a liquid crystal alignment film maintaining a voltage holding ratio can be obtained even when the imidization rate is low. In addition, the liquid crystal aligning agent of the present invention is excellent in solubility and seal adhesion.
Detailed Description
< specific Polymer >
The liquid crystal aligning agent of the present invention contains at least one polymer (hereinafter, also referred to as a specific polymer) selected from the group consisting of a polyimide precursor obtained by polymerizing a tetracarboxylic acid component with any one of a diamine component (1) and a diamine component (2) described below, and a polyimide obtained by imidizing the polyimide precursor.
Diamine component (1): a diamine component containing a diamine having a protecting group substituted with a hydrogen atom by heat and a diamine having a siloxane skeleton.
Diamine component (2): a diamine component containing a diamine having a protecting group substituted with a hydrogen atom by heat and a siloxane skeleton.
< diamine component (1) >)
The diamine having a protecting group substituted with a hydrogen atom by heat in the diamine component (1) is, for example, a diamine represented by the following formula [1 ]. The diamine having a siloxane skeleton in the diamine component (1) is, for example, a diamine represented by the following formula [2 ]. In the diamine component (1), the diamine having a protecting group substituted with a hydrogen atom by heat may be a diamine represented by the following formula [1], and the diamine having a siloxane skeleton may be a diamine represented by the following formula [2 ].
(diamine represented by the formula [1 ])
The diamine represented by the formula [1] is a diamine shown below.
(formula [1]]In, XDIs represented by a formula selected from the group consisting of [1a ]]Formula [1b ]]And formula [1c]An organic group having 1 to 50 carbon atoms having at least one structure of the group A1And A2Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. )
(formula [1a ]]-formula [1c]In, XaRepresents a hydrogen atom or an organic group having 1 to 20 carbon atoms. XdRepresents a single bond or an organic group having 1 to 20 carbon atoms. XeRepresents a hydrogen atom or an organic group having 1 to 20 carbon atoms. D represents a protecting group substituted by a hydrogen atom by heat. Denotes a bonding bond. )
In the present invention, the "protective group substituted with a hydrogen atom by heat" refers to a protective group which is released by heat and substituted with a hydrogen atom. The temperature at which the protecting group is thermally released and substituted with a hydrogen atom is the firing temperature for producing a liquid crystal alignment film, and is preferably 150 to 300 ℃, and more preferably 200 to 270 ℃. As the protecting group (D), a protecting group represented by the following formula [ P ] is preferable.
(in the formula, XAIs represented by a formula [ a-1] selected from]-formula [ a-6]Structure of the group consisting of R1Represents an alkylene group having 1 to 5 carbon atoms. )
Specifically, the diamine represented by the formula [1] is preferably a diamine represented by the following formulae [1a-1] to [1c-1 ].
Formula [1a-1]In, X1Represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R)1)-、-CON(R2)-、-N(R3)CO-、-CH2At least one of O-, -COO-and-OCO-. Wherein R is1、R2And R3Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In particular, a single bond, -O-, -CONH-, -NHCO-, -COO-or-OCO-is preferable.
Formula [1a-1]In, X2Represents a single bond or an alkylene group having 1 to 10 carbon atoms. Among them, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable. XaRepresents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and more preferably represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. The organic group having 1 to 10 carbon atoms is preferably- (CH)2)n-COO-tBu (n ═ represents an integer of 1 to 5, tBu represents a t-butyl group).
Formula [1a-1]In, XbRepresents a group selected from the above-mentioned formula [ a-1]-formula [ a-6]Structures in the group.
Formula [1a-1]Wherein m represents an integer of 1 or 2, and in this case, in the case where m is 2, X is absentaA substituent of (1). p represents an integer of 1 to 4. Among them, p is preferably 1 to 3 from the viewpoint of availability of raw materials and ease of synthesis. More preferably 1 to 2. q represents an integer of 1 to 4. Among them, q is preferably 1 to 3 from the viewpoint of availability of raw materials and ease of synthesis. More preferably 1 to 2.
Formula [1b-1]In, X3And X7Each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R)1)-、-CON(R2)-、-N(R3)CO-、-CH2At least one organic group selected from the group consisting of O-, -COO-and-OCO-. Wherein R is1、R2And R3Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among them, a single bond, -O-, -CONH-, -NHC is preferableO-, -COO-or-OCO-.
Formula [1b-1]In, X4And X6Each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms. In particular, a single bond or an alkyl group having 1 to 5 carbon atoms is preferable.
X5Represents a single bond or an alkylene group having 1 to 10 carbon atoms. Among them, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable. XcRepresents a group selected from the above-mentioned formula [ a-1]-formula [ a-6]Structures in the group.
In the formula [1b-1], r represents an integer of 1 to 4. Among them, r is preferably 1 to 3 from the viewpoint of availability of raw materials and ease of synthesis. More preferably 1 to 2.
Formula [1c-1]In, X8Represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R)1)-、-CON(R2)-、-N(R3)CO-、-CH2At least one organic group selected from the group consisting of O-, -COO-and-OCO-. Wherein R is1、R2And R3Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In particular, a single bond, -O-, -CONH-, -NHCO-, -COO-or-OCO-is preferable.
Formula [1c-1]In, X9Represents a single bond or an alkylene group having 1 to 10 carbon atoms, preferably a single bond or an alkylene group having 1 to 5 carbon atoms. XdRepresents a single bond or an organic group having 1 to 20 carbon atoms. Wherein, XdPreferably a single bond or an organic group having 1 to 10 carbon atoms. XdMore preferably represents a single bond or a carbon atom (> CH-). XeRepresents a hydrogen atom or an organic group having 1 to 20 carbon atoms. At this time, at XdIn the case of a single bond, no Xe. Among them, a hydrogen atom or NH-COO-tBu (tBu represents a t-butyl group) is preferable.
Formula [1c-1]In, XfRepresents a group selected from the above-mentioned formula [ a-1]-formula [ a-6]Structures in the group. n represents an integer of 1 to 4. Among them, n is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of availability of raw materials and ease of synthesis. s represents an integer of 1 to 4, and is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of availability of raw materials and ease of synthesis. t represents1 to 4, wherein t is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of availability of raw materials and ease of synthesis.
Formula [1a-1]-formula [1c-1]In (A)1～A6Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
More specifically, the diamine represented by the formula [1] includes diamines represented by the following formulae [1d-1] to [1d-11 ].
(formula [1d-1]]-formula [1d-5]In, R1～R7Each independently represents a group selected from the following formulae [ a-1]-formula [ a-6]At least one structure of the group [1d-1]]-formula [1d-5]In (A)1～A10Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. )
(formula [ a-2)]In, R1Represents an alkylene group having 1 to 5 carbon atoms. )
(formula [1d-6 ]]-formula [1d-9]In, R8～R14Each independently represents a group selected from the formula [ a-1]]-formula [ a-6]At least one structure of the group of structures shown, formula [1d-6]-formula [1d-9]In (A)11～A18Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
Among them, diamines represented by the above-mentioned formulae [1d-1] to [1d-5] are preferably used as the diamine represented by the formula [1 ].
Further, as the diamine represented by the formula [1], diamines represented by the following formulae [1d-10] and [1d-11] can be used.
(formula [1d-10]]And formula [1d-11]In, R15～R18Each independently represents a group selected from the formula [ a-1]]-formula [ a-6]At least one structure of the group of structures shown, formula [1d-11]In (A)19And A20Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. )
The content of the diamine represented by the formula [1] is preferably 5 to 70 mol% based on 100 mol% of the total diamine components. Among them, 5 to 30 mol% is preferable. More preferably 5 to 20 mol%.
The diamine represented by the formula [1] may be used alone or in combination of two or more depending on the solubility of the specific polymer in a solvent, the coatability of a liquid crystal aligning agent, and the properties such as liquid crystal alignment properties, voltage holding ratio, and accumulated charges in the case of forming a liquid crystal alignment film.
(diamine represented by the formula [2 ])
The diamine represented by the formula [2] is the following diamine.
(formula [2]]In, R1、R2、R3、R4Each independently represents a methyl group or an ethyl group. X1And X2Each independently represents a single bond, -NHCO-, -CONH-, -COO-or-OCO-. P1And P2Each independently represents-NH2Or the following formula [ Pa]-formula [ Pb]The structure shown. n1 and n2 each independently represent an integer of 0 to 6. m represents an integer of 1 to 5. Wherein, formula [ Pa]-formula [ Pb]Optionally substituted with halogen. )
(formula [ Pa ]]-formula [ Pb]In, XD2Is represented by a formula selected from the group consisting of [2a ]]Is of the formula [2b]And formula [2c]At least one organic group having 1 to 50 carbon atoms. p represents an integer of 0 to 1.
Denotes a bonding bond. )
(formula [2a ]]-formula [2c]In, XaRepresents a hydrogen atom or an organic group having 1 to 20 carbon atoms. XdRepresents a single bond or an organic group having 1 to 20 carbon atoms. XeRepresents a hydrogen atom or an organic group having 1 to 20 carbon atoms. D represents a protecting group substituted by a hydrogen atom by heat. Denotes a bonding bond. )
Wherein, the above formula [2]]In, R1、R2、R3、R4Preferably methyl. X1And X2Preferably a single bond, -CONH-or-COO-. P1And P2Is preferably-NH2Or formula [2a ]]. n1 and n2 are preferably 3 or 4. m represents 1 or 2, more preferably 1.
In the above formula [2]In the diamine shown, XD2Preferably represents a compound selected from the following formulae [2a-1]And [2b-1]The structure of (1).
(formula [2a-1 ]]In, X1Represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R)1)-、-CON(R2)-、-N(R3)CO-、-CH2At least one organic group selected from the group consisting of O-, -COO-and-OCO-. Wherein R is1、R2、R3Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X2A single bond, an alkylene group having 1 to 10 carbon atoms, XaX represents a hydrogen atom or an organic group having 1 to 20 carbon atomsbIs represented by the formula [1a-1]The group as defined in (1). m represents an integer of 1 or 2, in which case, X representsaRepresents a hydrogen atom. p represents an integer of 1 to 4, q represents1 to 4.
Formula [2b-1]In, X8Represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R)1)-、-CON(R2)-、-N(R3)CO-、-CH2At least one member selected from the group consisting of O-, -COO-and-OCO-. Wherein R is1、R2、R3Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X9A single bond, an alkylene group having 1 to 10 carbon atoms, XdRepresents a single bond or an organic group having 1 to 20 carbon atoms, XeX represents a hydrogen atom or an organic group having 1 to 20 carbon atomsfIs represented by the formula [1a-3]The group as defined in (1). n represents an integer of 1 to 4, s represents an integer of 1 to 4, and t represents an integer of 1 to 4. )
Formula [2]]In, XD2More preferably, it represents a group represented by the following formula (tB), and still more preferably it represents an-N-Boc group.
(A represents a single bond or a divalent group comprising a C1-4 hydrocarbon group.)
Preferred examples of the diamine represented by the formula [2] include the following diamines.
The content of the diamine represented by the formula [2] is preferably 1 to 50 mol% based on 100 mol% of the total diamine components. Among them, 5 to 30 mol% is preferable. More preferably 5 to 20 mol%.
The diamine represented by the formula [2] may be used alone or in combination of two or more depending on the solubility of the specific polymer in a solvent, the coatability of a liquid crystal aligning agent, the liquid crystal aligning property in the case of forming a liquid crystal alignment film, the voltage holding ratio, the accumulated charge, and other properties.
< diamine component (2) >)
The diamine having a protective group substituted with a hydrogen atom by heat and a siloxane skeleton in the diamine component (2) is, for example, a diamine represented by the following formula [3 ].
(diamine represented by the formula [3 ])
The diamine represented by the formula [3] is a diamine shown below.
(formula [3]]In, R1、R2、R3、R4Each independently represents a methyl group or an ethyl group. X represents-NHCO-, -CONH-, -COO-or-OCO-. XD2Is represented by the formula [ Pa]And [ Pb]A group as defined. n represents an integer of 0 to 6, and m represents an integer of 1 to 5. p represents an integer of 0 to 1, and q represents an integer of 0 to 1. Wherein at least one of p and q represents 1. )
The above formula [3]In the above formula, X is preferably-CONH-or-COO-. m is preferably 1 or 2, more preferably 1. R1～R4Preferably methyl. n is preferably 1 to 4.
The content of the diamine represented by the formula [3] is preferably 1 to 50 mol% based on 100 mol% of the total diamine components. Among them, 5 to 30 mol% is preferable. More preferably 5 to 20 mol%.
The diamine represented by the formula [3] may be used alone or in combination of two or more depending on the solubility of the specific polymer in a solvent, the coatability of a liquid crystal aligning agent, the liquid crystal aligning property in the case of forming a liquid crystal alignment film, the voltage holding ratio, the accumulated charge, and other properties.
(other diamines)
The diamine component (1) and the diamine component (2) for obtaining the specific polymer may contain a diamine other than the diamines represented by the above formulae [1] to [3] (hereinafter, also referred to as another diamine). As the other diamines, the following diamines having a side chain structure are first mentioned.
(diamine having a specific side chain structure exhibiting vertical alignment)
The diamine having a specific side chain structure exhibiting vertical orientation has at least one side chain structure selected from the group consisting of the following formulas [ S1] to [ S3 ]. Hereinafter, diamines represented by the formulae [ S1] to [ S3] will be described in order as examples of diamines having the above-mentioned specific side chain structure.
[A] The method comprises the following steps A diamine having a specific side chain structure represented by the following formula [ S1 ].
The above formula [ S1]In, X1And X2Each independently represents a single bond, - (CH)2)a- (a represents an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH)3) -, -NH-, -O-, -COO-, -OCO-or- ((CH)2)a1-A1)m1-. Wherein a1 s each independently represents an integer of 1 to 15. A plurality of A1Each independently represents an oxygen atom or-COO-. m1 represents 1 to 2.
Among them, X is X in view of availability of raw materials and ease of synthesis1And X2Each independently preferably represents a single bond, - (CH)2)a- (a represents an integer of 1 to 15), -O-, -CH2O-or-COO-, more preferably represents a single bond, - (CH)2)a- (a represents an integer of 1 to 10), -O-, -CH2O-or-COO-.
Further, the above formula [ S1]In (G)1And G2Each independently represents a divalent cyclic group selected from the group consisting of a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen atom in the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. m and n are each independently an integer of 0 to 3, and the sum of m and n is 1 to 4.
Further, the above formula [ S1]In, R1Represents the number of carbon atoms1 to 20 alkyl groups, 1 to 20 alkoxy groups having 1 to 20 carbon atoms, or 2 to 20 alkoxyalkyl groups having 2 to 20 carbon atoms. Form R1Optionally substituted with fluorine. Among them, examples of the divalent aromatic group having 6 to 12 carbon atoms include: phenylene, biphenylene, naphthalene, and the like. Examples of the divalent alicyclic group having 3 to 8 carbon atoms include: cyclopropyl, cyclohexyl, and the like.
Therefore, preferable specific examples of the formula [ S1] include the following formulae [ S1-x1] to [ S1-x7 ].
The above formula [ S1-x1]～[S1-x7]In, R1And the above formula [ S1]The same applies. Xp represents- (CH)2)a- (a represents an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH)3)-、-NH-、-O-、-CH2O-, -COO-or-OCO-. A. the1Represents an oxygen atom or a-COO- (-COO-) - (a bond having a group of a bond with a group of a fluorine atom and a group of a fluorine atom or a group of a fluorine atom and a group of a fluorine atom2)a2Bonding). A. the2Represents an oxygen atom or a bond of formula (I) to (CH)2)a2Bonding). a is1Represents an integer of 0 or 1, a2Represents an integer of 2 to 10. Cy represents a1, 4-cyclohexylene group or a1, 4-phenylene group.
[B] The method comprises the following steps A diamine having a specific side chain structure represented by the following formula [ S2 ].
-X3-R2 [S2]
The above formula [ S2]In, X3Represents a single bond, -CONH-, -NHCO-, -CON (CH)3)-、-NH-、-0-、-CH2O-, -COO-or-OCO-. Among them, X is X in terms of the liquid crystal aligning property of the liquid crystal aligning agent3preferably-CONH-, -NHCO-, -O-, -CH2O-, -COO-or-OCO-.
Further, the above formula [ S2]In, R2Represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms. Form R2Optionally substituted with fluorine. In which the liquid crystal is orientedIn view of the liquid crystal alignment of the agent, R2Preferably an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms.
[C] The method comprises the following steps A diamine having a specific side chain structure represented by the following formula [ S3 ].
-X4-R3 [S3]
The above formula [ S3]In, X4represents-CONH-, -NHCO-, -O-, -COO-or-OCO-. R3Represents a structure having a steroid (steroid) skeleton. The steroid skeleton herein has a skeleton represented by the following formula (st) in which three six-membered rings and one five-membered ring are bonded.
Examples of the formula [ S3] include the following formula [ S3-x ].
In the formula [ S3-X ], X represents the formula [ X1] or [ X2 ]. Further, Col represents at least one selected from the group consisting of the above-described formulas [ Col1] to [ Col3], and G represents at least one selected from the group consisting of the above-described formulas [ G1] to [ G4 ]. Denotes the site of bonding to other groups.
Examples of preferred combinations of X, Col and G in the above formula [ S3-x ] include the following combinations. Namely, [ X1], [ Col1] and [ G1 ]; [ X1], [ Col1] and [ G2 ]; [ X1], [ Col2] and [ G1 ]; [ X1], [ Col2] and [ G2 ]; [ X1], [ Col3] and [ G2 ]; [ X1], [ Col3] and [ G1 ]; [ X2], [ Col1] and [ G2 ]; [ X2], [ Col2] and [ G2 ]; [ X2], [ Col2] and [ G1 ]; [ X2], [ Col3] and [ G2 ]; [ X2], [ Col1] and [ G1 ].
Further, specific examples of the formula [ S3] include: a structure obtained by removing a hydroxyl group (hydroxyl group) from a steroid compound described in paragraph [0024] of Japanese patent laid-open No. 4-281427, a structure obtained by removing an acid chloride (acid chloride) from a steroid compound described in paragraph [0030] of the publication, a structure obtained by removing an amino group from a steroid compound described in paragraph [0038] of the publication, a structure obtained by removing a halogen group from a steroid compound described in paragraph [0042] of the publication, and structures described in paragraphs [0018] to [0022] of Japanese patent laid-open No. 8-146421.
As a representative example of the steroid skeleton, cholesterol (a combination of [ Col1] and [ G2] in the formula [ S3-x ] is given, but a steroid skeleton not containing cholesterol may be used. That is, examples of the diamine having a steroid skeleton include 3, 5-diaminocholesteryl benzoate and the like, and a diamine component containing no diamine having a cholesterol skeleton may be used. Further, as the diamine having a specific side chain structure, a diamine containing no amide at the position of linkage of the diamine and the side chain can be used. Even when such a diamine is used, the present embodiment can provide a liquid crystal alignment film and a liquid crystal alignment agent for a liquid crystal display device, which can ensure a high voltage holding ratio even after a long period of time, even when a diamine component containing no diamine having a cholesteric skeleton is used.
The diamines having the side chain structures represented by the above formulas [ S1] to [ S3] are represented by the structures represented by the following formulas [1-S1] - [1-S3 ].
The above formula [1-S1]In, X1、X2、G1、G2、R1M and n are the same as the above formula [ S1]]The same is true in (1). The above formula [1-S2]In, X3And R2And the above formula [ S2]The same is true in (1). The above formula [1-S3]In, X4And R3And the above formula [ S3]The same is true in (1).
(diamine having a characteristic side chain structure of a two-side chain type exhibiting vertical alignment)
The diamine having a characteristic side chain structure of a two-side chain type exhibiting vertical alignment is represented by, for example, the following formula [ N1 ].
The above formula [ N1]Wherein X represents a single bond, -O-, -C (CH)3)2-、-NH-、-CO-、-NHCO-、-COO-、-(CH2)m-、-SO2-or a divalent organic group consisting of any combination thereof. Wherein X preferably represents a single bond, -O-, -NH-, -O- (CH)2)m-O-. Examples of "any combination thereof" include: -O- (CH)2)m-O-、-O-C(CH3)2-、-CO-(CH2)m-、-NH-(CH2)m-、-SO2-(CH2)m-、-CONH-(CH2)m-、-CONH-(CH2)m-NHCO-、-COO-(CH2)m-OCO-, etc. m represents an integer of 1 to 8.
In the formula [ N1], two Y's each independently represent a structure represented by the following formula [1-1 ].
The above formula [1-1]In, Y1And Y3Each independently represents a single bond, - (CH)2)a- (a represents an integer of 1 to 15), -O-, -CH2O-, -COO-or-OCO-. Y is2Represents a single bond or- (CH)2)b- (b represents an integer of 1 to 15). Wherein at Y1Or Y3Represents a single bond or- (CH)2)aIn the case of-Y2Represents a single bond. In addition, in Y1represents-O-, -CH2O-, -COO-or-OCO-, and/or Y3represents-O-, -CH2In the case of O-, -COO-or-OCO-, Y2Represents a single bond or- (CH)2)b-。
Further, the formula [1-1]In, Y4Represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycle or a carbon atom having a steroid skeletonA divalent organic group having a numerator of 17 to 51. Any hydrogen atom forming the cyclic group is optionally substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, or a fluorine atom.
Further, the above formula [1-1]In, Y5Represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. Any hydrogen atom forming the cyclic group is optionally substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, or a fluorine atom.
Further, the above formula [1-1]In, Y6Represents at least one selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms and a fluorine-containing alkoxy group having 1 to 18 carbon atoms. n represents an integer of 0 to 4.
In the formula [ N1], Y and X may be in the meta-or ortho-position, and are preferably in the ortho-position. That is, the formula [ N1] is preferably the following formula [ 1' ].
Further, the above formula [ N1]Middle, two amino (-NH)2) The position (b) may be any position on the benzene ring, but is preferably represented by the following formula [1]]-a1～[1]The position represented by-a 3, more preferably the following formula [1]-a 1. In the following formula, X is the same as the above formula [ N1]]The same is true in (1). The following formula [1]]-a1～[1]A3 explanation of the positions of the two amino groups is omitted in the above formula [ N1]]Symbol of Y shown in (a).
Therefore, the formula [ N1] is preferably an arbitrary structure selected from the group consisting of the following formulas [1] -a1-1 to [1] -a3-2, and more preferably a structure represented by the following formula [1] -a1-1, based on the above formulas [ 1' ] and [1] -a1 to [1] -a 3. In the following formulae, X and Y are the same as those in the formula [ N1 ].
Examples of the above formula [1-1] include the following formulae [1-1] -1 to [1-1] -22. Among them, as examples of the above formula [1-1], the following formulae [1-1] -1 to [1-1] -4, [1-1] -8 or [1-1] -10 are preferable. In the following formulae, the bond position to the phenyl group in the formulae [1], [ 1' ] and [1] -a1 to [1] -a3 is shown.
The diamine component contains a diamine having a double chain of a predetermined structure, and thus the liquid crystal alignment film is less likely to decrease the ability to vertically align the liquid crystal even when exposed to excessive heating. Further, the diamine component contains the diamine having both side chains, and thus the liquid crystal alignment film is not likely to have a decreased ability to vertically align liquid crystals even when the film is damaged by contact with some foreign matter. That is, the diamine component contains the diamine having both side chains, whereby a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having various excellent characteristics can be provided.
As the other diamine, a diamine represented by the following general formula (Y) is secondly exemplified.
In the above formula (Y), A1And A2Each independently represents a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, or a carbon atomA number of 2 to 5 alkenyl groups or a number of 2 to 5 alkynyl groups. From the viewpoint of liquid crystal alignment properties, A1And A2Preferably a hydrogen atom or a methyl group. If Y is shown by way of example1The structure (D) is represented by the following formulae (Y-1) to (Y-68).
(Boc in the formula represents a tert-butoxycarbonyl group. multidot.represents a bond.)
As the other diamine, a diamine having a thiophene or furan structure described in international publication No. WO2018/092759, and preferably a diamine having a structure represented by the following formula (sf); 2, 3-diaminopyridine; 2, 6-diaminopyridine; 3, 4-diaminopyridine; 2, 4-diaminopyrimidine; diaminoorganosiloxanes such as 1, 3-bis (3-aminopropyl) -tetramethyldisiloxane; aliphatic diamines such as m-xylylenediamine; alicyclic diamines such as 4, 4-methylenebis (cyclohexylamine).
(Y1Represents a sulfur atom or an oxygen atom, R2Each independently represents a single bond or a group ". 1-R5-Ph-*2”，R5Represents a group selected from the group consisting of a single bond, -O-, -COO-, -OCO-, - (CH)2)l-、-O(CH2)mAnd a divalent organic group (l and m each represents an integer of 1 to 5) in the group consisting of O-, -CONH-, and-NHCO-, wherein 1 represents a site bonded to a benzene ring in the formula (pn), and 2 represents a site bonded to an amino group in the formula (pn). Ph represents phenyleneAnd (4) a base. n represents 1 to 3)
The other diamine may be one or two or more.
(tetracarboxylic acid component)
As the tetracarboxylic acid component for obtaining the specific polymer, a tetracarboxylic dianhydride represented by the following formula [4] or a derivative thereof (tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dihalide) (collectively referred to as specific tetracarboxylic acid) can be used.
(in the formula [4], Z represents at least one structure selected from the group consisting of the following formulas [4a ] to [4q ]
Formula [4a ]]In, Z1～Z4Each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring. Z5And Z6Each independently represents a hydrogen atom or a methyl group.
Formula [4]Z in (1)1Among them, the formula [4a ] is preferable from the viewpoint of ease of synthesis and ease of polymerization reaction in producing a polymer]Is of the formula [4c]-formula [4g]Is of the formula [4k]-formula [4m]Or formula [4p ]]Tetracarboxylic dianhydride of the structure and tetracarboxylic acid derivatives thereof. More preferably formula [4a]Formula [4e ]]-formula [4g]Formula [4l ]]Is of the formula [4m]Or formula [4p ]]Tetracarboxylic dianhydride of the structure and tetracarboxylic acid derivatives thereof. Particularly preferably [4a ]]Formula [4e ]]Is of the formula [4f]Formula [4l ]]Is of the formula [4m]Or formula [4p ]]Tetracarboxylic dianhydride of the structure and tetracarboxylic acid derivatives thereof.
More specifically, the following formula [4a-1] or formula [4a-2] is preferably used.
The specific tetracarboxylic acid is preferably 50 to 100 mol% based on 100 mol% of all tetracarboxylic acid components. Among them, it is preferably 70 to 100 mol%. More preferably 80 to 100 mol%.
The specific tetracarboxylic acid may be used alone or in combination of two or more depending on the solubility of the specific polymer in a solvent, the coatability of a liquid crystal aligning agent, the alignment properties of a liquid crystal when a liquid crystal alignment film is formed, the voltage holding ratio, the accumulated charge, and other properties.
As the tetracarboxylic acid component for obtaining the specific polymer, a tetracarboxylic acid other than the specific tetracarboxylic acid (hereinafter, also referred to as another tetracarboxylic acid) may be contained.
Examples of the other tetracarboxylic acid include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, and a tetracarboxylic acid dialkyl ester dihalide compound shown below.
That is, as other tetracarboxylic acids, there can be mentioned: 1, 2, 5, 6-naphthalenetetracarboxylic acid, 1, 4, 5, 8-naphthalenetetracarboxylic acid, 1, 2, 5, 6-anthracenetetracarboxylic acid, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic acid, 2, 3, 3 ', 4-biphenyltetracarboxylic acid, bis (3, 4-dicarboxyphenyl) ether, 3, 3 ', 4, 4 ' -benzophenonetetracarboxylic acid, bis (3, 4-dicarboxyphenyl) sulfone, bis (3, 4-dicarboxyphenyl) methane, 2-bis (3, 4-dicarboxyphenyl) propane, 1, 1, 1, 3, 3, 3-hexafluoro-2, 2-bis (3, 4-dicarboxyphenyl) propane, bis (3, 4-dicarboxyphenyl) dimethylsilane, bis (3, 4-dicarboxyphenyl) diphenylsilane, 2, 3, 4, 5-pyridinetetracarboxylic acid, 2, 6-bis (3, 4-dicarboxyphenyl) pyridine, 3, 3 ', 4, 4' -diphenylsulfonetetracarboxylic acid, 3, 4, 9, 10-perylenetetracarboxylic acid or 1, 3-diphenyl-1, 2, 3, 4-cyclobutanetetracarboxylic acid, etc.
The other tetracarboxylic acids may be used alone or in combination of two or more depending on the solubility of the specific polymer in a solvent, the coatability of a liquid crystal aligning agent, the liquid crystal alignment properties when a liquid crystal alignment film is formed, the voltage holding ratio, the accumulated charge, and other properties.
< method for producing specific Polymer >
The specific polymer is at least one selected from the group consisting of a polyimide precursor obtained by polymerizing a diamine component and a tetracarboxylic acid component, and a polyimide obtained by imidizing the polyimide precursor.
The reaction of the diamine component with the tetracarboxylic acid component is usually carried out in a solvent. The solvent used in this case is not particularly limited as long as the polyimide precursor formed by dissolution is obtained. Specific examples of the solvent used in the reaction are given below, but the solvent is not limited to these examples.
For example, there may be mentioned: n-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropane amide, 3-butoxy-N, N-dimethylpropane amide, dimethyl sulfoxide or 1, 3-dimethyl-imidazolidinone. When the polyimide precursor has high solubility in a solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and the like can be used.
These solvents may be used alone or in combination. Further, even if the solvent is a solvent that does not dissolve the polyimide precursor, the solvent may be used in a mixture with the polyimide precursor within a range where the polyimide precursor to be produced does not precipitate. Further, the solvent is preferably dehydrated and dried because moisture in the solvent inhibits the polymerization reaction and causes hydrolysis of the polyimide precursor to be produced.
When the diamine component and the tetracarboxylic acid component are reacted in a solvent, the following methods may be mentioned: a method of adding the tetracarboxylic acid component directly or by dispersing or dissolving the tetracarboxylic acid component in a solvent by stirring a solution obtained by dispersing or dissolving the diamine component in the solvent; on the contrary, any of a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in a solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component to a reaction system, and the like can be used. In addition, in the case of using a plurality of diamine components or tetracarboxylic acid components and reacting them, they may be reacted in a state of being mixed in advance, or may be reacted in sequence individually, or may be reacted by mixing low molecular weight substances obtained by reacting individually to produce a polymer.
The temperature for polycondensation of the diamine component and the tetracarboxylic acid component can be selected from any temperature of-20 to 150 ℃, preferably from-5 to 100 ℃. The reaction may be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, the concentration of the polymer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and then a solvent may be added.
In the polymerization reaction for obtaining the polyimide precursor, the ratio of the total mole number of the tetracarboxylic acid component to the total mole number of the diamine component is preferably 0.8 to 1.2. Similarly to the ordinary polycondensation reaction, the molecular weight of the polyimide precursor to be produced is increased as the molar ratio is closer to 1.0.
The imidized polymer is a polyimide obtained by ring-closing a polyimide precursor, and in this polyimide, the ring-closing ratio (also referred to as imidization ratio) of an amic acid (amic acid) group) does not need to be always 100%, and can be arbitrarily adjusted depending on the application and purpose.
Examples of the method for imidizing the polyimide precursor include: thermal imidization in which a solution of a polyimide precursor is directly heated, or imidization in which a catalyst is added to a solution of a polyimide precursor.
The temperature for thermal imidization of the polyimide precursor in the solution is preferably 100 to 400 ℃, more preferably 120 to 250 ℃, and a method of performing imidization while removing water generated by imidization reaction from the system is preferable. The catalyst imidization of the polyimide precursor can be carried out by: a basic catalyst and an acid anhydride are added to a solution of a polyimide precursor, and the mixture is stirred at-20 to 250 ℃, preferably at 0 to 180 ℃.
The amount of the basic catalyst is preferably 0.5 to 30 times, more preferably 2 to 20 times, the amount of the acid anhydride is preferably 1 to 50 times, more preferably 3 to 30 times, the amount of the acid amide group.
Examples of the basic catalyst include: pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has a moderate basicity for proceeding the reaction.
Examples of the acid anhydride include: acetic anhydride, trimellitic anhydride, pyromellitic anhydride (pyromellitic anhydride), and the like. In particular, the use of acetic anhydride is preferable because purification after completion of the reaction is easy. The imidization rate obtained by the imidization of the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.
The polyimide precursor or the imidized polymer thereof of the present invention has an imidization ratio of preferably 1 to 95%, more preferably 20% or more and 80% or less, and still more preferably 40% or more and 70% or less.
When the polyimide precursor or the imidized polymer thereof formed from the reaction solution is recovered, the reaction solution may be put into a solvent to precipitate the polyimide precursor or the imidized polymer thereof. As the solvent for precipitation, there may be mentioned: methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, etc. The polymer precipitated by charging the solvent may be recovered by filtration, and then dried at normal temperature or under reduced pressure or by heating. Further, the operation of dissolving the polymer recovered by precipitation in the solvent again and recovering the polymer by reprecipitation is repeated 2 to 10 times, whereby impurities in the polymer can be reduced. Examples of the solvent in this case include: alcohols, ketones, hydrocarbons, and the like. If three or more solvents selected from them are used, the purification efficiency is further improved, and therefore, it is preferable.
In the present invention, when the polyimide precursor is a polyamic acid alkyl ester, specific examples of a method for producing the polyimide precursor include methods described in paragraphs [0054] to [0062] of International publication No. WO 2011-115077.
< liquid Crystal Aligning agent >
The content of the specific polymer in the liquid crystal aligning agent of the present invention is preferably 2 to 10% by mass, and more preferably 3 to 8% by mass in the liquid crystal aligning agent.
The liquid crystal aligning agent of the present invention may contain other polymers than the specific polymer. Examples of the polymer other than the specific polymer include: cellulosic polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamides, polysiloxanes, and the like. The content of the polymer other than the specific polymer is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the specific polymer.
The liquid crystal aligning agent usually contains an organic solvent, but the content of the organic solvent is preferably 70 to 99.9 mass% with respect to the liquid crystal aligning agent. The content may be appropriately changed depending on the method of applying the liquid crystal aligning agent and the target film thickness of the liquid crystal alignment film.
The organic solvent used in the liquid crystal aligning agent is preferably a solvent (also referred to as a good solvent) that dissolves the specific polymer. For example, there may be mentioned: n, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ -butyrolactone, 1, 3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropane amide, 3-butoxy-N, N-dimethylpropane amide, and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropane amide, 3-butoxy-N, N-dimethylpropane amide or γ -butyrolactone is preferably used.
The preferable solvent in the liquid crystal aligning agent of the present invention is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the entire solvent contained in the liquid crystal aligning agent.
The liquid crystal aligning agent of the present invention may be a solvent (also referred to as a poor solvent) that improves the film coatability and surface smoothness of the liquid crystal alignment film when the liquid crystal aligning agent is applied. Specific examples thereof are listed below.
For example, there may be mentioned: diisopropyl ether, diisobutyl methanol (2, 6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1, 2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1- (2-butoxyethoxy) -2-propanol, di-isobutyl ether, di-isobutyl carbinol, di-4-methyl-2-pentanol, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoisoamyl acetate, ethylene glycol diacetate, propylene carbonate, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and mixtures thereof, 2- (2-butoxyethoxy) -1-propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2, 6-dimethyl-4-heptanone), and the like.
Among them, preferable combinations of solvents include: n-methyl-2-pyrrolidone with ethylene glycol monobutyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone, and ethylene glycol monobutyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone and propylene glycol monobutyl ether; n-ethyl-2-pyrrolidone with propylene glycol monobutyl ether; n-methyl-2-pyrrolidone, γ -butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and diethylene glycol diethyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone, propylene glycol monobutyl ether, and 2, 6-dimethyl-4-heptanone; n-methyl-2-pyrrolidone, gamma-butyrolactone, propylene glycol monobutyl ether, and diisopropyl ether; n-methyl-2-pyrrolidone, gamma-butyrolactone, propylene glycol monobutyl ether, and 2, 6-dimethyl-4-heptanol; n-methyl-2-pyrrolidone, gamma-butyrolactone and dipropylene glycol dimethyl ether; and the like. The poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass of the entire solvent contained in the liquid crystal aligning agent. The kind and content of such a solvent can be appropriately selected depending on the coating apparatus, coating conditions, coating environment, and the like of the liquid crystal aligning agent.
The liquid crystal aligning agent of the present invention may contain: a dielectric material for changing electrical characteristics such as dielectric constant and conductivity of the liquid crystal alignment film; a silane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate; a crosslinkable compound for the purpose of improving the hardness and density of the film when the liquid crystal alignment film is produced; and an imidization accelerator for efficiently performing imidization by heating a polyimide precursor when a coating film is fired.
Examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate include: examples of the functional silane-containing compound and the epoxy-containing compound include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-glycidoxypropyltrimethoxysilane, N-glycidoxypropyltriethoxysilane, N-glycidoxypropyltrimethoxysilane, 2-trimethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, 3-trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane, 3-alkoxysilane, and the like, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4, 7-triazodecane, 10-triethoxysilyl-1, 4, 7-triazodecane, 9-trimethoxysilyl-3, 6-diazanonylacetate, 9-triethoxysilyl-3, 6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-bis (oxyethylene) -3-amino-propyltrimethoxysilane, N-trimethoxysilylpropylsilane, N-bis (oxypropylene) -1-diazanone, N-triethoxysilyl-1, N-triethoxysilyl-3-triazacyclodecane, N-triethoxy-3-aminopropyltriethoxysilane, N-triethoxy-3-ethyl-1, N-triethoxy-1-3-triazacyclo-one, N-trimethylsilyl-3-1-triazacyclo-acetate, N-trisilane, N-triethoxy-3-amino-3-nonyl-ethyl-acetate, N-N-methyl-one, N-N-, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, 1, 3, 5, 6-tetraglycidyl-2, 4-hexanediol, N, n, N ' -tetraglycidyl m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N ' -tetraglycidyl-4, 4 ' -diaminodiphenylmethane, and the like.
In addition, the following additives (CL-1) to (CL-15) may be added to the liquid crystal aligning agent of the present invention in order to improve the mechanical strength of the liquid crystal alignment film.
The additive is preferably 0.1 to 30 parts by mass per 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. More preferably 0.5 to 20 parts by mass.
< method for producing liquid crystal alignment film >
The liquid crystal alignment film is obtained by coating the liquid crystal alignment agent on a substrate to form a coating film, preferably drying the coating film, and then baking the coating film. As the substrate, a substrate having high transparency is preferable, and as the material thereof, ceramics such as glass and silicon nitride; and plastics such as acrylic and polycarbonate. As the substrate, a substrate formed with an ITO (Indium Tin Oxide) electrode or the like for driving a liquid crystal is preferably used in view of simplification of the process. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used as a single-sided substrate, and a material that reflects light such as aluminum may be used as an electrode.
The method of forming a coating film on a substrate with a liquid crystal aligning agent may be industrially used, for example, screen printing, offset printing, flexographic printing, and inkjet printing, and may also be used, depending on the purpose, immersion, roll coating, slit coating, spin coating, and spray coating.
After the coating of the liquid crystal aligning agent is formed on the substrate, the coating is preferably dried by a heating means such as a hot plate, a thermal cycle oven, or an IR (infrared ray) oven, preferably at 30 to 120 ℃, more preferably at 50 to 120 ℃, for preferably 1 to 10 minutes, and more preferably for 1 to 5 minutes, to evaporate the solvent.
When the imide precursor in the polymer is thermally imidized, the coating film obtained from the liquid crystal aligning agent is then subjected to a firing treatment by the same heating means as the above-mentioned drying treatment, preferably at 120 to 250 ℃, more preferably at 150 to 230 ℃. The time of the firing treatment varies depending on the firing temperature, and is preferably 5 minutes to 1 hour, and more preferably 5 minutes to 40 minutes.
The thickness of the film after the baking treatment is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, and if it is too thick, the resistance of the obtained liquid crystal alignment film may be increased, and therefore, it is preferably 5 to 300nm, and more preferably 10 to 200 nm.
After the above-described firing treatment, the obtained coating film is subjected to an orientation treatment. Examples of the orientation treatment include: brushing treatment, photo-alignment treatment, and the like.
As a specific example of the photo-alignment treatment, the surface of the coating film is irradiated with radiation deflected in a certain direction. As the radiation, ultraviolet rays or visible rays having a wavelength of 100 to 800nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400nm are preferable, and ultraviolet rays having a wavelength of 200 to 400nm are more preferable. In order to improve the liquid crystal alignment properties, the substrate coated with the liquid crystal alignment film may be irradiated with ultraviolet rays while being heated at 50 to 250 ℃. The irradiation amount of the radiation is preferably 1 to 10000mJ/cm2. Among them, preferred is100～5000mJ/cm2. The liquid crystal alignment film thus produced can stably align liquid crystal molecules in a certain direction.
The higher the extinction ratio of the polarized ultraviolet ray, the higher the anisotropy can be imparted, and therefore, the higher the extinction ratio is preferable. Specifically, the extinction ratio of ultraviolet rays polarized in a straight line is preferably 10: 1 or more, and more preferably 20: 1 or more.
The film subjected to the alignment treatment may be further subjected to at least one treatment selected from the group consisting of a heating treatment and a contact treatment with a solvent.
The heat treatment after the orientation treatment may be performed by the same heating means as the above-mentioned drying treatment and firing treatment, and is preferably performed at 180 to 250 ℃, and more preferably at 180 to 230 ℃. When the temperature of the heat treatment is in the above range, the contrast of the liquid crystal display element obtained from the liquid crystal alignment film obtained can be improved.
The time of the heat treatment varies depending on the heating temperature, but is preferably 5 minutes to 1 hour, and more preferably 5 to 40 minutes.
The solvent used for the contact treatment with the solvent is not particularly limited as long as it dissolves impurities and the like adhering to the liquid crystal alignment film.
Specific examples thereof include: water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, and the like. Among them, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate is preferable from the viewpoint of versatility and safety of the solvent. More preferably water, 1-methoxy-2-propanol or ethyl lactate. One or two or more of these solvents may be used.
Examples of the contact treatment include: dipping treatment, and spraying treatment (also referred to as spray treatment). The treatment time in these treatments is preferably 10 seconds to 1 hour, and particularly, the immersion treatment may be performed for 1 to 30 minutes. The temperature during the contact treatment may be normal temperature or heating, and is preferably 10 to 80 ℃ and 20 to 50 ℃ may be mentioned. In the contact treatment, ultrasonic treatment or the like may be performed as necessary.
After the contact treatment, washing (also referred to as rinsing) with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone, and drying may be performed. In this case, either rinsing or drying may be performed, or both may be performed. The drying temperature is preferably 50 to 150 ℃, and 80 to 120 ℃ can be mentioned. The drying time is preferably 10 seconds to 30 minutes, and preferably 1 to 10 minutes.
After the contact treatment with the solvent, the heat treatment after the alignment treatment may be performed. By adopting such a constitution, a liquid crystal alignment film having excellent liquid crystal alignment properties can be obtained.
< liquid crystal display element >
The liquid crystal Alignment film of the present invention can be applied to various driving modes such as a TN (Twisted Nematic) mode, an STN (Super Twisted Nematic) mode, an IPS (In-Plane Switching) mode, an FFS (Fringe Field Switching) mode, a VA (Vertical Alignment) mode, an MVA (Multi-domain Vertical Alignment) mode, and a PSA (Polymer stabilized Alignment) mode, and is preferably used as a liquid crystal Alignment film of a liquid crystal display device of a transverse electric Field system such as an IPS mode and an FFS mode, and is particularly useful as a liquid crystal display device of an FFS mode. The liquid crystal display element of the present invention is an element produced by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment agent, then producing a liquid crystal cell (cell) by a known method, and using the liquid crystal cell.
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. Note that each pixel portion constituting image display may be a liquid crystal display element having an active matrix (active matrix) structure in which a conversion element such as a TFT (Thin Film Transistor) is provided.
Specifically, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. These electrodes may be, for example, ITO electrodes, and may be patterned so as to display a desired image. 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 formed of, for example, SiO formed by a sol-gel method2-TiO2And (3) a film of the composition. Next, under the above conditions, liquid crystal alignment films were formed on the respective substrates, one substrate and the other substrate were stacked so that the liquid crystal alignment films faced each other, and the peripheries thereof were bonded with a sealant. In the sealant, it is generally preferable to mix a spacer in order to control the substrate gap. Further, it is preferable that spacers for controlling the substrate gap are scattered also in the surface portion where the sealing agent is not provided. An opening capable of being filled with liquid crystal from the outside is provided in advance in a part of the sealant.
Then, a liquid crystal material is injected into a space surrounded by the two substrates and the sealant through an opening provided in the sealant. Next, the opening is sealed with an adhesive. For the injection, there may be mentioned: the vacuum infusion method, a method utilizing the capillary phenomenon in the atmosphere, or an ODF (One Drop Fill: liquid crystal Drop) method may be used. As the liquid crystal material, either positive or negative dielectric anisotropy may be used. In the present invention, from the viewpoint of liquid crystal alignment properties, one having negative dielectric anisotropy is preferable, and can be used depending on the application.
After the liquid crystal material is injected into the liquid crystal cell, the polarizing plate is disposed. Specifically, a pair of polarizing plates is preferably attached to the surfaces of the two substrates opposite to the liquid crystal layer.
[ examples ]
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the contents explained herein. The compounds used and the like are abbreviated as follows.
(diamine component)
(tetracarboxylic acid component)
(solvent)
NMP: n-methyl-2-pyrrolidone.
BCS: ethylene glycol monobutyl ether.
< determination of molecular weight of polyimide >
The molecular weight of the polyimide was measured as follows using a Normal temperature Gel Permeation Chromatography (GPC) apparatus (SSC-7200) manufactured by SENSHU scientific Co., Ltd., and a column (KD-803, KD-805) manufactured by Shodex Co., Ltd.
Temperature of the column: at 50 ℃.
Eluent: n, N' -dimethylformamide (as additive, lithium bromide-hydrate (LiBr. H)2O) 30mmol/L, phosphoric acid/anhydrous crystals (O-phosphoric acid) 30mmol/L, Tetrahydrofuran (THF) 10 ml/L).
Flow rate: 1.0 ml/min.
Calibration curve preparation standard sample: TSK-standard polyethylene oxides (molecular weights of about 9000000, 150000, 100000, 30000, manufactured by Tosoh corporation) and polyethylene glycols (molecular weights of about 12000, 4000, 1000, manufactured by Polymer Laboratory corporation).
< measurement of imidization Rate >
To an NMR sample tube (NMR standard sample tube φ 5 manufactured by Stachypodia) was added 20mg of polyimide powder, and deuterated dimethyl sulfoxide (DMSO-d) was added60.05% TMS mixture) was added to 0.53ml, and ultrasonic waves were applied thereto to completely dissolve the TMS mixture.
The proton NMR of the solution at 500MHz was measured by using an NMR measuring instrument (JNW-ECA500) manufactured by electronic DATUM of Japan. The imidization ratio was determined as follows: the proton derived from a structure that does not change before and after imidization is determined as a reference proton, and the peak integrated value of the proton derived from the NH group of amic acid present in the vicinity of 9.5 to 10.0ppm are used to calculate the proton from the following calculation formula.
Imidization ratio (%) - (1-. alpha.x/y). times.100
< Synthesis of polyimide-based Polymer >
< Synthesis example 1 >
D1(9.14g), DA-1(4.68g, molar ratio to the total diamine component: 0.3), DA-2(3.25g, molar ratio to the total diamine component: 0.4), DA-3(1.95g, molar ratio to the total diamine component: 0.2), DA-4(1.02g, molar ratio to the total diamine component: 0.1) were mixed in NMP solvent (80.17g), and reacted at 60 ℃ for 12 hours to obtain a polyamic acid solution.
NMP (103.85g) was added to the polyamic acid solution (50.0g) to dilute the solution to 6.5 mass%, and then acetic anhydride (20.84g) and pyridine (3.23g) were added as imidization catalysts to react at 80 ℃ for 5 hours. The reaction solution was poured into methanol (622.70g), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 60 ℃ to obtain a polyimide powder (a). The polyimide had an imidization ratio of 72%, Mn of 11800 and Mw of 41800.
< Synthesis examples 2 to 4, comparative Synthesis examples 1 and 2 >
In synthetic example 1, polyimide powders (B to D) of synthetic examples 2 to 4 and polyimide powders (E, F) of comparative synthetic examples 1 and 2 were obtained in the same manner as in synthetic example 1, except that the materials and the proportions were changed as shown in tables 1 and 2.
< Synthesis example 5 >
D2(5.12G), DA-7(3.26G, molar ratio to all diamine components 0.4), DA-8(3.97G, molar ratio to all diamine components 0.4), DA-9(3.24G, molar ratio to all diamine components 0.2) were mixed in NMP solvent (62.43G), reacted at 60 ℃ for 3 hours, cooled to room temperature, D3(3.86G) and NMP solvent (15.44G) were added, and reacted at 40 ℃ for 12 hours to obtain polyamic acid solution (G). The polyamic acid solution (G) had Mn of 10600 and Mw of 35700.
[ Table 1]
In table 1, the right side in parentheses after the name of the diamine component indicates the molar ratio of each diamine used in the reaction to the entire diamine component.
[ Table 2]
< example 1 >
NMP (44.0g) was added to the polyimide powder (A) (6.0g) obtained in Synthesis example 1, and the mixture was stirred at 70 ℃ for 40 hours to dissolve the powder. BCS (50.0g) was added to the solution, and stirred for 5 hours, thereby obtaining a liquid crystal aligning agent [1] of example 1. The liquid crystal aligning agent was observed not to have any abnormality such as clouding and precipitation, and it was confirmed that the resin component was uniformly dissolved.
< examples 2 to 4, comparative examples 1 and 2 >
Liquid crystal aligning agents [2] to [4] of examples 2 to 4 and liquid crystal aligning agents [5] and [6] of comparative examples 1 and 2 were obtained in the same manner as in example 1 except that the polyimide material was changed as shown in table 3 in example 1. These liquid crystal aligning agents were not observed in abnormalities such as clouding and precipitation, and it was confirmed that the resin component was uniformly dissolved.
< example 5 >
NMP (29.0G) was added to the polyamic acid solution (G) (21.0G) obtained in synthesis example 5, and stirred for 30 minutes, and BCS (35.0G) was added thereto, and further stirred for 30 minutes, followed by addition of the liquid crystal aligning agent [1] (30.0G) and stirring for 5 hours, thereby obtaining the liquid crystal aligning agent [7] of example 5. The liquid crystal aligning agent was observed not to have any abnormality such as clouding and precipitation, and it was confirmed that the resin component was uniformly dissolved.
< manufacture of liquid Crystal cell >
The liquid crystal aligning agents of examples 1 to 5 and comparative examples 1 and 2 were each spin-coated on an ITO surface of an ITO-coated glass substrate (30 mm in length, 40mm in width, and 0.7mm in thickness) cleaned with pure water and IPA (isopropyl alcohol), and the substrate was baked on a hot plate at 70 ℃ for 90 seconds and then in an infrared heating furnace at 230 ℃ for 20 minutes to produce a polyimide coated substrate having a film thickness of 100 nm.
Two polyimide-coated substrates were prepared by the above method, and after spreading 4 μm bead spacers on the liquid crystal alignment film surface of one substrate, a thermosetting sealing material (XN-1500T, Co., Ltd.) was printed thereon. Next, the other substrate was bonded to the previous substrate with the surface on which the liquid crystal alignment film was formed being the inside, and the sealing material was cured to produce an empty cell. The empty cell was filled with liquid crystal MLC-3023 (trade name, manufactured by MERCK) containing a polymerizable compound for PSA by a reduced pressure injection method to prepare a liquid crystal cell. The voltage holding ratio of the liquid crystal cell was measured.
Then, the cell was irradiated with a DC voltage of 15V from the outside thereof to a depth of 10J/cm2UV (also referred to as primary PSA treatment) passing through a 325nm cut filter (cut filter) was measured for UV illuminance using UV-MO3A manufactured by ORC corporation.
Then, the residual unreacted polymerizable compound in the liquid crystal cell was irradiated with UV (UV lamp: FLR40SUV32/A-1) for 30 minutes using a UV-FL irradiation apparatus manufactured by Toshiba Lighting & Technology company in a state where no voltage was applied (referred to as secondary PSA treatment). Then, the voltage holding ratio was measured.
< evaluation of Voltage holding ratio >
The liquid crystal cell prepared above was applied with a voltage of 1V for 60 μ s in a hot air circulating oven at 60 ℃, and then the voltage after 1667msec was measured, and how much the voltage could be held was calculated as a voltage holding ratio. VHR-1 manufactured by TOYO Corporation was used for the measurement of the voltage holding ratio.
< evaluation of high temperature and high humidity resistance >
The liquid crystal cell prepared in the above was allowed to stand in a constant temperature and humidity apparatus (PR-2 KP, ESPEC) having a temperature of 85 ℃ and a humidity of 85% for 7 days, and then the voltage holding ratio was measured. The difference between the voltage holding ratio measured here and the voltage holding ratio after the secondary PSA treatment was taken as the VHR variation.
[ Table 3]
As shown in table 3, although VHR after the secondary PSA treatment was less than 86% in comparative examples 1 and 2, it was 86% or more in examples 1 to 5. Further, it was confirmed that: in comparative examples 1 and 2, the amount of change in VHR was greatly changed to 65% or more by placing the liquid crystal cell under high temperature/high humidity, and in examples 1 to 5, the amount of change in VHR was small, i.e., 50% or less.
< production of liquid Crystal cell for estimating Tilt Angle >
Spin-coating the liquid crystal alignment agents of examples 1 to 5 and comparative examples 1 and 2 on 3.5 × 3mm ITO electrode substrates (35 mm in length, 30mm in width, and 0.5mm in thickness) on which ITO electrode patterns having a pixel size of 200 μm × 600 μm and a line width/line space (line/space) of 3 μm were formed, respectively, which were cleaned with pure water and IPA (isopropyl alcohol); and an ITO surface of a glass substrate (35 mm in length, 30mm in width, 0.7mm in thickness) having an ITO electrode in which spacer pillars (photo spacers) having a height of 3.2 μm were patterned. Then, the film was baked on a hot plate at 70 ℃ for 90 seconds and then baked in an infrared heating furnace at 230 ℃ for 20 minutes or 60 minutes to produce a polyimide coated substrate having a film thickness of 100 nm.
The ITO electrode substrate on which the ITO electrode pattern is formed is divided into four cross-grid (checkered) patterns, and can be driven for each of the four regions.
Two polyimide-coated substrates were produced by the above method, and a thermosetting sealing material (XN-1500T, Co., Ltd.) was printed thereon. Next, the other substrate was bonded to the former substrate with the surface on which the liquid crystal alignment film was formed being the inner side, and then the sealing material was cured to produce an empty cell. The empty cell was filled with liquid crystal MLC-3023 (trade name, manufactured by MERCK) containing a polymerizable compound for PSA by a reduced pressure injection method to prepare a liquid crystal cell. The voltage holding ratio of the liquid crystal cell was measured.
Then, the cell was irradiated with a DC voltage of 15V from the outside thereof to a depth of 10J/cm2UV passed through a 325nm cut-off filter (also known as primary PSA treatment). The UV illuminance was measured by using UV-MO3A manufactured by ORC.
Then, the residual unreacted polymerizable compound in the liquid crystal cell was irradiated with UV (UV lamp: FLR40SUV32/A-1) for 30 minutes under a condition of no voltage application using a UV-FL irradiation apparatus manufactured by Toshiba Lighting & Technology (referred to as secondary PSA treatment). Then, measurement of the pretilt angle was performed.
< evaluation of pretilt Angle >
The pretilt angle of the liquid crystal cell prepared as described above was evaluated by using an LCD analyzer (LCA-LUV 42A manufactured by Citsubishi Technica). The difference between the pretilt angle measured here and the pretilt angle obtained by subtracting the pretilt angle obtained by coating the substrate with the polyimide after firing for 20 minutes in an infrared heating furnace at 230 ℃ from the pretilt angle obtained by coating the substrate with the polyimide after firing for 60 minutes was defined as the pretilt angle. The evaluation results are shown in table 4.
[ Table 4]
As shown in table 4, it was confirmed that: in comparative example 1 in which no siloxane skeleton was introduced, the difference in pretilt angle was 2.0 °, and in examples 1 to 5, the difference in pretilt angle was 0.4 ° or less.
< evaluation of solubility >
BCS was added dropwise to 10g of each of the liquid crystal aligning agents of examples 1 to 5 and comparative examples 1 and 2 while stirring, and the solubility was calculated from the weight of the white turbidity by the following formula. The evaluation results are shown in table 5.
Solubility (%) - (amount of BCS in liquid crystal aligning agent + amount of BCS added dropwise)/(amount of liquid crystal aligning agent + amount of BCS added dropwise) × 100
< production of substrate for measuring seal adhesion >
The liquid crystal aligning agents of examples 1 to 5 and comparative examples 1 and 2 were each spin-coated on an ITO surface of an ITO-coated glass substrate (30 mm in length, 40mm in width, and 0.7mm in thickness) cleaned with pure water and IPA (isopropyl alcohol), and the substrate was fired on a hot plate at 70 ℃ for 90 seconds and then in an infrared heating furnace at 230 ℃ for 20 minutes to produce a polyimide coated substrate having a film thickness of 100 nm.
Two polyimide-coated substrates were prepared by the above method, and a 4 μmb bead spacer was applied to the liquid crystal alignment film surface of one of the substrates, followed by dropwise addition of a sealing agent (XN-1500T, manufactured by Co., Ltd.). Then, the liquid crystal alignment film surface of the other substrate was bonded so that the width of the substrates stacked was 1cm and the diameter of the sealant became a circle of approximately 3mm, with the substrates placed inside. After fixing the two laminated polyimide-coated substrates, the substrates were baked in a hot air circulating oven at 150 ℃ for 1 hour to prepare samples for evaluating adhesion.
< evaluation of seal adhesion >
The sample for evaluation of adhesion was fixed to the substrate for evaluation of adhesion at a distance of 64cm in the lower part of a three-point bending jig of a bench-top precision universal tester (AGS-X500N, manufactured by Shimadzu corporation), and then pressed from the upper part of the central part of the substrate at a speed of 5 mm/min, and the force (N) at peeling was measured. The value obtained by dividing the force (N) at peeling measured by the above method by the diameter of the sealant was evaluated as the seal adhesion. The sealing evaluation results are shown in table 5.
[ Table 5]
As shown in table 5, it was confirmed that: the solubility was less than 60% in comparative examples 1 and 2, but the solubility was 60% or more in examples 1 to 5. For the seal adhesion, it was also confirmed that: in comparative examples 1 and 2, the N/mm was less than 2, but in examples 1 to 5, the N/mm was 2.5 or more.
The entire contents of the specification, claims and abstract of japanese patent application No. 2019-021819, filed on 8/2/2019, are incorporated herein as disclosure of the specification of the present invention.
Claims (16)
1. A liquid crystal aligning agent comprising at least one polymer selected from the group consisting of a polyimide precursor obtained by polymerizing a tetracarboxylic acid component with either one of a diamine component (1) and a diamine component (2) described below and a polyimide obtained by imidizing the polyimide precursor,
diamine component (1): a diamine component containing a diamine having a protecting group substituted with a hydrogen atom by heat and a diamine having a siloxane skeleton,
diamine component (2): a diamine component containing a diamine having a protecting group substituted with a hydrogen atom by heat and a siloxane skeleton.
2. The liquid crystal aligning agent according to claim 1,
the diamine having a protecting group substituted with a hydrogen atom by heat in the diamine component (1) is a diamine represented by the following formula [1],
formula [1]In, XDIs represented by a formula selected from the group consisting of [1a ]]Formula [1b ]]And formula [1c]An organic group having 1 to 50 carbon atoms having at least one structure of the group A1And A2Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
formula [1a]-formula [1c]In, XaX represents a hydrogen atom or an organic group having 1 to 20 carbon atomsdRepresents a single bond or an organic group having 1 to 20 carbon atoms, XeRepresents a hydrogen atom or an organic substance having 1 to 20 carbon atomsD represents a protecting group substituted by a hydrogen atom by heat, and represents a bonding bond.
3. The liquid crystal aligning agent according to claim 1 or 2,
the diamine having a siloxane skeleton in the diamine component (1) is a diamine represented by the following formula [2],
formula [2]]In, R1、R2、R3、R4Each independently represents methyl or ethyl, X1And X2Each independently represents a single bond, -NHCO-, -CONH-, -COO-or-OCO-, P1And P2Each independently represents-NH2Or the following formula [ Pa]-formula [ Pb]In the structure, n1 and n2 independently represent an integer of 0 to 6, and m represents an integer of 1 to 5, wherein [ Pa ]]-formula [ Pb]The phenyl group of (a) is optionally substituted by halogen,
formula [ Pa]-formula [ Pb]In, XD2Is represented by a formula selected from the group consisting of [2a ]]Is of the formula [2b]And formula [2c]An organic group having 1 to 50 carbon atoms having at least one structure of the group, p represents an integer of 0 to 1, represents a bonding bond,
formula [2a ]]-formula [2c]In, XaX represents a hydrogen atom or an organic group having 1 to 20 carbon atomsdRepresents a single bond or an organic group having 1 to 20 carbon atoms, XeRepresents a hydrogen atom or an organic group having 1 to 20 carbon atoms, D represents a protecting group substituted with a hydrogen atom by heat, and x represents a bonding bond.
4. The liquid crystal aligning agent according to claim 2 or 3,
the diamine represented by the formula [1] is at least one diamine selected from the group consisting of the following formulas [1a-1] to [1c-1],
formula [1a-1]In, X1Represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R)1)－、－CON(R2)－、－N(R3)CO－、－CH2At least one organic group selected from the group consisting of O-, -COO-and-OCO-, wherein R1、R2、R3Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X2A single bond, an alkylene group having 1 to 10 carbon atoms, XaX represents a hydrogen atom or an organic group having 1 to 20 carbon atomsbIs represented by a formula [ a-1] selected from]-formula [ a-6]A structure in the group consisting of m represents an integer of 1 or 2, in which case X represents 2aRepresents a hydrogen atom, p represents an integer of 1 to 4, q represents an integer of 1 to 4,
formula [1b-1]In, X3And X7Each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R)1)－、－CON(R2)－、－N(R3)CO－、-CH2At least one member selected from the group consisting of O-, -COO-and-OCO-, wherein R1、R2、R3Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X4And X6Each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, X5Represents a single bond or an alkylene group having 1 to 10 carbon atoms, XcIs represented by a formula [ a-1] selected from]-formula [ a-6]In the group, r represents an integer of 1 to 4,
formula [1c-1]In, X8Is selected from the group consisting of a single bond, the number of carbon atoms1 to 10 alkylene groups, -O-, -N (R)1)－、－CON(R2)－、－N(R3)CO-、－CH2At least one member selected from the group consisting of O-, -COO-and-OCO-, wherein R1、R2、R3Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X9A single bond, an alkylene group having 1 to 10 carbon atoms, XdRepresents a single bond or an organic group having 1 to 20 carbon atoms, XeX represents a hydrogen atom or an organic group having 1 to 20 carbon atomsfIs represented by a formula [ a-1] selected from]-formula [ a-6]Wherein n represents an integer of 1 to 4, s represents an integer of 1 to 4, t represents an integer of 1 to 4,
formula [1a-1]-formula [1c-1]In (A)1～A6Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R1represents an alkylene group having 1 to 5 carbon atoms.
5. The liquid crystal aligning agent according to claim 4,
the diamine represented by the formulae [1a-1] to [1c-1] is at least one diamine selected from the group consisting of the formulae [1d-1] to [1d-5],
formula [1d-1]-formula [1d-5]In, R1～R7Each independently represents a group selected from the following formulae [ a-1]-formula [ a-6]At least one structure of the group [1d-1]]-formula [1d-5]In (A)1～A10Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
formula [ a-2]In, R1Represents an alkylene group having 1 to 5 carbon atoms.
6. The liquid crystal aligning agent according to any one of claims 3 to 5,
in the diamine represented by the formula [2], m represents 1.
7. The liquid crystal aligning agent according to any one of claims 3 to 6,
in the formula [2]In the diamine shown, XD2Is represented by a formula [2a-1 ] selected from]And [2b-1]The structure (2) in (1),
formula [2a-1]In, X1Represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R)1)－、－CON(R2)－、－N(R3)CO－、－CH2At least one organic group selected from the group consisting of O-, -COO-and OCO-, wherein R1、R2、R3Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X2A single bond, an alkylene group having 1 to 10 carbon atoms, XaX represents a hydrogen atom or an organic group having 1 to 20 carbon atomsbIs represented by the formula [1a-1]M represents an integer of 1 or 2, in which case X is X in the case where m is 2aRepresents a hydrogen atom, p represents an integer of 1 to 4, q represents an integer of 1 to 4,
formula [2b-1]In, X8Represents a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R)1)－、－CON(R2)－、－N(R3)CO－、－CH2At least one member selected from the group consisting of O-, -COO-and-OCO-, wherein R1、R2、R3Each independently represents a hydrogen atom or a carbon atomAlkyl of a sub-number of 1 to 3, X9A single bond, an alkylene group having 1 to 10 carbon atoms, XdRepresents a single bond or an organic group having 1 to 20 carbon atoms, XeX represents a hydrogen atom or an organic group having 1 to 20 carbon atomsfIs represented by the formula [1a-3]N represents an integer of 1 to 4, s represents an integer of 1 to 4, and t represents an integer of 1 to 4.
8. The liquid crystal aligning agent according to any one of claims 3 to 7,
the diamine represented by the formula [2] is a diamine represented by the following formula,
9. the liquid crystal aligning agent according to claim 1,
the diamine having a protecting group substituted with a hydrogen atom by heat and a siloxane skeleton in the diamine component (2) is a diamine represented by the following formula [3],
formula [3]In, R1、R2、R3、R4Each independently represents a methyl group or an ethyl group, X represents-NHCO-, -CONH-, -COO-or-OCO-, XD2Is of the formula [ Pa]And [ Pb]N represents an integer of 0 to 6, m represents an integer of 1 to 5, p represents an integer of 0 to 1, and q represents an integer of 0 to 1, wherein at least one of p and q represents 1.
10. The liquid crystal aligning agent according to any one of claims 1 to 9,
the tetracarboxylic acid component is a tetracarboxylic acid compound represented by the following formula [4],
in the formula [4], Z represents at least one structure selected from the group consisting of the following formulas [4a ] to [4q ],
formula [4a ]]In, Z1～Z4Each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, formula [4g]In, Z5And Z6Each independently represents a hydrogen atom or a methyl group.
11. The liquid crystal aligning agent according to any one of claims 1 to 10,
the diamine component (1) and the diamine component (2) further contain at least one diamine selected from the group consisting of diamines having specific side chain structures represented by the following formulas [ S1] to [ S3] and diamine having a side chain represented by the following formula [ N1],
the formula [ S1]In, X1And X2Each independently represents a single bond, - (CH)2)a－、－CONH－、－NHCO－、－CON(CH3) -, -NH-, -O-, -COO-, -OCO-or- ((CH)2)a1-A1)m1-, CIs (CH)2)aWherein a represents an integer of 1 to 15, a plurality of a1 each independently represents an integer of 1 to 15, and a plurality of A1Independently represent an oxygen atom or-COO-, m1 represents 1 to 2,
-X3-R2 [S2]
the formula [ S2]In, X3Represents a single bond, -CONH-, -NHCO-, -CON (CH)3)-、－NH－、-O-、-CH2O-, -COO-or-OCO-,
-X4-R3 [S3]
the formula [ S3]In, X4represents-CONH-, -NHCO-, -O-, -COO-or-OCO-, R3It is represented as a structure having a steroid skeleton,
the formula [ N1]Wherein X represents a single bond, -O-, -C (CH)3)2-、-NH-、-CO-、-NHCO-、-COO-、-(CH2)m-、-SO2Or a divalent organic group composed of any combination thereof, m represents an integer of 1 to 8, and Y each independently represents the following formula [ 1-1%]In the structure of (a) to (b),
the formula [1-1]In, Y1And Y3Each independently represents a single bond, - (CH)2)a－、-O-、-CH2O-, -COO-or-OCO-, the group- (CH)2)aWherein a represents an integer of 1 to 15, Y2Represents a single bond or- (CH)2)b-, said- (CH)2)bIn the formula (I), b represents an integer of 1 to 15, wherein Y represents1Or Y3Represents a single bond or- (CH)2)aIn the case of-Y2Represents a single bond, furthermore, in Y1represents-O-, -CH2O-, -COO-or-OCO-, and/or Y3Indication-O－、－CH2In the case of O-, -COO-or-OCO-, Y2Represents a single bond or- (CH)2)b-，
Y4Represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton, any hydrogen atom forming the cyclic group being optionally substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms or a fluorine atom,
Y5represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocycle, any hydrogen atom forming the cyclic group being optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom,
Y6represents at least one selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms and a fluorine-containing alkoxy group having 1 to 18 carbon atoms, and n represents an integer of 0 to 4.
12. The liquid crystal aligning agent according to any one of claims 2 to 11,
the content of the diamine represented by the formula [1] is 5 to 70 mol% in 100 mol% of all diamine components.
13. The liquid crystal aligning agent according to any one of claims 3 to 12,
the content of the diamine represented by the formula [2] is 1 to 50 mol% based on 100 mol% of all diamine components.
14. The liquid crystal aligning agent according to any one of claims 1 to 13,
the polyimide contained in the polymer has an imidization rate of 1 to 95%.
15. A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of claims 1 to 14.
16. A liquid crystal display element having the liquid crystal alignment film according to claim 15.
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| PCT/JP2020/004416 WO2020162508A1 (en) | 2019-02-08 | 2020-02-05 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device using same |
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| CN105385454A (en) * | 2014-08-25 | 2016-03-09 | Jsr株式会社 | Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element |
| CN105849631A (en) * | 2013-10-23 | 2016-08-10 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| WO2018062353A1 (en) * | 2016-09-29 | 2018-04-05 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
| WO2018135657A1 (en) * | 2017-01-23 | 2018-07-26 | 日産化学工業株式会社 | Liquid crystal aligning agent and method for producing liquid crystal alignment film |
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| JP4671015B2 (en) | 2003-12-17 | 2011-04-13 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| CN104220488B (en) | 2012-02-01 | 2017-05-31 | 日产化学工业株式会社 | New diamine, polymer, aligning agent for liquid crystal, liquid crystal orientation film and use its liquid crystal display cells |
| CN109564368B (en) * | 2016-08-10 | 2021-11-05 | 日产化学株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
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| CN105849631A (en) * | 2013-10-23 | 2016-08-10 | 日产化学工业株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN105385454A (en) * | 2014-08-25 | 2016-03-09 | Jsr株式会社 | Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element |
| WO2018062353A1 (en) * | 2016-09-29 | 2018-04-05 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
| WO2018135657A1 (en) * | 2017-01-23 | 2018-07-26 | 日産化学工業株式会社 | Liquid crystal aligning agent and method for producing liquid crystal alignment film |
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| JPWO2020162508A1 (en) | 2021-12-09 |
| TW202043333A (en) | 2020-12-01 |
| KR102814925B1 (en) | 2025-05-29 |
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