CN113168052A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
- Publication number
- CN113168052A CN113168052A CN201980076518.4A CN201980076518A CN113168052A CN 113168052 A CN113168052 A CN 113168052A CN 201980076518 A CN201980076518 A CN 201980076518A CN 113168052 A CN113168052 A CN 113168052A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- group
- aligning agent
- hydrogen atom
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 200
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 50
- 150000004985 diamines Chemical class 0.000 claims abstract description 48
- 229920001721 polyimide Polymers 0.000 claims abstract description 33
- 239000004642 Polyimide Substances 0.000 claims abstract description 31
- -1 imide compound Chemical class 0.000 claims abstract description 30
- 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 claims abstract description 27
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 27
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 54
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 42
- 125000000962 organic group Chemical group 0.000 claims description 25
- 238000010304 firing Methods 0.000 claims description 17
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 150000002430 hydrocarbons Chemical group 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 206010047571 Visual impairment Diseases 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 77
- 229920000642 polymer Polymers 0.000 description 49
- 239000000758 substrate Substances 0.000 description 44
- 238000011282 treatment Methods 0.000 description 27
- 229920005575 poly(amic acid) Polymers 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- 210000002858 crystal cell Anatomy 0.000 description 8
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 8
- 239000000565 sealant Substances 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- LDQMZKBIBRAZEA-UHFFFAOYSA-N 2,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C(N)=C1 LDQMZKBIBRAZEA-UHFFFAOYSA-N 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229940116333 ethyl lactate Drugs 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 3
- FXKQPQOOZSXQAG-UHFFFAOYSA-N 4-methyltriazine Chemical compound CC1=CC=NN=N1 FXKQPQOOZSXQAG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- UONVFNLDGRWLKF-UHFFFAOYSA-N 2,5-diaminobenzoic acid Chemical compound NC1=CC=C(N)C(C(O)=O)=C1 UONVFNLDGRWLKF-UHFFFAOYSA-N 0.000 description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229940057867 methyl lactate Drugs 0.000 description 2
- ILRLVKWBBFWKTN-UHFFFAOYSA-N n-benzyl-3-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCC1=CC=CC=C1 ILRLVKWBBFWKTN-UHFFFAOYSA-N 0.000 description 2
- CLYWMXVFAMGARU-UHFFFAOYSA-N n-benzyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC1=CC=CC=C1 CLYWMXVFAMGARU-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000003566 oxetanyl group Chemical group 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 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
- 230000005855 radiation Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- FADNCTVVKDWKIX-UHFFFAOYSA-N (2,4-diaminophenyl)methanol Chemical compound NC1=CC=C(CO)C(N)=C1 FADNCTVVKDWKIX-UHFFFAOYSA-N 0.000 description 1
- OHLQBRYVKXJYHZ-UHFFFAOYSA-N (3,5-diaminophenyl)methanol Chemical compound NC1=CC(N)=CC(CO)=C1 OHLQBRYVKXJYHZ-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- KAIRYYCVSCXLHZ-UHFFFAOYSA-N 1,4-diazecane Chemical compound C1CCCNCCNCC1 KAIRYYCVSCXLHZ-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- 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
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- MTVLEKBQSDTQGO-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol Chemical compound CCOC(C)COC(C)CO MTVLEKBQSDTQGO-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
- IEFWDQQGFDLKFK-UHFFFAOYSA-N 2-n,2-n-dimethyl-1,3,5-triazine-2,4,6-triamine Chemical compound CN(C)C1=NC(N)=NC(N)=N1 IEFWDQQGFDLKFK-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 description 1
- CRORGGSWAKIXSA-UHFFFAOYSA-N 3-methylbutyl 2-hydroxypropanoate Chemical compound CC(C)CCOC(=O)C(C)O CRORGGSWAKIXSA-UHFFFAOYSA-N 0.000 description 1
- RAMLHCQVJWEUAO-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione;styrene Chemical class C=CC1=CC=CC=C1.O=C1NC(=O)C(C=2C=CC=CC=2)=C1 RAMLHCQVJWEUAO-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 1
- FNXHOOKYOVVCED-UHFFFAOYSA-N 4-(1,3,5-triazin-2-yl)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC=C1C1=NC=NC=N1 FNXHOOKYOVVCED-UHFFFAOYSA-N 0.000 description 1
- POLIXZIAIMAECK-UHFFFAOYSA-N 4-[2-(2,6-dioxomorpholin-4-yl)ethyl]morpholine-2,6-dione Chemical compound C1C(=O)OC(=O)CN1CCN1CC(=O)OC(=O)C1 POLIXZIAIMAECK-UHFFFAOYSA-N 0.000 description 1
- YFBMJEBQWQBRQJ-UHFFFAOYSA-N 4-n-(4-aminophenyl)-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=CC=C1 YFBMJEBQWQBRQJ-UHFFFAOYSA-N 0.000 description 1
- FTHBTDDIVWLRLP-UHFFFAOYSA-N 5,6-diaminopyrazine-2,3-dicarbonitrile Chemical compound NC1=NC(C#N)=C(C#N)N=C1N FTHBTDDIVWLRLP-UHFFFAOYSA-N 0.000 description 1
- BBTNLADSUVOPPN-UHFFFAOYSA-N 5,6-diaminouracil Chemical compound NC=1NC(=O)NC(=O)C=1N BBTNLADSUVOPPN-UHFFFAOYSA-N 0.000 description 1
- ZXLYUNPVVODNRE-UHFFFAOYSA-N 6-ethenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=C)=N1 ZXLYUNPVVODNRE-UHFFFAOYSA-N 0.000 description 1
- XVMFICQRQHBOOT-UHFFFAOYSA-N 6-methoxy-1,3,5-triazine-2,4-diamine Chemical compound COC1=NC(N)=NC(N)=N1 XVMFICQRQHBOOT-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- OPGTXRAKKZSBOS-UHFFFAOYSA-N 6-phenyl-1h-triazine-2,4-diamine Chemical compound NC1=NN(N)NC(C=2C=CC=CC=2)=C1 OPGTXRAKKZSBOS-UHFFFAOYSA-N 0.000 description 1
- CPNAVTYCORRLMH-UHFFFAOYSA-N 6-phenylphenanthridine-3,8-diamine Chemical compound C=1C(N)=CC=C(C2=CC=C(N)C=C22)C=1N=C2C1=CC=CC=C1 CPNAVTYCORRLMH-UHFFFAOYSA-N 0.000 description 1
- ATCQNYLEZRQALQ-UHFFFAOYSA-N 6-propan-2-yloxy-1,3,5-triazine-2,4-diamine Chemical compound CC(C)OC1=NC(N)=NC(N)=N1 ATCQNYLEZRQALQ-UHFFFAOYSA-N 0.000 description 1
- VYQYKCAZJQOVJO-UHFFFAOYSA-N 9-ethylcarbazole-3,6-diamine Chemical compound NC1=CC=C2N(CC)C3=CC=C(N)C=C3C2=C1 VYQYKCAZJQOVJO-UHFFFAOYSA-N 0.000 description 1
- KPIAHQAOODFLBZ-UHFFFAOYSA-N 9-methylcarbazole-3,6-diamine Chemical compound NC1=CC=C2N(C)C3=CC=C(N)C=C3C2=C1 KPIAHQAOODFLBZ-UHFFFAOYSA-N 0.000 description 1
- YCZUWQOJQGCZKG-UHFFFAOYSA-N 9h-carbazole-3,6-diamine Chemical compound C1=C(N)C=C2C3=CC(N)=CC=C3NC2=C1 YCZUWQOJQGCZKG-UHFFFAOYSA-N 0.000 description 1
- IYLLULUTZPKQBW-UHFFFAOYSA-N Acrinol Chemical compound CC(O)C(O)=O.C1=C(N)C=CC2=C(N)C3=CC(OCC)=CC=C3N=C21 IYLLULUTZPKQBW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- WDVSHHCDHLJJJR-UHFFFAOYSA-N Proflavine Chemical compound C1=CC(N)=CC2=NC3=CC(N)=CC=C3C=C21 WDVSHHCDHLJJJR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 description 1
- 229960004012 amifampridine Drugs 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000005676 cyclic carbonates Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- XYVDNBKDAAXMPG-UHFFFAOYSA-M decyl 2-(1-heptylazepan-1-ium-1-yl)acetate;hydroxide Chemical compound [OH-].CCCCCCCCCCOC(=O)C[N+]1(CCCCCCC)CCCCCC1 XYVDNBKDAAXMPG-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- MVUXVDIFQSGECB-UHFFFAOYSA-N ethyl n-(3-triethoxysilylpropyl)carbamate Chemical compound CCOC(=O)NCCC[Si](OCC)(OCC)OCC MVUXVDIFQSGECB-UHFFFAOYSA-N 0.000 description 1
- MHBPZEDIFIPGSX-UHFFFAOYSA-N ethyl n-(3-trimethoxysilylpropyl)carbamate Chemical compound CCOC(=O)NCCC[Si](OC)(OC)OC MHBPZEDIFIPGSX-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- MSQACBWWAIBWIC-UHFFFAOYSA-N hydron;piperazine;chloride Chemical compound Cl.C1CNCCN1 MSQACBWWAIBWIC-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- VNRDAMBPFDPXSM-UHFFFAOYSA-N n'-[2-(3-triethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCNCCN VNRDAMBPFDPXSM-UHFFFAOYSA-N 0.000 description 1
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- DTPZJXALAREFEY-UHFFFAOYSA-N n-methyl-3-triethoxysilylpropan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNC DTPZJXALAREFEY-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- PVCOXMQIAVGPJN-UHFFFAOYSA-N piperazine-1,4-diamine Chemical compound NN1CCN(N)CC1 PVCOXMQIAVGPJN-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- YAAWASYJIRZXSZ-UHFFFAOYSA-N pyrimidine-2,4-diamine Chemical compound NC1=CC=NC(N)=N1 YAAWASYJIRZXSZ-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- 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
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
- G02F1/134309—Electrodes characterised by their geometrical arrangement
- G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Polymers & Plastics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Geometry (AREA)
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Provided are a liquid crystal aligning agent for photo-alignment, a liquid crystal alignment film, and a liquid crystal display element, which can suppress afterimages caused by long-term AC driving generated in the liquid crystal display element of an IPS driving method or an FFS driving method. A liquid crystal aligning agent, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film, wherein the liquid crystal aligning agent contains a polyimide, the polyimide is an imide compound of a polyimide precursor obtained by a polymerization reaction of a tetracarboxylic acid component and a diamine component, the tetracarboxylic acid component contains: a tetracarboxylic dianhydride represented by the following formula (1) or a derivative thereof, a tetracarboxylic dianhydride represented by the following formula (2) or a derivative thereofA derivative thereof, and an aromatic tetracarboxylic dianhydride represented by the following formula (6). (X)1Is any one of the formulae (X1-1) to (X1-4), X2Is of formula (X2-1) or (X2-2), X3Is aromatic ring radical with 4 valence. )
Description
Technical Field
The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element provided with the liquid crystal alignment film.
Background
Liquid crystal display elements used in liquid crystal televisions, liquid crystal displays, and the like are generally provided with a liquid crystal alignment film for controlling the alignment state of liquid crystal in the element.
The liquid crystal alignment film which is currently most widely used in industry is produced by rubbing the surface of a film formed of polyamic acid and/or polyimide imidized from the polyamic acid and formed on an electrode substrate with a cloth such as cotton, nylon, or polyester in one direction, so-called rubbing treatment.
The brushing treatment is a simple and industrially useful method with excellent productivity. However, as the liquid crystal display element has been improved in performance, refined in precision, and increased in size, various problems such as damage to the surface of the alignment film, dust generation, influence by mechanical force and static electricity, and further unevenness in the alignment treatment surface, which are caused during the rubbing treatment, have become apparent.
As a method for replacing the rubbing treatment, a photo-alignment method is known in which a polarized radiation is irradiated to impart a liquid crystal alignment ability. As treatments by the photo-alignment method, treatments using a photoisomerization reaction, treatments using a photo-crosslinking reaction, treatments using a photo-decomposition reaction, and the like have been proposed (see non-patent document 1).
Patent document 1 proposes that a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain is used for the photo-alignment method.
As for the photo alignment method as described above, as an alignment treatment method by a brushless rubbing, not only industrial production can be realized by a simple production process, but also in a liquid crystal display element of an IPS driving method or an FFS (fringe field switching) driving method, improvement of contrast and viewing angle characteristics of the liquid crystal display element can be expected as compared with a liquid crystal alignment film obtained by a rubbing treatment method, and therefore, attention is paid to the photo alignment method as a promising liquid crystal alignment treatment method.
Liquid crystal alignment films used in liquid crystal display devices of the IPS driving method and the FFS driving method need to have not only excellent basic characteristics such as liquid crystal alignment properties and electrical characteristics, but also suppression of afterimages due to long-term ac driving.
However, the liquid crystal alignment film obtained by the photo-alignment method has the following problems: the polymer film has a smaller anisotropy with respect to the alignment direction than a liquid crystal alignment film obtained by brushing. If the anisotropy is small, sufficient liquid crystal alignment properties cannot be obtained, and problems such as image sticking occur when a liquid crystal display element is produced. In contrast, patent document 2 proposes, as a method for improving the anisotropy of a liquid crystal alignment film obtained by a photo-alignment method, a method in which low-molecular-weight components generated by cleaving the main chain of polyimide by light irradiation are removed after the light irradiation.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 9-297313
Patent document 2: japanese patent laid-open publication No. 2011-107266
Non-patent document
Non-patent document 1: "liquid crystal photo-alignment film" functional material for "Muhuihua", Shanmura No.11, page 13-22 in 1997
Disclosure of Invention
Problems to be solved by the invention
In the case of performing a photo-alignment treatment of an organic film such as a polyimide precursor or polyimide, it has been clarified from the knowledge of the present inventors that: the effect of photo-alignment is sensitive to the irradiation amount of light used, and an optimum irradiation amount with a relatively narrow range is required, and if the irradiation amount is out of the optimum range, the alignment of a part or the whole of the liquid crystal alignment film may be incomplete, and stable alignment of the liquid crystal may not be achieved.
Moreover, it was found that: in particular, when a large-sized panel is treated by the photo-alignment method, it is difficult to perform photo-alignment irradiation in which the amount of light irradiation is uniformly controlled, and as a result, it is difficult to perform alignment treatment by a stable photo-alignment method.
Accordingly, an object of the present invention is to provide a liquid crystal aligning agent which can provide a stable liquid crystal aligning ability with good quality even in a case of a panel having a particularly large size by providing a wide irradiation amount margin by widening a range of irradiation amount (hereinafter, also referred to as an optimum irradiation amount margin) in which a good alignment controllability can be obtained. That is, an object of the present invention is to provide a liquid crystal aligning agent which has a wide range of light irradiation amount to stably generate alignment controllability and can efficiently obtain a high-quality liquid crystal alignment film.
Means for solving the problems
The present inventors have made extensive studies and, as a result, have found that the above object can be achieved by a liquid crystal aligning agent containing the following features.
A liquid crystal aligning agent comprising a polyimide which is an imide compound of a polyimide precursor obtained by a polymerization reaction of a tetracarboxylic acid component and a diamine component, wherein the tetracarboxylic acid component comprises: a tetracarboxylic dianhydride represented by the following formula (1) or a derivative thereof, a tetracarboxylic dianhydride represented by the following formula (2) or a derivative thereof, and an aromatic tetracarboxylic dianhydride represented by the following formula (6).
Wherein, X1Is a structure represented by any one of the following formulae (X1-1) to (X1-4). X2Is a structure represented by the following formula (X2-1) or (X2-2). X3Is an aromatic ring having 4 linkages.
Wherein R is3～R6Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a 1-valent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and is optionally the same or different, but at least one is not a hydrogen atom. R7～R23Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a 1-valent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group.
ADVANTAGEOUS EFFECTS OF INVENTION
The liquid crystal aligning agent of the present invention can provide a liquid crystal alignment film having a good residual image characteristic, which can increase the margin of light irradiation amount for providing excellent photo-alignment treatment which has been difficult in the past. Therefore, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention has a high yield in the production of liquid crystal panels, and can reduce the image sticking caused by ac driving generated in the liquid crystal display elements of the IPS driving method and the FFS driving method, thereby obtaining the liquid crystal display elements of the IPS driving method and the FFS driving method having excellent image sticking characteristics.
Detailed Description
As described above, the liquid crystal aligning agent of the present invention is characterized by containing a polyimide (hereinafter, also referred to as a specific polymer) which is an imide compound of a polyimide precursor obtained from a tetracarboxylic acid having a specific structure or a tetracarboxylic acid component derivative having a derivative thereof and a diamine component.
< specific Polymer >
The specific polymer used in the present invention is polyimide, which is an imide compound of a polyimide precursor having a specific structure. The polyimide precursor is not particularly limited as long as it is a polyimide precursor that forms an imide ring by heating, or chemical imidization with a catalyst, such as polyamic acid or polyamic acid ester. From the viewpoint of ease of heating or chemical imidization, polyamic acid or polyamic acid ester is more preferable as the polyimide precursor.
The imidization ratio of the polyimide is not particularly limited, but is preferably 10 to 100%, more preferably 50 to 100%, and further preferably 50 to 80%.
Hereinafter, each component as a raw material for forming the above-mentioned specific polymer will be described.
< tetracarboxylic acid component >
The tetracarboxylic acid component used for the polymerization of the specific polymer of the present invention may be not only tetracarboxylic dianhydride but also tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dihalide as a derivative thereof.
The tetracarboxylic acid component used for the polymerization of the specific polymer of the present invention contains: a tetracarboxylic dianhydride represented by the following formula (1) or a derivative thereof, a tetracarboxylic dianhydride represented by the following formula (2) or a derivative thereof, and an aromatic tetracarboxylic dianhydride represented by the following formula (6) or a derivative thereof. By containing the tetracarboxylic dianhydride or the derivative thereof represented by the formula (1), the amount of light irradiation required for the photoreaction of the specific polymer can be reduced, and a liquid crystal alignment film exhibiting high liquid crystal alignment properties can be obtained. By containing the tetracarboxylic dianhydride or derivative thereof represented by the formula (2) and the tetracarboxylic dianhydride or derivative thereof represented by the formula (6), the photoreactivity of a specific polymer can be adjusted, and a liquid crystal alignment film having a wide irradiation dose margin can be obtained.
X1Is a structure represented by any one of the following formulae (X1-1) to (X1-4).
R3～R6Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a 1-valent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and at least one of them is not a hydrogen atom. R7～R23Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a 1-valent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group.
To suppress afterimage due to long-term AC drive, X1Preferably at least 1 selected from the structures represented by any of the following formulae (X1-12) to (X1-16), and particularly preferably the following formula (X1-12).
The content ratio of the tetracarboxylic dianhydride or derivative thereof represented by the formula (1) is preferably 50 to 98 mol%, more preferably 60 to 93 mol%, and still more preferably 65 to 87 mol% based on the tetracarboxylic acid component reacted with the diamine component.
In the formula (2), X2Is a structure of the following formula (X2-1) or (X2-2).
To suppress afterimage due to long-term AC drive, X2The formula (X2-1) is preferred.
The content ratio of the tetracarboxylic dianhydride or the derivative thereof represented by the formula (2) is preferably 1 to 30 mol%, more preferably 5 to 25%, and still more preferably 10 to 20% based on 1 mol of the total tetracarboxylic acid component.
X3An aromatic ring having 4 connecting bonds, which is a 4-valent organic group, is preferably an aromatic ring having at least 1 benzene ring or naphthalene ring and having 4 connecting bonds on the benzene ring or naphthalene ring. Specific examples thereof include arbitrary structures represented by the following formulae (X3-1) to (X3-26). In order to improve the liquid crystal alignment, X3 is preferably any of (X3-1), (X3-5) to (X3-11), and (X3-14) to (X3-26). More preferably, (X3-1), (X3-7) and (X3-8) have a structure in which n is 1 to 4, preferably (X3-9) to (X3-10) or (X3-14) to (X3-26).
The content ratio of the aromatic tetracarboxylic dianhydride or the derivative thereof represented by the formula (6) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 15 mol% based on 1 mol of the tetracarboxylic acid component.
The tetracarboxylic acid component used for the polymerization of the specific polymer of the present invention may contain a tetracarboxylic dianhydride represented by the following formula (7) or a derivative thereof in addition to the above formulae (1), (2) and (6).
Wherein, X4Is a 4-valent organic radical of the formula X1～X3The structure of the organic group other than the above groups is not particularly limited. Specific examples thereof include the following formulae (X4-1) to (X4-26) and a group having a valence of 4 derived from ethylenediaminetetraacetic dianhydride. For improving the liquid crystal alignment, X4 includes (X4-8) - (X4-12), (X4-17)～(X4-19)、(X4-24)～(X4-26)。
< diamine >
The diamine component used for producing the specific polymer of the present invention is not particularly limited as long as it is a known diamine. From the viewpoint of suppressing afterimage due to long-term ac driving, at least 1 kind of diamine selected from the group consisting of the following formula (3), the following formula (4), and the following formula (5) is preferably contained.
In the above formulae (3) to (5), A1And A4Each independently represents a single bond, -CO-O-, -OCO-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS-, -NR-1-CO-NR2-(R1And R2Each independently represents a hydrogen atom or a methyl group. ) A 2-valent chain hydrocarbon group having 2 to 20 carbon atoms or-CH of the 2-valent chain hydrocarbon group2-is selected from-O-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl-), -NRCOO- (R represents a hydrogen atom or a methyl-), -CONR- (R represents a hydrogen atom or a methyl-), -COS-, -NR-1-CO-NR2-(R1And R2Each independently represents a hydrogen atom or a methyl group. ) -NR- (R represents a methyl group). ) And pyrrolidine, piperidine, and piperazine (h 1). In addition, the above-mentioned A1And A4Some or all of the hydrogen atoms of the chain hydrocarbon group and the group (h1) may be substituted with a halogen atom such as an alkyl group having 1 to 3 carbon atoms, e.g., a methyl group, a fluorine atom, a chlorine atom, or the like. A. the2The organic group is hydrogen atom, halogen atom, hydroxyl, amino, sulfydryl, nitro, phosphate group or 1-valent organic group with 1-20 carbon atoms. A. the3A chain alkyl group having 2 valence of 1 to 20 carbon atoms or-CH of the chain alkyl group having 2 valence2Is selected from-O-, -CO-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS-, -NR1-CO-NR2-(R1And R2Each independently represents a hydrogen atom or a methyl group. ) -NR- (R represents a methyl group). ) And pyrrolidine, piperidine, and piperazine (h 2). In addition, the above-mentioned A3The chain hydrocarbon group(s) and the hydrogen atoms of the group (h2) are partially or wholly optionally substituted with a halogen atom such as an alkyl group having 1 to 3 carbon atoms, e.g., a methyl group, a fluorine atom, a chlorine atom, etc. a is an integer of 1 to 4, and when a is 2 or more, A is2Optionally the same or different. b and c are integers of 1 or 2. d is an integer of 0 or 1. )
Examples of the chain hydrocarbon group having a valence of 2 and having 1 to 20 carbon atoms include alkanediyl groups such as methanediyl group, ethanediyl group, n-propanediyl group, isopropanediyl group, n-butanediyl group, isobutane diyl group, sec-butanediyl group, and tert-butanediyl group; an alkenediyl group such as a vinyldiyl group, or a butenediyl group; and alkynediyl groups such as ethynyldiyl, propynediyl, and butynediyl.
As A2In (A), the C1-20 1-valent organic group is exemplified by3And a group obtained by adding 1 hydrogen atom to a group exemplified by a 2-valent chain hydrocarbon group having 1 to 20 carbon atoms, a group (h2), or a group obtained by substituting a part or all of hydrogen atoms of the 2-valent chain hydrocarbon group having 1 to 20 carbon atoms and the group (h2) with an alkyl group having 1 to 3 carbon atoms such as a methyl group, or a halogen atom such as a fluorine atom or a chlorine atom.
In order to suppress afterimages caused by long-term AC driving, the following expressions (DA-3-1), (DA-4-1) to (DA-4-24), and (DA-5-1) to (DA-5-3) are preferable as the above expressions (3) and (4). Among them, (DA-3-1), (DA-4-1) to (DA-4-11), (DA-4-13) to (DA-4-24), and (DA-5-1) to (DA-5-2) are more preferable.
The content of the diamine represented by the formula (3), the formula (4) or the formula (5) is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, based on 1 mol of the diamine component.
The diamine used for producing the specific polymer of the present invention preferably contains a diamine represented by the following formula (8) from the viewpoint of improving the solubility of the polymer.
In the above formula (8), Y6Is a 2-valent organic group having a structure represented by the following formula (9). A. the6Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. From the viewpoint of liquid crystal alignment, A6Preferably a hydrogen atom, or a methyl group.
D is tert-butoxycarbonyl.
Specific examples of the 2-valent organic group having the structure represented by the above (9) include the following formula (J-1) and formula (J-2).
In the above formulae (J-1) and (J-1), 1 represents a group represented by the formula (I) and NH-A6Bonded bond, Q5Is a single bond, - (CH)2)n- (n is an integer of 1 to 20), or- (CH)2)nAny of-CH2And each of the groups is a group substituted by-O-, -COO-, -OCO-, -NR-, -NRCO-, -CONR-, -NRCONR-, -NRCOO-, -OCOO-, wherein R represents a hydrogen atom or a 1-valent organic group.
Q6、Q7Each independently represents a compound having-H, -NHD, -N (D)2A radical of-NHD, or having the formula-N (D)2A group of (1). Q8Is represented by having the formula-NHD, -N (D)2A radical of-NHD, or having the formula-N (D)2A group of (1). D represents a tert-butoxycarbonyl group. Wherein Q is5、Q6And Q7Has a tert-butoxycarbonyl group (Boc) in at least one group. More preferably a 2-valent organic group represented by the following formulae (J-1-a) to (J-1-d) or (J-2-1).
The diamine used for the polymerization of the specific polymer of the present invention may contain a diamine represented by the following formula (10) in addition to the above formulae (3) to (5) and (8).
In the above formula (10), A8Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. From the viewpoint of liquid crystal alignment, A8Preferably a hydrogen atom or a methyl group.
Y8Examples of the organic group having a valence of 2 include those represented by any of the formulae (Y-1) to (Y-167) described in WO 2018/117239.
< Process for producing Polyamide acid ester, Polyamide acid, and polyimide >
Polyamic acid esters, polyamic acids, and polyimides as polyimide precursors used in the present invention can be synthesized by a known method described in, for example, international publication WO 2013/157586.
< liquid Crystal alignment agent >
The liquid crystal aligning agent of the present invention is in the form of a solution in which a polymer component such as a specific polymer is dissolved in an organic solvent. The molecular weight of the specific polymer is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and further preferably 10,000 to 100,000 in terms of weight average molecular weight. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
The liquid crystal aligning agent of the present invention is a composition containing the above-mentioned specific polymer and an organic solvent, and may contain 2 or more different structures of the specific polymer. The liquid crystal aligning agent of the present invention may contain a polymer other than the specific polymer (hereinafter, also referred to as "2 nd polymer") and various additives.
When the liquid crystal aligning agent of the present invention contains the No. 2 polymer, the ratio of the specific polymer to the total polymer components is preferably 5% by mass or more, and examples thereof include 5 to 95% by mass.
Examples of the 2 nd polymer include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or a derivative thereof, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like.
Particularly, a polyamic acid (hereinafter, also referred to as a 2 nd polyamic acid) obtained from a tetracarboxylic dianhydride component and a diamine component is preferable as the 2 nd polymer.
Examples of the tetracarboxylic acid component for obtaining the 2 nd polyamic acid include tetracarboxylic dianhydrides represented by the following formula (11). The tetracarboxylic dianhydride may be 2 or more.
In the formula (11), A is a 4-valent organic group, preferably a 4-valent organic group having 4 to 30 carbon atoms.
The following shows a preferable structure of the above a, but the present invention is not limited to this.
Of the above-described structures, (a-1) and (a-2) are preferable from the viewpoint of further improving the photo-alignment property, (a-4) are preferable from the viewpoint of further improving the relaxation rate of charge accumulation, and (a-15) to (a-17) are preferable from the viewpoint of further improving the liquid crystal alignment property and the relaxation rate of charge accumulation. The tetracarboxylic dianhydride component used to obtain the 2 nd polyamic acid may be one type of tetracarboxylic dianhydride, or 2 or more types of tetracarboxylic dianhydrides may be used in combination.
The diamine component for obtaining the 2 nd polyamic acid can be appropriately determined according to the purpose, and for example, a diamine represented by the following formula (12) can be used.
(Y9Represents an organic group having a valence of 2. A. the9Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. From the viewpoint of liquid crystal alignment, A9More preferably a hydrogen atom or a methyl group. )
For the purpose of improving electrical characteristics and relaxation characteristics, Y9It is preferably an organic group having a valence of 2 of a tertiary nitrogen atom, or an organic group having a valence of 2 of-NH-CO-NH-in the molecule. As Y9Specific examples of the formula (12) in the case of an organic group having a valence of 2 of a tertiary nitrogen atom include diamines having an azole structure described in international publication No. WO2017/126627, and preferably diamines represented by the following formula (pr).
In the above formula (pr), R1Represents a hydrogen atom, hydrogen, a fluorine atom, a cyano group, a hydroxyl group, or a methyl group. R2Each independently represents a single bond or a group ". 1-R3-Ph-*2”，R3Represents a single bond selected from-O-, -COO-, -OCO-, - (CH)2)l-、-O(CH2)m2-valent organic of O-, -CONH-, and-NHCO-The group (l, m represents an integer of 1 to 5), the group 1 represents a site bonded to the benzene ring in the formula (pr), and the group 2 represents a site bonded to the amino group in the formula (pr). Ph represents a phenylene group. n represents 1 to 3.
Examples thereof include: the diamine having an azole structure described in international publication WO2018/062197, preferably a diamine having a structure represented by the following formula (pn):
(R1and R2Each independently represents a hydrogen atom or a methyl group, R3Represents a single bond or a group ". 1-R4-Ph-*2”，R4Represents a single bond selected from-O-, -COO-, -OCO-, - (CH)2)l-、-O(CH2)mAnd 2-valent organic groups (l and m each represents an integer of 1 to 5) in 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 a phenylene group. n represents 1 to 3. ) A
The diamine having a carbazole structure described in international publication WO2018/110354, preferably a diamine having a structure represented by the following formula (cz):
(R1represents a hydrogen atom or a methyl group, R2Represents a methyl group. ) A
A diamine having a nitrogen-containing heterocycle described in paragraphs [0173] to [0188] of International publication No. WO2015/046374, a diamine having a nitrogen-containing structure described in paragraph [0050] of Japanese patent laid-open publication No. 2016-218149, and a diamine represented by the following formula (BP):
(X is a biphenyl ring or a fluorene ring, and Y is selected from a benzene ring, a biphenyl ring, or-phenyl-Z-phenyl-)The radical Z is-O-, -NH-, -CH2-、-SO2-、-C(CH3)2-or C (CF)3)2-a group having a valence of 2 as indicated. A and B are a hydrogen atom or a methyl group), 2, 3-diaminopyridine, 2, 6-diaminopyridine, 3, 4-diaminopyridine, 2, 4-diaminopyrimidine, 5, 6-diamino-2, 3-dicyanopyrazine, 5, 6-diamino-2, 4-dihydroxypyrimidine, 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine, 1, 4-bis (3-aminopropyl) piperazine, 4 '- [4, 4' -propane-1, 3-diyl bis (piperidine-1, 4-diyl)]Diphenylamine, 2, 4-diamino-6-isopropoxy-1, 3, 5-triazine, 2, 4-diamino-6-methoxy-1, 3, 5-triazine, 2, 4-diamino-6-phenyl-1, 3, 5-triazine, 2, 4-diamino-6-methyl-s-triazine, 2, 4-diamino-1, 3, 5-triazine, 4, 6-diamino-2-vinyl-s-triazine, 3, 5-diamino-1, 2, 4-triazole, 6, 9-diamino-2-ethoxyacridine lactate, 3, 8-diamino-6-phenylphenanthridine, 1, 4-diaminopiperazine, piperazine hydrochloride, 2, 4-diamino-6-phenyl-triazine, 2, 4-diamino-phenyl-1, 3, 5-triazine, 2, 4-triazine, 2, 4-diamino-methyl-s-triazine, 2, 4-diamino-1, 4-methyl-2, 5-triazine, 2, 4-methyl-triazine, 2, 4-methyl-triazine, 2,3, 2, 4-methyl-triazine, 2-methyl-one, 2-methyl-one, ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-, 3, 6-diaminoacridine, bis (4-aminophenyl) phenylamine, 4 '-diphenylmethylamine, 4' -diphenylamine, 3, 6-diaminocarbazole, 9-methyl-3, 6-diaminocarbazole, 9-ethyl-3, 6-diaminocarbazole, diamines represented by the following formulae (w1) to (w2), and the like.
(Sp represents phenylene, pyrrolidine, piperidine, piperazine, 2-valent chain hydrocarbon group having 2 to 20 carbon atoms, or-CH of the 2-valent chain hydrocarbon group2A group substituted with a group selected from-O-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS-, -NR- (R represents a methyl group), pyrrolidine, piperidine, and piperazine. )
As Y9Specific examples of the above formula (12) in which the molecule has an organic group having a valence of 2-NH-CO-NH-, include those represented by formula (4) wherein A is1-CH being-NH-CO-NH-, or C2-20 chain alkyl2-CH having at least one group substituted with-NH-CO-NH-or a chain hydrocarbon group having 2 to 20 carbon atoms2At least one of-is-NH-CO-NH-metathesis and other-CH2And diamines in which at least one of the above-mentioned groups is substituted with a group selected from the group consisting of-O-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS-, -NR- (R represents a methyl group), and the like. Specific examples of more preferable diamines include diamines represented by the following formulas (U-1) to (U-9).
Preferable examples of the diamines represented by the above formulae (w1) to (w2) include diamines represented by the following formulae (n3-1) to (n3-7) and diamines represented by the following formulae (n4-1) to (n 4-6).
For the purpose of improving printability, a diamine compound having a carboxyl group (COOH group) and a hydroxyl group (OH group) may also be used. Specific examples thereof include 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid and 3, 5-diaminobenzoic acid. Among them, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, or 3, 5-diaminobenzoic acid is preferable. Further, diamine compounds represented by the following formulas [3b-1] to [3b-4] and diamine compounds in which the amino group is a secondary amino group can also be used.
(formula [3b-1]]In, Q1Represents a single bond, -CH2-、-C2H4-、-C(CH3)2-、-CF2-、-C(CF3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、-OCO-、-CON(CH3) -or N (CH)3)CO-，m1And m2Each independently represents an integer of 0 to 4, and m1+m2Represents an integer of 1 to 4, formula [3b-2 ]]M in3And m4Each independently represents an integer of 1 to 5, formula [3b-3]In, Q2M represents a linear or branched alkylene group having 1 to 5 carbon atoms5Represents an integer of 1 to 5, formula [3b-4]]In, Q3And Q4Each independently represents a single bond, -CH2-、-C2H4-、-C(CH3)2-、-CF2-、-C(CF3)2-、-O-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-OCH2-、-COO-、-OCO-、-CON(CH3) -or N (CH)3)CO-，m6Represents an integer of 1 to 4. )
The diamine component used for obtaining the 2 nd polyamic acid may be any of the diamines used for the specific polymers and known diamines, in addition to the above, but the present invention is not limited to these. The diamine component for obtaining the 2 nd polyamic acid may be one kind of diamine, or 2 or more kinds of diamines may be used in combination.
The molecular weight of the 2 nd polymer contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as a uniform and defect-free coating film can be formed on a substrate, and the preferable weight average molecular weight and number average molecular weight are the same as those of the specific polymer.
Examples of the various additives to be added to the liquid crystal alignment agent include dielectric or conductive substances for the purpose of 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 the purpose of efficiently imidizing a polyamic acid when a coating film is baked.
The crosslinkable compound is preferably added with at least 1 compound selected from the group consisting of crosslinkable compounds having a substituent such as an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a blocked isocyanate group, a hydroxyl group or an alkoxy group, and crosslinkable compounds having a polymerizable unsaturated group.
When the crosslinkable compound has 2 or more of these substituents and polymerizable unsaturated bonds, it is preferable from the viewpoint of improving the crosslinkability. Specific examples of the crosslinkable compound include compounds having an epoxy group or an isocyanate group described in paragraphs [0169] to [0190] of International patent publication No. 2011/132751; a compound having an oxetanyl group; amino resins having a hydroxyl group, an alkoxy group or a lower alkoxyalkyl group; a benzene or phenol compound having a hydroxyl group or an alkoxy group; compounds having a cyclic carbonate group described in paragraphs [0103] to [0112] of International publication No. 2012/014898; a compound having a hydroxyalkylamide group described in International publication No. 2015/072554; a compound having a blocked isocyanate group described in International publication No. 2015/141598.
More preferred examples of the crosslinkable compound include compounds represented by the following formulas (CL-1) to (CL-13), TAKENATE B-830 and TAKENATE B-882 (all of which are available from Mitsui chemical Co., Ltd.).
The content of the crosslinkable compound is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the total polymer components contained in the liquid crystal aligning agent, and more preferably 0.1 to 50 parts by mass, and even more preferably 1 to 50 parts by mass, from the viewpoint of improving the alignment property of the liquid crystal.
Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 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-triethoxysilylpropyltriethylenetriamine, and mixtures thereof, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4, 7-triazadecane, 10-triethoxysilyl-1, 4, 7-triazadecane, 9-trimethoxysilyl-3, 6-diazisononyl acetate, 9-triethoxysilyl-3, 6-diazisononyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, N-bis (oxy-3-hydroxy-ethyl-1, 4, 7-diazacyclodecane, N-triethoxysilyl-3, 6-diazisononyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-bis (oxy-3-aminopropyltrimethoxysilane, N-bis (oxy-methyl-ethoxysilane, N-methyl-3-amino-propyl-triethoxysilane, N-3-triethoxy-methyl-3-amino-propyl-triethoxysilane, N-phenyl-3-triethoxy-bis (oxy-phenyl-3-amino-propyl) trimethoxysilane, N-bis (oxy-phenyl-3-amino-triethoxy-methyl-phenyl-ethyl-3-ethyl-methyl-phenyl-ethyl-phenyl-ethyl-tri-phenyl-ethyl-phenyl-ethyl-phenyl-3-ethyl-phenyl-ethyl-phenyl-ethyl-phenyl-ethyl-phenyl-ethyl-phenyl-ethyl-tri-phenyl-ethyl-phenyl-ethyl-phenyl-ethyl-phenyl-ethyl-phenyl-ethyl-phenyl-ethyl-phenyl-N-ethyl-N-ethyl-, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-vinyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxytriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxytriethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, and 3-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, and a-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxytrimethoxysilane, 3-epoxypropyltriethoxysilane, 3-epoxypropyl, Trans- (trimethoxysilylpropyl) isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like. When these silane coupling agents are used, from the viewpoint of ensuring liquid crystal alignment properties, the amount of the silane coupling agent is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total polymer components contained in the liquid crystal alignment agent.
The concentration of the polymer containing the specific polymer in the liquid crystal aligning agent of the present invention can be appropriately changed according to the setting of the thickness of the coating film to be formed. Among them, it is preferably 1 mass% or more in terms of the formation of a uniform and defect-free coating film, and 10 mass% or less in terms of the storage stability of the solution. The concentration of the polymer is particularly preferably 2 to 8 mass%.
The organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, γ -butyrolactone, 1, 3-dimethyl-imidazolidinone, and 3-methoxy-N, N-dimethylpropanamide. These may be used in 1 kind or in combination of 2 or more kinds. In addition, even if the solvent is a solvent which cannot uniformly dissolve the polymer component alone, the solvent may be mixed with the organic solvent as long as the polymer is not precipitated.
The liquid crystal aligning agent of the present invention may contain a solvent for improving the uniformity of a coating film when the liquid crystal aligning agent is applied to a substrate, in addition to an organic solvent for dissolving the polymer component. The solvent is generally a solvent having a lower surface tension than the above organic solvent. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, diacetone alcohol, diisobutyl ketone, dipropylene glycol monomethyl ether, Diisobutylcarbinol and the like. These solvents may be used in combination of 2 or more.
< method for producing liquid Crystal alignment film >
As described above, the method for producing a liquid crystal alignment film using the liquid crystal aligning agent of the present invention is characterized by sequentially performing the following steps: a step (A)) of applying a liquid crystal aligning agent; a step (B)) of baking the coating film obtained in step (A); irradiating the film obtained in the step (B) with polarized ultraviolet rays (step (C)); and (D) firing the film obtained in step (C) at a temperature of 100 ℃ or higher than that in step (B).
< Process (A) >
The substrate to which the liquid crystal aligning agent used in the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used together with a glass substrate or a silicon nitride substrate. In this case, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed, from the viewpoint of simplification of the process. In the reflective liquid crystal display element, if the substrate is a single-sided substrate, an opaque object such as a silicon wafer may be used, and in this case, a material that reflects light such as aluminum may be used for the electrodes.
The method of applying the liquid crystal aligning agent is not particularly limited, and a method of applying the liquid crystal aligning agent by screen printing, offset printing, flexographic printing, inkjet method, or the like is generally industrially used. As other coating methods, there are a dipping method, a roll coating method, a slit coating method, a spinner method, a spray method, and the like, and these methods can be used according to the purpose.
< Process (B) >
The step (B) is a step of firing the liquid crystal aligning agent applied to the substrate to form a film. After the liquid crystal aligning agent is applied to the substrate, the solvent can be evaporated or the amic acid or amic acid ester in the polymer can be thermally imidized by heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven. The drying and firing steps after the application of the liquid crystal aligning agent of the present invention may be carried out at any temperature and for any time, or may be carried out several times. The temperature for removing the organic solvent of the liquid crystal aligning agent may be, for example, 40 to 150 ℃. From the viewpoint of shortening the process, the reaction may be carried out at 40 to 120 ℃. The firing time is not particularly limited, and may be 1 to 10 minutes or 1 to 5 minutes. In the case of thermal imidization of amic acid or amic acid ester in the polymer, the step of removing the organic solvent may be followed by a step of firing at a temperature in the range of, for example, 190 to 250 ℃ or 200 to 240 ℃. The firing time is not particularly limited, and may be 5 to 40 minutes or 5 to 30 minutes.
< Process (C) >
The step (C) is a step of irradiating the film obtained in the step (B) with polarized ultraviolet rays. As the ultraviolet ray, ultraviolet rays having a wavelength of 200 to 400nm are preferably used, and among them, ultraviolet rays having a wavelength of preferably 200 to 300nm are more preferred. In order to improve the liquid crystal alignment property, 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 10,000mJ/cm2. Among them, it is preferably 100 to 5,000mJ/cm2. The liquid crystal alignment film thus produced can stably align liquid crystal molecules in a certain direction.
The higher the extinction ratio of polarized ultraviolet light, the more anisotropic the polarization can be imparted, and therefore, the higher the extinction ratio is preferable. Specifically, the extinction ratio of the linearly polarized ultraviolet ray is preferably 10: 1 or more, more preferably 20: 1 or more.
< Process (D) >
The step (D) is a step of firing the film obtained in the step (C) at a temperature of 100 ℃ or higher than that in the step (B). The firing temperature is not particularly limited as long as it is 100 ℃ or higher and higher than the firing temperature in the step (B), and is preferably 150 to 300 ℃, more preferably 150 to 250 ℃, and still more preferably 200 to 250 ℃. The firing time is preferably 5 to 120 minutes, more preferably 5 to 60 minutes, and further preferably 5 to 30 minutes.
If the thickness of the liquid crystal alignment film after firing is too thin, the reliability of the device may be lowered by the liquid crystal, and therefore, it is preferably 5 to 300nm, more preferably 10 to 200 nm.
Further, after any of the above-mentioned steps (C) or (D) is performed, the obtained liquid crystal alignment film may be subjected to a contact treatment with water or a solvent.
The solvent used in the contact treatment is not particularly limited as long as it dissolves a decomposition product formed from the liquid crystal alignment film by irradiation with ultraviolet rays. 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. The number of the solvents may be 1, or 2 or more may be used in combination.
The contact treatment, that is, the treatment of the liquid crystal alignment film irradiated with the polarized ultraviolet ray with water or a solvent, includes a dipping treatment and a spraying treatment (also referred to as a spray treatment). The treatment time of these treatments is preferably 10 seconds to 1 hour from the viewpoint of efficiently dissolving the decomposition product generated from the liquid crystal alignment film by the ultraviolet rays. Among them, the immersion treatment is preferably performed for 1 to 30 minutes. The solvent used in the contact treatment may be heated at normal temperature, but is preferably 10 to 80 ℃. Among them, the preferable range is 20 to 50 ℃. Further, ultrasonic treatment or the like may be performed as necessary in view of the solubility of the decomposition product.
After the contact treatment, it is preferable to perform rinsing (also referred to as rinsing) with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone, or to perform baking of the liquid crystal alignment film. In this case, either one of washing and firing may be performed, or both may be performed. The firing temperature is preferably 150 to 300 ℃. Among them, it is preferably 180 to 250 ℃. More preferably 200 to 230 ℃. The time for firing is preferably 10 seconds to 30 minutes. Among them, 1 to 10 minutes is preferable.
The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a liquid crystal display element of a transverse electric field system such as an IPS system or an FFS system, and is particularly useful as a liquid crystal alignment film for a liquid crystal display element of an FFS system. The liquid crystal display element is obtained as follows: the liquid crystal cell can be obtained by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention, then producing a liquid crystal 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 the liquid crystal display element may be an active matrix liquid crystal display element in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting an image display.
Specifically, a transparent glass substrate is prepared, a common electrode is provided on one substrate, and segment electrodes are provided on the other substrate. These electrodes, which may be patterned using, for example, ITO electrodes, enable a desired image representation. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode. The insulating film may be, for example, SiO formed by a sol-gel method2-TiO2The film of (1).
Next, a liquid crystal alignment film is formed on each substrate, and one substrate is overlaid on the other substrate so that the liquid crystal alignment films face each other, and the periphery is bonded with a sealant. In order to control the substrate gap, it is preferable that spacers are mixed in the sealant in advance, and spacers for controlling the substrate gap are also dispersed in advance in the surface portion where the sealant is not provided. An opening portion into which liquid crystal can be filled from the outside is provided in advance in a part of the sealant. Next, a liquid crystal material was injected into the space surrounded by the 2 substrates and the sealant through the opening provided in the sealant, and then the opening was sealed with an adhesive. The injection may be performed by a vacuum injection method or a method using a capillary phenomenon in the atmosphere. As the liquid crystal material, any of positive type liquid crystal materials and negative type liquid crystal materials can be used. Next, a polarizing plate is provided. Specifically, a pair of polarizing plates was attached to 2 substrates on the opposite side of the liquid crystal layer.
As described above, the following liquid crystal alignment film can be obtained by the manufacturing method of the present invention: a liquid crystal alignment film which can be produced by a smaller number of steps than conventional liquid crystal alignment films while suppressing image sticking due to long-term AC drive occurring in liquid crystal display elements of the IPS drive system and the FFS drive system and eliminating defects such as bright spots due to the remaining low molecular weight compounds.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. The following compounds are abbreviated and the respective properties are measured as follows.
(diamine)
(Boc represents a tert-butoxycarbonyl group.)
(tetracarboxylic dianhydride)
CA-X-1: a compound represented by the following formula (CA-X-1)
(Compound C)
c-1: a compound represented by the following formula (c-1)
(other additives)
LS-4668: 3-glycidoxypropyltriethoxysilane (Compound represented by the following (s-1))
(organic solvent)
NMP: n-methyl-2-pyrrolidone, GBL: gamma-butyrolactone,
BCS: butyl cellosolve,
< measurement of imidization Rate >
20mg of the polyimide powder was put into an NMR sample tube (NMR sample tube standard,
(manufactured by SoftySet corporation)), 0.53ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) was added thereto, and the mixture was dissolved completely by applying ultrasonic waves. The solution was subjected to 500MHz proton NMR measurement with an NMR spectrometer (JNW-ECA500, manufactured by JEOL DATUM LTD.). The imidization ratio is determined by using a proton derived from a structure which does not change before and after imidization as a reference proton, and obtaining the peak cumulative value of the proton and the peak cumulative value of the proton derived from the NH group of amic acid appearing in the vicinity of 9.5ppm to 10.0ppm by the following formula.
Imidization ratio (%) - (1-. alpha.x/y). times.100
In the above formula, x is a peak cumulative value of a proton derived from an NH group of amic acid, y is a peak cumulative value of a reference proton, and α is a number ratio of 1 proton of the NH group of amic acid to the reference proton in the case of polyamic acid (imidization ratio of 0%).
[ Synthesis of Polymer ]
< Synthesis example 1>
In a four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.62g (14.8mmol) of DA-h-1, 4.75g (14.8mmol) of DA-h-2, 1.92g (17.8mmol) of DA-i-1, and 4.05g (11.9mmol) of DA-j-1 were weighed, and NMP was added so that the solid content concentration became 12 mass%, and the mixture was dissolved by stirring while feeding nitrogen. While stirring the resulting solution, 10.1g (45.2mmol) of CA-1-1, 2.12g (8.5mmol) of CA-2-1, and 0.83g (2.8mmol) of CA-3-1 were added, and NMP was further added so that the solid content concentration became 15 mass%. Subsequently, stirring was performed at 40 ℃ for 24 hours to obtain a polyamic acid solution.
30.0g of the obtained polyamic acid solution was taken out from a 100mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and NMP was added thereto so that the solid content concentration became 10% by mass, and the mixture was stirred for 30 minutes. To the obtained polyamic acid solution were added 2.80g of acetic anhydride and 1.50g of pyridine, and the mixture was heated at 55 ℃ for 3 hours to effect chemical imidization. The obtained reaction solution was stirred and poured into methanol in an amount of 3.5 times the mass of the reaction solution, and the precipitated precipitate was collected by filtration and washed with methanol 3 times. The obtained resin powder was dried at 60 ℃ for 12 hours, thereby obtaining a powder of polyimide (PI-A-1). The imidization ratio of the polyimide resin powder was 62%. NMP was added to the obtained polyimide (PI-A-1), and the mixture was stirred at 70 ℃ for 24 hours to obtain a polyimide (PI-A-1) solution having a solid content of 12 mass%.
< Synthesis examples 2 to 5>
The preparation of polyimide solutions (PI-A-2) to (PI-A-4) and (R-PI-1) and polyamic acids (PAA-B-1) to (PAA-B-3) shown in Table 1 were carried out in the same manner as in Synthesis example 1 using the diamine component, the tetracarboxylic acid component and the organic solvent shown in Table 1. In addition, LS-4668 was added to each of the polyamic acids (PAA-B-1) to (PAA-B-3) so as to be 1 mass% based on the solid content of the polyamic acid.
In table 1, the parenthesized numerical values indicate the blending ratio (molar parts) of each compound to 100 molar parts of the total amount of the tetracarboxylic acid component used in the synthesis for the tetracarboxylic acid component, and indicate the blending ratio (molar parts) of each compound to 100 molar parts of the total amount of the diamine component used in the synthesis for the diamine acid component. The organic solvents were mixed in a proportion (parts by mass) of each organic solvent to 100 parts by mass of the total amount of the organic solvent used in the synthesis.
[ Table 1]
[ preparation of liquid Crystal Aligning agent ]
< example 1>
The solution of the polyimide (PI-a-1) obtained in synthesis example 1 was diluted with NMP and BCS, and stirred at room temperature. Then, the obtained solution was filtered through a filter having a pore size of 0.5 μm, thereby obtaining a liquid crystal aligning agent (1) having a solvent composition ratio (NMP: BCS: 80: 20 (mass ratio)) and a polymer solid content concentration of 6 mass% (see table 2 below). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as clouding and precipitation.
< examples 2 to 4 and comparative example 1>
Liquid crystal alignment agents (2) to (4) and (R1) were obtained in the same manner as in example 1, except that each polymer shown in table 2 below was used.
< examples 5 to 7 and comparative example 2>
The solution of polyimide (PI-a-2) obtained in synthesis example 2 and the solution of polyamic acid (PAA-B-1) obtained in synthesis example 6 were diluted with NMP, GBL, and BCS, and compound (c-1) was added in an amount of 3 parts by mass per 100 parts by mass of the total polymer, and stirred at room temperature. Then, the obtained solution was filtered through a filter having a pore size of 0.5 μm, whereby a polymer having a component ratio of (PI-A-2): (PAA-B-1) ═ 40: 60 (solid content conversion mass ratio) and a solvent composition ratio of NMP: GBL: BCS 50: 30: 20 (mass ratio) and a polymer solid content concentration of 6 mass% (see table 2 below). The liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as clouding and precipitation.
In table 2, the numerical values in parentheses show the blending ratio (parts by mass) of each polymer component or compound (C) to 100 parts by mass of the total of the polymer components used in the production of the liquid crystal aligning agent for the polymer and compound (C), respectively. The blending ratio (parts by mass) of each organic solvent to 100 parts by mass of the total amount of organic solvents used in the preparation of the liquid crystal aligning agent is shown for the organic solvents.
[ Table 2]
[ production of liquid Crystal display element ]
A liquid crystal cell having a structure including an FFS mode liquid crystal display element was produced.
First, a substrate with an electrode is prepared. The substrate was a glass substrate having dimensions of 30mm × 50mm and a thickness of 0.7 mm. An ITO electrode having a solid pattern is formed on the substrate as the 1 st layer constituting the counter electrode. A SiN (silicon nitride) film formed by a CVD method is formed as a 2 nd layer on the counter electrode of the 1 st layer. The SiN film of the 2 nd layer has a film thickness of 500nm and functions as an interlayer insulating film. On the SiN film of the 2 nd layer, a comb-teeth-shaped pixel electrode formed by patterning an ITO film is disposed as a 3 rd layer, and 2 pixels of the 1 st pixel and the 2 nd pixel are formed. For each pixel size, the vertical direction is 10mm and the horizontal direction is about 5 mm. At this time, the counter electrode of the 1 st layer and the pixel electrode of the 3 rd layer are electrically insulated by the SiN film of the 2 nd layer.
The pixel electrode of the layer 3 has a comb-teeth shape in which a plurality of "く -shaped" electrode elements each having a central portion bent at an internal angle of 160 ° are arranged. The width of each electrode element in the short side direction was 3 μm, and the interval between the electrode elements was 6 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of "く -shaped" electrode elements each having a bent central portion, each pixel has a shape similar to a thick "く -shaped" electrode element bent at a central portion, similarly to the electrode elements, instead of a rectangular shape. Each pixel is divided into upper and lower parts with a curved portion at the center thereof as a boundary, and has an upper 1 st region and a lower 2 nd region of the curved portion.
Next, a liquid crystal aligning agent was applied by spin coating to the substrate with electrodes and the glass substrate having a column spacer with a height of 4 μm on the back surface of which an ITO film was formed. After drying the film on a hot plate at 80 ℃ for 2 minutes, the film surface was irradiated with a polarizing plate to give an extinction ratio of 26: 1, then, the substrate was fired in a thermal peak circulation oven at 230 ℃ for 30 minutes to obtain a substrate having a liquid crystal alignment film with a film thickness of 100 nm. The liquid crystal alignment film formed on the electrode-provided substrate was aligned so that the direction bisecting the inner angle of the bent portion of the pixel was orthogonal to the alignment direction of the liquid crystal, and the liquid crystal alignment film formed on the 2 nd glass substrate was aligned so that the alignment direction of the liquid crystal on the 1 st substrate was aligned with the alignment direction of the liquid crystal on the 2 nd substrate when the liquid crystal cell was manufactured. The obtained 2 substrates with liquid crystal alignment films were set to 1 group, a sealant was printed on the substrates with a liquid crystal injection port left, and another 1 substrate was attached with the liquid crystal alignment films facing each other. Thereafter, the sealant was cured to prepare an empty cell having a cell gap of 4 μm. The empty cell was injected with liquid crystal MLC-3019 (manufactured by Merck) by a reduced pressure injection method, and the injection port was sealed to obtain an FFS type liquid crystal display element. Thereafter, the resulting liquid crystal display element was heated at 120 ℃ for 1 hour and placed at 23 ℃ late for evaluation.
[ evaluation ]
Evaluation of remaining dose of irradiation
The liquid crystal display element obtained above was applied with an alternating voltage of ± 5V for 120 hours at a frequency of 60Hz in a constant temperature environment of 60 ℃. Thereafter, the liquid crystal display element was short-circuited between the pixel electrode and the counter electrode, and was left as it was at room temperature for one day.
The liquid crystal display element subjected to the above-described processing was subjected to angle calculation to calculate the deviation between the alignment direction of the liquid crystal in the 1 st region and the alignment direction of the liquid crystal in the 2 nd region of the pixel in the state where no voltage was applied.
Specifically, a liquid crystal display element is provided between 2 polarizing plates arranged so that the polarizing axes are orthogonal to each other, the backlight is turned on, the arrangement angle of the liquid crystal cell is adjusted so as to minimize the transmitted light intensity in the 1 st region of the pixel, and then the rotation angle (hereinafter referred to as Δ) required for rotating the liquid crystal cell so as to minimize the transmitted light intensity in the 2 nd region of the pixel is obtainedac)。
By the use of this deltaacMinimum light irradiation E of less than 0.15 DEGmin(mJ/cm2) And the highest light irradiation amount Emax(mJ/cm2) Evaluation was performed according to the following 3-level index. The evaluation results are shown in table 3 below.
And (3) excellent: emaxAnd EminThe difference of (A) is 300mJ/cm2The above.
Good: emaxAnd EminThe difference of (A) is 200mJ/cm2Above and less than 300mJ/cm2。
Poor: emaxAnd EminDifference of (2)Less than 200mJ/cm2。
[ Table 3]
As described above, the liquid crystal alignment films obtained from the liquid crystal aligning agents (1) to (7) used in examples 1 to 7 of the present invention were irradiated with 150 to 350mJ/cm2Or 150 to 450mJ/cm2At the amount of light irradiation of (D), ΔacAre all less than 0.15 DEG, and show good afterimage characteristics. The liquid crystal aligning agents (R1) - (R2) used in comparative examples 1-2 were irradiated at 150-250 mJ/cm2Δ when amount of light irradiation is measuredacLess than 0.15 DEG, shows good afterimage characteristics, but is irradiated at 350mJ/cm2Δ when amount of light irradiation is measuredacIs 0.15 DEG or more, and good afterimage characteristics cannot be obtained. As described above, the liquid crystal alignment agent of the present invention can provide a liquid crystal alignment film having a good residual image characteristic while increasing the light irradiation dose margin. Therefore, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention has a high yield in the production of liquid crystal panels, and can reduce the residual image due to ac driving generated in the liquid crystal display elements of the IPS driving method and the FFS driving method, thereby obtaining the liquid crystal display elements of the IPS driving method and the FFS driving method having excellent residual image characteristics.
Industrial applicability
The liquid crystal aligning agent of the present invention is useful for forming a liquid crystal alignment film of a wide variety of liquid crystal display devices such as IPS drive systems and FFS drive systems.
The entire contents of the specification, claims, drawings and abstract of japanese patent application No. 2018-216789, which was filed on 11/19/2018, are incorporated herein as the disclosure of the specification of the present invention.
Claims (15)
1. A liquid crystal aligning agent comprising a polyimide which is an imide compound of a polyimide precursor obtained by a polymerization reaction of a tetracarboxylic acid component and a diamine component, wherein the tetracarboxylic acid component comprises: a tetracarboxylic dianhydride represented by the following formula (1) or a derivative thereof, a tetracarboxylic dianhydride represented by the following formula (2) or a derivative thereof, and an aromatic tetracarboxylic dianhydride represented by the following formula (6),
X1is a structure represented by any one of the following formulae (X1-1) to (X1-4), X2Is a structure represented by the following formula (X2-1) or (X2-2), X3Is an aromatic ring having 4 linkages,
R3～R6each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a 1-valent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, and at least one of them is not a hydrogen atom, R7～R23Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a 1-valent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group,
2. the liquid crystal aligning agent according to claim 1, wherein the polyimide has an imidization ratio of 10 to 100%.
3. The liquid crystal aligning agent according to claim 1 or 2, wherein the tetracarboxylic acid component contains 1 to 30 mol% of the tetracarboxylic dianhydride represented by the formula (2) or the derivative thereof with respect to the tetracarboxylic acid component.
4. The liquid crystal aligning agent according to claim 1 or 2, wherein the tetracarboxylic acid component contains 1 to 20 mol% of the tetracarboxylic dianhydride represented by the formula (6) or the derivative thereof with respect to the tetracarboxylic acid component.
5. The liquid crystal aligning agent according to claim 1 to 4, wherein X in the formula (1)1Is at least 1 selected from the structures represented by any one of the following formulae (X1-12) to (X1-16),
6. the liquid crystal aligning agent according to claim 1 to 4, wherein X in the formula (1)1Is at least 1 selected from the structures represented by any one of the formulae (X1-12) to (X1-16).
7. The liquid crystal aligning agent according to claim 1 to 6, wherein in the formula (2), X2Is a structure represented by the formula (X2-1).
8. The liquid crystal aligning agent according to claim 1 to 7, wherein the diamine component contains at least 1 kind of diamine selected from the group consisting of the structures represented by any one of the following formulae (3), (4) and (5),
A1and A4Each independently represents a single bond, -CO-O-, -OCO-, -NRCO-, -NRCOO-, -CONR-, -COS-, -NR-1-CO-NR2-, a C2-20 chain hydrocarbon group having a valence of 2 or-CH of the C2 chain hydrocarbon group2Is selected from-O-, -CO-O-, -NRCO-, -NRCOO-, -CONR-, -COS-, -NR-, -1-CO-NR2-, -NR-, pyrrolidine, piperidine, piperazineA group (h1) wherein in the group-NRCO-, R represents a hydrogen atom or a methyl group, in the group-NRCOO-, R represents a hydrogen atom or a methyl group, in the group-CONR-, R represents a hydrogen atom or a methyl group, and the group-NR1-CO-NR2In (A) R1And R2Each independently represents a hydrogen atom or a methyl group, and in the formula-NR-, R represents a methyl group; a. the2Hydrogen atom, halogen atom, hydroxyl group, amino group, mercapto group, nitro group, phosphate group, or C1-20 organic group; wherein, A is1And A4The chain hydrocarbon group (b) and the group (h1) have hydrogen atoms, part or all of which are optionally substituted by C1-3 alkyl groups or halogen atoms; a. the3Is a 2-valent chain hydrocarbon group having 1 to 20 carbon atoms or-CH of the 2-valent chain hydrocarbon group2Is selected from-O-, -CO-O-, -NRCO-, -NRCOO-, -CONR-, -COS-, -NR-, -1-CO-NR2A group (h2) wherein R in the group-NRCO-represents a hydrogen atom or a methyl group, R in the group-NRCOO-represents a hydrogen atom or a methyl group, R in the group-CONR-represents a hydrogen atom or a methyl group, and the group-NR-1-CO-NR2In (A) R1And R2Each independently represents a hydrogen atom or a methyl group, and in the formula-NR-, R represents a methyl group; wherein A is3A part or all of hydrogen atoms of the chain hydrocarbon group and the group (h2) are optionally substituted by an alkyl group having 1 to 3 carbon atoms or a halogen atom; a is an integer of 1 to 4, and when a is 2 or more, A is2Optionally the same or different; b and c are each independently an integer of 1 or 2; d is an integer of 0 or 1.
9. The liquid crystal aligning agent according to claim 1 to 8, wherein the diamine component contains at least 1 diamine selected from the group consisting of the following formulas (DA-3-1), (DA-4-1) to (DA-4-24), (DA-5-1) to (DA-5-3),
10. a method for producing a liquid crystal alignment film, comprising the steps of (A), (B), (C) and (D),
step (A): a step of applying the liquid crystal aligning agent according to any one of claims 1 to 9;
a step (B): firing the coating film obtained in the step (a);
step (C): irradiating the film obtained in the step (B) with polarized ultraviolet rays;
a step (D): and (C) firing the film obtained in step (C) at a temperature of 100 ℃ or higher than that in step (B).
11. The method of producing a liquid crystal alignment film according to claim 10, wherein in the step (B), the firing is performed at 50 to 150 ℃.
12. The method for producing a liquid crystal alignment film according to claim 10 or 11, wherein in the step (D), the film is fired at 150 to 300 ℃.
13. A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of claims 1 to 9.
14. A liquid crystal display element comprising the liquid crystal alignment film according to claim 13.
15. A liquid crystal display element according to claim 14, which drives the liquid crystal with a lateral electric field.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-216789 | 2018-11-19 | ||
| JP2018216789 | 2018-11-19 | ||
| PCT/JP2019/044925 WO2020105561A1 (en) | 2018-11-19 | 2019-11-15 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113168052A true CN113168052A (en) | 2021-07-23 |
Family
ID=70773182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980076518.4A Pending CN113168052A (en) | 2018-11-19 | 2019-11-15 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7414006B2 (en) |
| KR (1) | KR20210092194A (en) |
| CN (1) | CN113168052A (en) |
| TW (1) | TWI816939B (en) |
| WO (1) | WO2020105561A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116042235A (en) * | 2023-01-31 | 2023-05-02 | 长沙道尔顿电子材料有限公司 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method for producing liquid crystal alignment film |
| CN117567741A (en) * | 2024-01-11 | 2024-02-20 | 武汉柔显科技股份有限公司 | Polyamic acid and preparation method thereof, liquid crystal aligning agent, alignment film and display device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105408811A (en) * | 2013-05-22 | 2016-03-16 | 日产化学工业株式会社 | Liquid crystal alignment agent, and liquid crystal alignment film and liquid crystal display element using same |
| CN107209423A (en) * | 2015-02-06 | 2017-09-26 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal represent that element and liquid crystal represent the manufacture method of 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 |
| WO2018159733A1 (en) * | 2017-03-02 | 2018-09-07 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3893659B2 (en) | 1996-03-05 | 2007-03-14 | 日産化学工業株式会社 | Liquid crystal alignment treatment method |
| JP5654228B2 (en) | 2009-11-13 | 2015-01-14 | 株式会社ジャパンディスプレイ | Liquid crystal display device and method of manufacturing liquid crystal display device |
| JP6252752B2 (en) | 2013-04-09 | 2017-12-27 | Jsr株式会社 | Liquid crystal alignment agent |
| CN108604028A (en) | 2015-11-30 | 2018-09-28 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal indicate element |
| JP6565730B2 (en) * | 2016-02-18 | 2019-08-28 | Jnc株式会社 | Diamine, polyamic acid or derivative thereof, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
-
2019
- 2019-11-15 WO PCT/JP2019/044925 patent/WO2020105561A1/en active Application Filing
- 2019-11-15 KR KR1020217008817A patent/KR20210092194A/en unknown
- 2019-11-15 CN CN201980076518.4A patent/CN113168052A/en active Pending
- 2019-11-15 JP JP2020558354A patent/JP7414006B2/en active Active
- 2019-11-18 TW TW108141741A patent/TWI816939B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105408811A (en) * | 2013-05-22 | 2016-03-16 | 日产化学工业株式会社 | Liquid crystal alignment agent, and liquid crystal alignment film and liquid crystal display element using same |
| CN107209423A (en) * | 2015-02-06 | 2017-09-26 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal represent that element and liquid crystal represent the manufacture method of 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 |
| WO2018159733A1 (en) * | 2017-03-02 | 2018-09-07 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116042235A (en) * | 2023-01-31 | 2023-05-02 | 长沙道尔顿电子材料有限公司 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method for producing liquid crystal alignment film |
| CN117567741A (en) * | 2024-01-11 | 2024-02-20 | 武汉柔显科技股份有限公司 | Polyamic acid and preparation method thereof, liquid crystal aligning agent, alignment film and display device |
| CN117567741B (en) * | 2024-01-11 | 2024-04-19 | 武汉柔显科技股份有限公司 | Polyamic acid and preparation method thereof, liquid crystal aligning agent, alignment film and display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7414006B2 (en) | 2024-01-16 |
| TW202035519A (en) | 2020-10-01 |
| TWI816939B (en) | 2023-10-01 |
| WO2020105561A1 (en) | 2020-05-28 |
| KR20210092194A (en) | 2021-07-23 |
| JPWO2020105561A1 (en) | 2021-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7392646B2 (en) | Liquid crystal alignment agent, manufacturing method thereof, liquid crystal alignment film, and liquid crystal display element | |
| JPWO2020158818A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element using it | |
| JP2024059669A (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same | |
| JP7414006B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| WO2021177080A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| CN111133373B (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same | |
| WO2022176680A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| WO2020158819A1 (en) | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element | |
| CN113423763B (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same | |
| CN115968453A (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element | |
| WO2021177113A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| TW201630979A (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element | |
| JP7428138B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| JP7469736B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| JP7409375B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same | |
| WO2022181311A1 (en) | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element | |
| WO2022190896A1 (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| WO2022085674A1 (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element | |
| WO2021215280A1 (en) | Novel diamine, polymer, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |