CN102893208A - Liquid crystal alignment agent containing polyamic acid ester and polyamic acid, and liquid crystal alignment film - Google Patents
Liquid crystal alignment agent containing polyamic acid ester and polyamic acid, and liquid crystal alignment film Download PDFInfo
- Publication number
- CN102893208A CN102893208A CN201180024057XA CN201180024057A CN102893208A CN 102893208 A CN102893208 A CN 102893208A CN 201180024057X A CN201180024057X A CN 201180024057XA CN 201180024057 A CN201180024057 A CN 201180024057A CN 102893208 A CN102893208 A CN 102893208A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- polyamic acid
- acid ester
- aligning agent
- poly amic
- 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.)
- Granted
Links
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 284
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 233
- 150000002148 esters Chemical class 0.000 title claims abstract description 154
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 115
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 17
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 16
- 125000000962 organic group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 230000010287 polarization Effects 0.000 claims description 6
- 230000002285 radioactive effect Effects 0.000 claims description 6
- 230000003252 repetitive effect Effects 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 150
- 239000000243 solution Substances 0.000 description 127
- 230000015572 biosynthetic process Effects 0.000 description 73
- 238000003786 synthesis reaction Methods 0.000 description 72
- 238000003756 stirring Methods 0.000 description 71
- -1 diamine compound Chemical class 0.000 description 50
- 239000000758 substrate Substances 0.000 description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 43
- 238000000034 method Methods 0.000 description 41
- 210000004027 cell Anatomy 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 238000009835 boiling Methods 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- 239000006087 Silane Coupling Agent Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 19
- 150000001412 amines Chemical class 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 150000004985 diamines Chemical class 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 229920001721 polyimide Polymers 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 125000001309 chloro group Chemical group Cl* 0.000 description 9
- 239000000470 constituent Substances 0.000 description 9
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 150000003672 ureas Chemical class 0.000 description 4
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-methylmorpholine Substances CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- IXUOOKWOOJAKIB-UHFFFAOYSA-N 2-methoxycarbonylterephthalic acid Chemical compound COC(=O)C1=CC(C(O)=O)=CC=C1C(O)=O IXUOOKWOOJAKIB-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- WVOLTBSCXRRQFR-SJORKVTESA-N Cannabidiolic acid Natural products OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@@H]1[C@@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-SJORKVTESA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WVOLTBSCXRRQFR-DLBZAZTESA-N cannabidiolic acid Chemical compound OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-DLBZAZTESA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000005493 condensed matter Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 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 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-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
- SBHHKGFHJWTZJN-UHFFFAOYSA-N 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1(C)C(C(O)=O)C(C)(C(O)=O)C1C(O)=O SBHHKGFHJWTZJN-UHFFFAOYSA-N 0.000 description 1
- MISTZQJSHHTDCF-UHFFFAOYSA-N 1-(1-propoxyethoxy)propane Chemical compound CCCOC(C)OCCC MISTZQJSHHTDCF-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- QVSOLLSKUUJXQA-UHFFFAOYSA-N 2,3-dimethoxy-4-methyl-3-(1,3,5-triazin-2-yl)morpholine Chemical compound COC1C(N(CCO1)C)(C1=NC=NC=N1)OC QVSOLLSKUUJXQA-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- CRORGGSWAKIXSA-UHFFFAOYSA-N 3-methylbutyl 2-hydroxypropanoate Chemical compound CC(C)CCOC(=O)C(C)O CRORGGSWAKIXSA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CTTNDYQVJLFCHW-UHFFFAOYSA-N 3-triethoxysilylpropyl n-tert-butylcarbamate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)NC(C)(C)C CTTNDYQVJLFCHW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- DNGJVDGPCGXBFF-UHFFFAOYSA-N 4-methyl-n-(methyldiazenyl)aniline Chemical class CN=NNC1=CC=C(C)C=C1 DNGJVDGPCGXBFF-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- VAVOYRCCWLRTMS-UHFFFAOYSA-N 4-piperazin-1-ylaniline Chemical class C1=CC(N)=CC=C1N1CCNCC1 VAVOYRCCWLRTMS-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 206010001557 Albinism Diseases 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-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
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- GTZOZDOTOWNSJH-UHFFFAOYSA-N [O].CCCCCCC Chemical compound [O].CCCCCCC GTZOZDOTOWNSJH-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic 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
- 239000004411 aluminium Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000011088 calibration curve Methods 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-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
- 230000003467 diminishing effect Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 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
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QGGUMTNPIYCTSF-UHFFFAOYSA-N hexylsilane Chemical compound CCCCCC[SiH3] QGGUMTNPIYCTSF-UHFFFAOYSA-N 0.000 description 1
- 229960002885 histidine Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IPLONMMJNGTUAI-UHFFFAOYSA-M lithium;bromide;hydrate Chemical compound [Li+].O.[Br-] IPLONMMJNGTUAI-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 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
- BPOZIJBDYFHEJR-UHFFFAOYSA-N n-(ethyldiazenyl)-4-methylaniline Chemical class CCN=NNC1=CC=C(C)C=C1 BPOZIJBDYFHEJR-UHFFFAOYSA-N 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000002345 steroid group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XBXCNNQPRYLIDE-UHFFFAOYSA-N tert-butylcarbamic acid Chemical compound CC(C)(C)NC(O)=O XBXCNNQPRYLIDE-UHFFFAOYSA-N 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Disclosed is a liquid crystal alignment agent which can reduce microscopic irregularities on the surface of liquid crystal alignment films, improves liquid crystal alignment properties as well as having improved electrical characteristics, and provides increased reliability. The liquid crystal alignment agent contains a polyamic acid ester having a repeating group represented by general formula (1), a polyamic acid having a repeating group represented by general formula (2), and an organic solvent. The liquid crystal alignment agent is characterised in the weight average molecular weight of the polyamic acid ester being smaller than the weight average molecular weight of the polyamic acid. (In general formulae (1, 2) X1 and X2 independently represent a tetravalent organic group, and Y1 and Y2 independently represent a divalent organic group. R1 represents a C1-5 alkyl group, A1 and A2 independently represent a hydrogen atom or an optionally substituted C1-10 alkyl group, alkenyl group or alkynyl group).
Description
Invention field
The present invention relates to contain the aligning agent for liquid crystal of poly amic acid ester and polyamic acid and the liquid crystal orientation film that is made by this aligning agent for liquid crystal.
Background of invention
The liquid crystal display cells that is used for liquid crystal TV set, liquid crystal display etc. is provided for suppressing the liquid crystal orientation film of the state of orientation of liquid crystal usually in element.All the time, mainly use the polyimide liquid crystal orientation film that to coat glass substrate etc. and to burn till as the aligning agent for liquid crystal of principal ingredient with the solution of the polyimide precursors such as polyamic acid (polyamic acid) or soluble polyimide as liquid crystal orientation film.
Be accompanied by the high resolving power of liquid crystal display cells, require to consider from inhibition that the contrast of liquid crystal display cells is reduced or the reduction of ghost phenomena etc., following characteristic becomes important gradually in the liquid crystal orientation film: namely, except presenting excellent liquid crystal aligning and stable tilt angle, also comprise high voltage holding ratio, to by exchange the inhibition that drives the ghost that causes, the characteristic of the quick release of less residual charge and/or the residual charge put aside because of DC voltage when applying DC voltage.
In order to cater to above-mentioned requirements, various schemes have been proposed the polyimide liquid crystal orientation film.For example, as the required short liquid crystal orientation film of time of the ghost disappearance that is caused by DC voltage, proposed to use except polyamic acid and contain the tertiary amine that also contains ad hoc structure the polyamic acid of imide aligning agent for liquid crystal liquid crystal orientation film (for example, with reference to patent documentation 1), and use and to contain the liquid crystal orientation film (for example, with reference to patent documentation 2) etc. of aligning agent for liquid crystal that the specific diamine compound with pyridine skeleton etc. is used for the soluble polyimide of raw material.In addition, as the voltage retention height and by the required short liquid crystal orientation film of time of ghost disappearance that DC voltage causes following liquid crystal orientation film has been proposed: namely, used the liquid crystal orientation film (for example, referring to Patent Document 3) of aligning agent for liquid crystal of the compound of the compound that has a tertiary amine groups in the compound that has a carboxylic acid anhydrides in the compound that except polyamic acid or its imide amination polymer etc., also contains being selected from of minute quantity and have a carboxylic acid group in the molecule, the molecule and the molecule.In addition, excellent as liquid crystal aligning, voltage retention is high, ghost is few, reliability is excellent and show the liquid crystal orientation film of high tilt angle, the known liquid crystal orientation film that has used the aligning agent for liquid crystal that contains polyamic acid or its imide amination polymer, described polyamic acid makes (for example, referring to Patent Document 4) by tetracarboxylic dianhydride and the specific diamine compound of the tetracarboxylic dianhydride with ad hoc structure and cyclo-butane.In addition, as occur in the liquid crystal display cells that suppresses the transverse electric field drive pattern by exchanging the method that drives the ghost that causes, proposed to use the method (referring to Patent Document 5) of the large specific liquid crystal orientation film of interaction between the good and liquid crystal molecule of liquid crystal aligning.
But giant-screen and high-resolution liquid crystal TV set become main body in recent years, and to the increasingly stringent that requires of ghost, and requirement can tolerate the characteristic of the long-term use under the harsh environment for use.Simultaneously, it is higher day by day to require employed liquid crystal orientation film and liquid crystal orientation film in the past to compare reliability, many characteristics for liquid crystal orientation film also not only require initial characteristic good, even also can keep good after also requiring for example to be exposed to for a long time under the high temperature.
On the other hand, reported as the component of polymer that consists of the polyimide aligning agent for liquid crystal, the reliability of poly amic acid ester heat treated high and during with its imidizate can not cause the minimizing of molecular weight, so the orientation stability reliability of liquid crystal excellent (referring to Patent Document 6).But, poly amic acid ester has the problems such as specific insulation height, the residual charge when applying DC voltage are many usually, but not yet knows the method for the characteristic of the aligning agent for liquid crystal that improves the polyimide that contains described poly amic acid ester.
The prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 9-316200 communique
Patent documentation 2: Japanese patent laid-open 10-104633 communique
Patent documentation 3: Japanese patent laid-open 8-76128 communique
Patent documentation 4: Japanese patent laid-open 9-138414 communique
Patent documentation 5: Japanese patent laid-open 11-38415 communique
Patent documentation 6: Japanese Patent Laid-Open 2003-26918 communique
Summary of the invention
Invent technical matters to be solved
Contain the method for characteristic of the aligning agent for liquid crystal of poly amic acid ester as above-mentioned improvement, the inventor pays close attention to the aligning agent for liquid crystal of the polyamic acid that has mixed poly amic acid ester and electrical characteristics aspect excellence.But the liquid crystal orientation film that described aligning agent for liquid crystal by having mixed poly amic acid ester and polyamic acid makes is met in the method that all there is no aspect liquid crystal aligning and the electrical characteristics.
Namely, the liquid crystal orientation film that is made by the aligning agent for liquid crystal that contains poly amic acid ester and polyamic acid except causing albinism, the generation of the reduction of the voltage retention when also occuring to use film under the high temperature, the ghost that caused by accumulating of DC voltage and unusual by exchanging the generation that drives the ghost that causes etc.
The object of the present invention is to provide as containing the aligning agent for liquid crystal of poly amic acid ester and polyamic acid, it is all good and do not have an aligning agent for liquid crystal of the liquid crystal orientation film with transparency of albefaction to make liquid crystal aligning and electrical characteristics aspect.
The technical scheme that the technical solution problem adopts
According to the inventor's research, the liquid crystal orientation film that is formed by the aligning agent for liquid crystal that contains poly amic acid ester and polyamic acid is analyzed, results verification to the film Surface Creation trickle concavo-convex.The inventor also finds, the weight-average molecular weight by making the contained poly amic acid ester of aligning agent for liquid crystal can suppress littlely with being created on the trickle concavo-convex of film surface less than the weight-average molecular weight of described polyamic acid.In addition, the inventor finds, when making described trickle concavo-convex the diminishing that is created on the film surface, can solve the defective that aligning agent for liquid crystal has that contains poly amic acid ester and polyamic acid.
So the present invention is based on above-mentioned discovery and the invention finished, comprises following technology contents.
1. aligning agent for liquid crystal, it is characterized in that, contain the poly amic acid ester with the repetitive that is represented by following formula (1), polyamic acid and the organic solvent with the repetitive that is represented by following formula (2), the weight-average molecular weight of described poly amic acid ester is less than the weight-average molecular weight of described polyamic acid.
[changing 1]
In formula (1) and formula (2), X
1And X
2Be respectively the organic group of 4 valencys independently, Y
1And Y
2Be the organic group of divalent independently respectively.R
1Be the alkyl of carbon number 1～5, A
1And A
2Alkyl, alkenyl or the alkynyl that maybe can have independently respectively substituent carbon number 1～10 for hydrogen atom.
2. above-mentioned 1 described aligning agent for liquid crystal, wherein, in the mass ratio of (content of the content/polyamic acid of poly amic acid ester), the content of described poly amic acid ester and the content of polyamic acid are 1/9～9/1.
3. above-mentioned 1 or 2 described aligning agent for liquid crystal, wherein, the total content of described poly amic acid ester and polyamic acid is 0.5～15 quality % with respect to organic solvent.
4. each described aligning agent for liquid crystal in above-mentioned 1～3, wherein, the weight-average molecular weight of described poly amic acid ester is less by 1000～100000 than the weight-average molecular weight of described polyamic acid.
5. each described aligning agent for liquid crystal in above-mentioned 1～4, wherein, the X in formula (1) and the formula (2)
1And X
2Respectively independently for being selected from least a kind of the structure that represented by following formula.
[changing 2]
6. each described aligning agent for liquid crystal in above-mentioned 1～5, wherein, in the formula (1), Y
1For being selected from least a kind of the structure that represented by following formula.
[changing 3]
7. each described aligning agent for liquid crystal in above-mentioned 1～6, wherein, in the formula (2), Y
2For being selected from least a kind of the structure that represented by following formula.
[changing 4]
8. liquid crystal orientation film is with each described aligning agent for liquid crystal coating in above-mentioned 1～7 and burn till and make.
9. liquid crystal orientation film is to each described aligning agent for liquid crystal coating in above-mentioned 1～7 and burn till and the tunicle irradiation that obtains makes through the radioactive ray of polarization.
The effect of invention
According to the present invention, the electrical characteristics such as residual of the ghost that voltage retention in trickle concavo-convex minimizing on the liquid crystal orientation film surface that makes, the liquid crystal aligning raising, ion concentration is provided, has caused because of alternating current, DC voltage also are enhanced, Reliability Enhancement aligning agent for liquid crystal.
Why the weight-average molecular weight that is still not clear by making poly amic acid ester can make described be created on the film surface trickle concavo-convex diminish, solve the defective that the aligning agent for liquid crystal that contains poly amic acid ester and polyamic acid has less than the weight-average molecular weight of described polyamic acid, but thinks roughly as follows.
Namely, be dissolved in desolventizing the aligning agent for liquid crystal of organic solvent and in the liquid crystal orientation film that forms from poly amic acid ester and polyamic acid, although poly amic acid ester concentrated the be positioned at surface lower with polyamic acid phase specific surface free energy, but by being separated between poly amic acid ester and the polyamic acid, poly amic acid ester form in mutually polyamic acid condensed matter or polyamic acid mutually in the condensed matter of formation poly amic acid ester, become thus the film of the protruding a large amount of existence of film surface detail nick.
Relative therewith, in aligning agent for liquid crystal of the present invention, by so that the weight-average molecular weight of poly amic acid ester less than the weight-average molecular weight of described polyamic acid, when forming liquid crystal orientation film from this aligning agent for liquid crystal desolventizing, promote being separated of poly amic acid ester and polyamic acid, poly amic acid ester is present in the film near surface with the state that does not mix with polyamic acid, and polyamic acid is present in film inside and substrate interface with the state that does not mix with poly amic acid ester.
Therefore, can not form on the surface of the liquid crystal orientation film that makes by cause concavo-convex of being separated of poly amic acid ester and polyamic acid and become level and smooth surface, the albefaction of the film that is caused by concavo-convex generation is also reduced.And, think because orientation stability, poly amic acid ester coverlay surface that reliability is excellent, and the polyamic acid of electrical characteristics excellence being present in film inside and electrode interface, the liquid crystal orientation film that therefore possesses the smooth surface of no concave-convex has excellent characteristic.
The preferred embodiment for the present invention
＜poly amic acid ester and polyamic acid 〉
Being used for poly amic acid ester of the present invention is for the polyimide precursor that obtains polyimide, for having the polymkeric substance that can carry out the position of following imidization reaction by heating.
[changing 5]
The poly amic acid ester that aligning agent for liquid crystal of the present invention is contained and polyamic acid have respectively following formula (1) and following formula (2).
[changing 6]
In the formula (1), R
1For carbon number 1～5, better be 1～2 alkyl.Along with the increase of the carbon number of alkyl, the temperature that imidizate carries out raises in the poly amic acid ester.Therefore, from being easy to consider R by the hot viewpoint of imidizate that causes
1The spy is methyl well.In formula (1) and formula (2), A
1And A
2Alkyl, alkenyl or the alkynyl that maybe can have independently respectively substituent carbon number 1～10 for hydrogen atom.As the concrete example of abovementioned alkyl, but exemplified by methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, decyl, cyclopentyl, cyclohexyl, dicyclohexyl etc.Can exemplify and to be present in the CH more than 1 of abovementioned alkyl as alkenyl
2-CH
2Structure replaces the group of CH=CH structure, more specifically, but exemplified by vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl group, 1,3-butadiene base, 2-pentenyl, 2-hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc.Can exemplify and to be present in the CH more than 1 of described alkyl as alkynyl
2-CH
2Structure replaces the group of C ≡ C-structure, more specifically, can exemplify ethinyl, 1-propinyl, 2-propynyl etc.
Total carbon number of abovementioned alkyl, alkenyl or alkynyl is can have substituting group in 1～10 the situation, also can form ring structure by substituting group.Forming ring structure by substituting group represents between the substituting group or the part of substituting group and precursor skeleton combines and becomes the implication of ring structure.
As this substituent example, can exemplify halogen group, hydroxyl, sulfydryl, nitro, aryl, organic alkoxy, organic alkylthio group, organosilicon alkyl, acyl group, ester group, thioester substrate, phosphate-based, amide group, alkyl, alkenyl, alkynyl.
As substituent halogen group, can exemplify fluorine atom, chlorine atom, bromine atoms, iodine atom.
But as substituent aryl exemplified by phenyl.This aryl can further be replaced by aforesaid other substituting groups.
Can be represented by-structure that O-R represents as substituent organic alkoxy.This R can be identical or different, can exemplify out aforesaid alkyl, alkenyl, alkynyl, aryl etc.These R can further be replaced by aforesaid substituting group.As the concrete example of organic alkoxy, can exemplify methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy etc.
Can be represented by-structure that S-R represents as substituent organic alkylthio group.Can exemplify out aforesaid alkyl, alkenyl, alkynyl, aryl etc. as this R.These R can further be replaced by aforesaid substituting group.As the concrete example of organic alkylthio group, can exemplify methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, heptan sulfenyl, hot sulfenyl etc.
Can be by-Si-(R) as substituent organosilicon alkyl
3The structure of expression represents.This R can be identical or different, can exemplify out aforesaid alkyl, alkenyl, alkynyl, aryl etc.These R can further be replaced by aforesaid substituting group.As the concrete example of organosilicon alkyl, can exemplify TMS, triethyl silyl, tripropyl silylation, tributyl silylation, three amyl group silylation, three hexyl silane bases, amyl group dimethylsilyl, hexyl dimethylsilyl etc.
As substituent acyl group can by-C(O)-structure that R represents represents.As this R, can exemplify out aforesaid alkyl, alkenyl, aryl etc.These R can further be replaced by aforesaid substituting group.As the concrete example of acyl group, can exemplify formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc.
As substituent ester group can by-C(O) O-R or-structure that OC (O)-R represents represents.As this R, can exemplify out aforesaid alkyl, alkenyl, alkynyl, aryl etc.These R can further be replaced by aforesaid substituting group.
As substituent mercapto ester group can by-C(S) O-R or-structure shown in OC (S)-R represents.As this R, can exemplify out aforesaid alkyl, alkenyl, alkynyl, aryl etc.These R can further be replaced by aforesaid substituting group.
As substituent phosphate can by-OP(O)-(OR)
2Shown structure represents.This R can be identical or different, can exemplify out aforesaid alkyl, alkenyl, alkynyl, aryl etc.These R can further be replaced by aforesaid substituting group.
Can be by-C (O) NH as substituent amide group
2, or-C (O) NHR ,-NHC (O) R ,-C (O) N (R)
2Structure shown in ,-NRC (O) R represents.This R can be identical or different, can exemplify out aforesaid alkyl, alkenyl, alkynyl, aryl etc.These R can further be replaced by aforesaid substituting group.
As substituent aryl, can exemplify the group identical with aforesaid aryl.This aryl can further be replaced by aforesaid other substituting groups.
As substituent alkyl, can exemplify the group identical with aforesaid alkyl.This alkyl can further be replaced by aforesaid other substituting groups.
As substituent alkenyl, can exemplify the group identical with aforesaid alkenyl.This alkenyl can further be replaced by aforesaid other substituting groups.
As substituent alkynyl, can exemplify the group identical with aforesaid alkynyl.This alkynyl can further be replaced by aforesaid other substituting groups.
Usually, if introduce bulky structure, then have and reduce amino reactivity and the possibility of liquid crystal aligning, therefore as A
1And A
2Be more preferably the alkyl that hydrogen atom maybe can have substituent carbon number 1～5, the spy is well hydrogen atom, methyl or ethyl.
In above-mentioned formula (1) and formula (2), X
1And X
2Be respectively the organic group of 4 valencys independently, Y
1And Y
2Be the organic group of divalent independently respectively.X
1And X
2Be the organic group of 4 valencys, be not particularly limited.In the polyimide precursor, X
1And X
2Can mix has more than 2 kinds.If enumerate X
1And X
2Concrete example then can exemplify X-1～X-46 shown below respectively independently.
[changing 7]
[changing 8]
[changing 9]
[changing 10]
Wherein, consider X from the complexity that obtains monomer
1And X
2Better be to be independently respectively X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X-21, X-25, X-26, X-27, X-28 or X-32.Have these preferred X
1And X
2Tetracarboxylic dianhydride's use amount better be 2～100 % by mole of tetracarboxylic dianhydride's total amount, be more preferably 40～100 % by mole.
In addition, in the formula (1), Y
1And Y
2Be the organic group of divalent independently respectively, be not particularly limited.If enumerate Y
1And Y
2Concrete example, then can exemplify following Y-1～Y-103.As Y
1And Y
2, can mix independently respectively has more than 2 kinds.
[changing 11]
[changing 12]
[changing 13]
[changing 14]
[changing 15]
[changing 16]
[changing 17]
[changing 18]
[changing 19]
[changing 20]
[changing 21]
[changing 22]
[changing 23]
Wherein, in order to introduce in the poly amic acid ester, as Y as purpose diamines that rectilinearity is high to obtain good liquid crystal aligning
1It better is the diamines with Y-7, Y-10, Y-11, Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75 or Y-98.As Y
1The use amount of preferred these diamines better is 1～100 % by mole of diamines total amount, is more preferably 50～100 % by mole.
Wherein, when wanting to improve tilt angle, better be that the diamines that will have the structure that chain alkyl, aromatic ring, aliphatics ring, steroid skeleton or they combine on the side chain is incorporated into poly amic acid ester, at this moment, better be Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97 as Y1.
Wherein, the spy is selected from least a kind of the structure that is expressed from the next.
[changing 24]
By reducing the specific insulation of polyamic acid, can reduce the ghost that the savings by DC voltage causes, therefore introduce polyamic acid in order to have the diamines that comprises heteroatomic structure, Ppolynuclear aromatic structure or comprise the bis-phenol skeleton, as Y
2Be more preferably Y-19, Y-23, Y-25, Y-26, Y-27, Y-30, Y-31, Y-32, Y-33, Y-34, Y-35, Y-36, Y-40, Y-41, Y-42, Y-44, Y-45, Y-49, Y-50, Y-51 or Y-61, preferred Y
2Diamines for Y-31 or Y-40.As Y
2The use amount of preferred these diamines better is 1～100 % by mole of diamines total amount, is more preferably 50～100 % by mole.
Wherein, for the film surface that is separated and makes coating and burn till the liquid crystal orientation film that makes that further promotes poly amic acid ester and polyamic acid by the surface free energy that improves polyamic acid becomes more level and smooth, better be that the diamines that will have secondary amino group, hydroxyl, amide group, urea groups or carboxyl is introduced polyamic acid.Therefore, as Y
2Be more preferably Y-19, Y-31, Y-40, Y-45, Y-98 or Y-99, the spy is well Y-98 or the Y-99 that contains carboxyl.Wherein, Y
2Be preferably selected from least a kind of the structure that represented by following formula.
[changing 25]
The manufacture method of＜poly amic acid ester 〉
By the poly amic acid ester of above-mentioned formula (1) expression can by by the tetracarboxylic acid derivatives of following formula (6)～(8) expression any and obtained by the reaction of the diamine compound of formula (9) expression.
[changing 26]
[changing 27]
In the formula, X
1, Y
1, R
1, A
1And A
2Identical with the definition in the above-mentioned formula (1) respectively.
Poly amic acid ester by above-mentioned formula (1) expression can by using above-mentioned monomer, adopt the method for (1) shown below～(3) synthetic.
(1) by the synthetic situation of polyamic acid
Poly amic acid ester can be by being synthesized by the polyamic acid esterification that tetracarboxylic dianhydride and diamines obtain.
Particularly, in the presence of organic solvent, in-20 ℃～150 ℃, better be under 0 ℃～50 ℃, make polyamic acid and esterifying agent reaction 30 minutes～24 hours, better be that reaction was synthesized in 1～4 hour.
Better be can be by the esterifying agent of purifying and to remove easily as esterifying agent, can exemplify N, the dinethylformamide dimethylacetal, N, the dinethylformamide diethyl acetal, N, dinethylformamide dipropyl acetal, N, dinethylformamide di neo-pentyl butyl acetal, N, dinethylformamide di-t-butyl acetal, 1-methyl-3-p-methylphenyl triazenes, 1-ethyl-3-p-methylphenyl triazenes, 1-propyl group-3-p-methylphenyl triazenes, 4-(4, the 6-dimethoxy)-1,3,5-triazine-2 base)-4-methyl morpholine chloride (モ Le ホ リ ニ ウ system Network ロ リ De) etc.The repetitive of the polyamic acid of the addition of esterifying agent with respect to 1 mole is 2～6 molar equivalents.
From the structure adaptability consideration, employed solvent better is DMF, METHYLPYRROLIDONE or gamma-butyrolacton in the above-mentioned reaction, and these can use in one kind or two or more mixing.From being difficult to cause the viewpoint consideration of separating out and obtain easily the high molecular body of polymkeric substance, the concentration when synthetic better is 1～30 quality %, is more preferably 5～20 quality %.
(2) by the synthetic situation of the reaction of dichloride tetrabasic carboxylic acid diester and diamines
Poly amic acid ester can be synthetic by dichloride tetrabasic carboxylic acid diester and diamines.
Particularly, in the presence of alkali and organic solvent, in-20 ℃～150 ℃, better be under 0 ℃～50 ℃, make dichloride tetrabasic carboxylic acid diester and diamine reactant 30 minutes～24 hours, it is synthetic better to be that reaction came in 1～4 hour.
Described alkali can use pyridine, triethylamine, 4-dimethylaminopyridine etc., leniently carries out preferred pyridine in order to make reaction.The viewpoint that easily obtains the high molecular body from the amount with easy removal considers that the addition of alkali better is 2～4 times of moles with respect to dichloride tetrabasic carboxylic acid diester.
From monomer and structure adaptability consideration, employed solvent better is METHYLPYRROLIDONE or gamma-butyrolacton in the above-mentioned reaction, and these can use in one kind or two or more mixing.From being difficult to cause the viewpoint consideration of separating out and obtain easily the high molecular body of polymkeric substance, polymer concentration better is 1～30 quality % when synthetic, is more preferably 5～20 quality %.In addition, in order to prevent the hydrolysis of dichloride tetrabasic carboxylic acid diester, better be the state of dehydration as far as possible for the synthesis of the solvent of poly amic acid ester, better be in nitrogen atmosphere, prevent sneaking into of external gas.
(3) by the situation of tetrabasic carboxylic acid diester and the acid of diamines synthesizing polyamides
Poly amic acid ester can synthesize by polycondensation tetrabasic carboxylic acid diester and diamines.
Particularly, in the presence of condensation agent, alkali and organic solvent, in 0 ℃～150 ℃, better be under 0 ℃～100 ℃, make tetrabasic carboxylic acid diester and diamine reactant 30 minutes～24 hours, it is synthetic better to be that reaction came in 3～15 hours.
Described condensation agent can use triphenyl phosphate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazinyl methyl morpholine, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) tetrafluoroborate, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) hexafluorophosphate, (2,3-dihydroxy-2-sulfo--3-benzoxazolyl) phosphonic acid diphenyl ester etc.The addition of condensation agent better is 2～3 times of moles with respect to the tetrabasic carboxylic acid diester.
Described alkali can use the tertiary amines such as pyridine, triethylamine.The viewpoint that obtains easily the high molecular body from the amount with easy removal considers that the addition of alkali better is 2～4 times of moles with respect to two amine components.
In addition, in above-mentioned reaction, by lewis acid is added as adjuvant, effectively react.As lewis acid, better be the halogen lithiums such as lithium chloride, lithium bromide.Lewis acidic addition better is 0～1.0 times of mole with respect to two amine components.
In the synthetic method of above-mentioned 3 kinds of poly amic acid esters, in order to obtain the poly amic acid ester of high molecular, the spy is well the synthetic method of above-mentioned (1) or above-mentioned (2).
The solution of the poly amic acid ester that makes as mentioned above can be by separating out polymkeric substance at the well-beaten Weak solvent that injects simultaneously.By after carrying out that several is separated out and cleaning with Weak solvent, obtain the powder of sublimed poly amic acid ester at normal temperature or heat drying.Weak solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.
The manufacture method of＜polyamic acid 〉
The polyamic acid of above-mentioned formula (2) expression can obtain by the reaction of the tetracarboxylic dianhydride who is represented by following formula (10) and the diamine compound that is represented by formula (11).
[changing 28]
In the formula, X
2, Y
2, A
1And A
2Identical with the definition in the above-mentioned formula (2) respectively.
Particularly, in the presence of organic solvent, in-20 ℃～150 ℃, better be under 0 ℃～50 ℃, make tetracarboxylic dianhydride and diamine reactant 30 minutes～24 hours, it is synthetic better to be that reaction came in 1～12 hour.
From monomer and structure adaptability consideration, employed organic solvent better is DMF, METHYLPYRROLIDONE or gamma-butyrolacton in the above-mentioned reaction, and these can use in one kind or two or more mixing.From being difficult to cause the viewpoint consideration of separating out and obtain easily the high molecular body of polymkeric substance, polymer concentration better is 1～30 quality %, is more preferably 5～20 quality %.
The polyamic acid that makes as mentioned above can make polymkeric substance separate out and reclaim by inject Weak solvent in abundant stirring reaction solution.In addition, after carrying out that several is separated out and cleaning with Weak solvent, by obtain the powder of sublimed polyamic acid at normal temperature or heat drying.Weak solvent is not particularly limited, can exemplifies water, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention comprises by the poly amic acid ester of above-mentioned formula (1) expression and the polyamic acid that is represented by formula (2).
The weight-average molecular weight of poly amic acid ester better is 5000～300000, better is 10000～200000.In addition, number-average molecular weight better is 2500～150000, is more preferably 5000～100000.
On the other hand, the weight-average molecular weight of polyamic acid better is 10000～305000, better is 20000～210000.In addition, number-average molecular weight better is 5000～152500, is more preferably 10000～105000.
In the present invention, must make the weight-average molecular weight of poly amic acid ester less than the weight-average molecular weight of polyamic acid.The difference of the weight-average molecular weight of poly amic acid ester and polyamic acid better is 1000～100000, is more preferably 3000～80000, and the spy is 5000～60000 well.The difference of this weight-average molecular weight is in 1000～100000 scope the time, and is by trickle concavo-convexly being suppressed significantly that being separated of poly amic acid ester and polyamic acid causes, therefore good.
The content of the aforementioned poly amic acid ester in the aligning agent for liquid crystal of the present invention and the content of aforementioned polyamic acid better are 1/9～9/1 in the mass ratio of (poly amic acid ester/polyamic acid), are more preferably 2/8～8/2, and the spy is 3/7～7/3 well.By with described proportional control in 1/9～9/1 scope, all good aligning agent for liquid crystal of liquid crystal aligning and electrical characteristics can be provided.
Aligning agent for liquid crystal of the present invention is the state that above-mentioned poly amic acid ester and polyamic acid are dissolved in the solution in the organic solvent.As long as have described state, can be the reaction solution itself that for example in organic solvent, obtains when synthesizing polyamides acid esters and/or polyamic acid, or with suitable solvent dilution should the broad liquid of reaction and solution.In addition, during with Powdered acquisition poly amic acid ester and/or polyamic acid, can be it is dissolved in organic solvent and solution.
Polyamic acid in the aligning agent for liquid crystal of the present invention and poly amic acid ester (below, be also referred to as polymkeric substance) content (concentration) can suitably change according to the setting of the thickness of the polyimide film that will form, but consider from making it form even and flawless angle of filming, with respect to organic solvent, the content of component of polymer better is more than the 0.5 quality %, consider that from the angle of the storage stability of solution be more preferably below the 15 quality %, the spy is well 1～10 quality %.At this moment, can prepare in advance the highly concentrated solution of polymkeric substance, dilute when making aligning agent for liquid crystal by highly concentrated solution.The concentration of the highly concentrated solution of described component of polymer better is 10～30 quality %, is more preferably 10～15 quality %.Can heat when in addition, the powder dissolution of component of polymer being prepared solution at organic solvent.Heating-up temperature better is at 20 ℃～150 ℃, and the spy is well 20～80 ℃.
The above-mentioned organic solvent that aligning agent for liquid crystal of the present invention is contained so long as the solvent of component of polymer uniform dissolution then be not particularly limited.Its concrete example can exemplify N, dinethylformamide, N, N-diethylformamide, N, N-dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-Pyrrolidone, NVP, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, 3-methoxyl-N, N-dimethyl propylene acid amides etc.These can use one kind or two or more mixing to use.In addition, even can't be separately the solvent of dissolve polymer composition equably, as long as in the scope that polymkeric substance is not separated out, also can mix with above-mentioned organic solvent.
Aligning agent for liquid crystal of the present invention also can comprise to improve the solvent that film uniformity is purpose that is coated with when aligning agent for liquid crystal coated substrate except comprising the organic solvent take the dissolve polymer composition as purpose.Described solvent uses the solvent of comparing low surface tension with described organic solvent usually.Enumerate its concrete example, then can exemplify ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, butyl carbitol, the ethyl carbitol acetic acid esters, ethylene glycol, the 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, single acetic acid propylene glycol ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, the single ether of propylene glycol-1--2-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.These solvents can be also with more than 2 kinds.
Aligning agent for liquid crystal of the present invention can comprise the various adjuvants such as silane coupling agent or crosslinking chemical.Silane coupling agent is coated with the substrate of aligning agent for liquid crystal and the adaptation between the liquid crystal orientation film formed thereon take raising to be added as purpose.The below exemplifies the object lesson of silane coupling agent, but is not limited to this.
The amine silane coupling agents such as APTES, 3-(2-amino-ethyl) TSL 8330,3-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, 3-TSL 8330,3-phenyl amino propyl trimethoxy silicane, 3-triethoxysilicane alkyl-N-(1,3-dimethyl-butylidene) propylamine, 3-aminopropyl diethoxymethyl silane; The vinyl silane coupling agents such as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyl methyl dimethoxysilane, vinyltriacetoxy silane, vinyl silane triisopropoxide, allyltrimethoxysilanis, p-styryl trimethoxy silane; The epoxies silane coupling agents such as 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane; The methacrylic silane coupling agents such as 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane; The acrylic compounds silane coupling agents such as 3-acryloxy propyl trimethoxy silicane; The ureas silane coupling agents such as 3-urea groups propyl-triethoxysilicane; Two (3-(triethoxysilicane alkyl) propyl group) disulfide, two (3-(triethoxysilicane alkyl) propyl group) tetrasulfide sulfides one type of silane coupling agent; 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane, the 3-caprylyl sulfo--mercapto one type of silane coupling agents such as 1-propyl-triethoxysilicane; The isocyanates silane coupling agents such as 3-isocyanate group propyl-triethoxysilicane, 3-isocyanate group propyl trimethoxy silicane; The aldehydes silane coupling agents such as triethoxysilicane alkyl butyraldehyde; The tri-ethoxy silylpropyl methyl carbamic acid tert-butyl ester, (3-tri-ethoxy silylpropyl)-t-butyl carbamate one type of silane coupling agents such as tert-butyl group t-butyl carbamate.
When the addition of above-mentioned silane coupling agent is too much, unreacted reactant causes harmful effect to liquid crystal aligning, therefore when very few, can't embody the effect to adaptation, the solid constituent with respect to polymkeric substance better is 0.01～5.0 % by weight, is more preferably 0.1～1.0 % by weight.
When adding above-mentioned silane coupling agent, in order to prevent separating out of polymkeric substance, better be to add before the solvent of purpose in the aforementioned homogeneity of filming take raising of interpolation.In addition, when adding silane coupling agent, can before mixed polyamide acid esters solution and polyamic acid solution, add polyamic acid ester solution, polyamic acid solution or polyamic acid ester solution and polyamic acid solution both sides.In addition, can add in poly amic acid ester-polyamic acid mixed solution.In order to add silane coupling agent take the adaptation between raising polymkeric substance and the substrate as purpose, adding method as silane coupling agent, better be to add to concentrate the polyamic acid solution that is positioned at film inside and substrate interface, after polymkeric substance and silane coupling agent are fully reacted, the method for mixing with the polyamic acid ester solution.
For burning till the imidizate that effectively carries out poly amic acid ester when filming, can add imidizate promoter.Below, exemplify the concrete example of the imidizate promoter of poly amic acid ester, but be not limited to these.
[changing 29]
[changing 30]
D is tert-butoxycarbonyl or 9-fluorenylidene methoxycarbonyl respectively independently in the above-mentioned formula (B-1)～(B-17).In (B-14)～(B-17), there are a plurality of D in the formula, they can be identical or different.
The content of imidizate promoter is as long as in the scope of the effect of the hot-imide that can obtain to promote poly amic acid ester, be not particularly limited, but the amic acid esters position of the following formula (12) that the poly amic acid ester in the aligning agent for liquid crystal with respect to 1 mole is contained, better be more than 0.01 mole, be more preferably more than 0.05 mole, further be more preferably more than 0.1 mole.In addition, residue in the dysgenic angle consideration that the imidizate promoter itself the film after burning till is caused many characteristics of liquid crystal orientation film from minimally control, the amic acid esters position of the following formula (12) that the poly amic acid ester in the aligning agent for liquid crystal with respect to 1 mole is contained, imidizate promoter is more fortunately below 2 moles, better below 1 mole, further better below 0.5 mole.
[changing 31]
When adding imidizate promoter, might carry out imidizate by heating, therefore better be with adding after good solvent and the Weak solvent dilution.
＜liquid crystal orientation film 〉
Liquid crystal orientation film of the present invention is that above-mentioned aligning agent for liquid crystal is coated substrate, and dry, burn till and the film that makes.Substrate as coating aligning agent for liquid crystal of the present invention, so long as the high substrate of the transparency then limits without special, can use the plastic bases such as glass substrate, silicon nitride board, acrylic acid substrate, polycarbonate substrate etc., from the angle that production technology is simplified, the preferred substrate that is formed with for the ITO electrode of liquid crystal drive etc. that uses.In addition, in the reflection type liquid crystal display element, if only limit to the substrate of a side then can use the opaque material such as silicon wafer, the electrode of this moment also can use the catoptrical materials such as aluminium.
Coating process as aligning agent for liquid crystal of the present invention can exemplify spin-coating method, print process, ink-jet method etc.Be coated with dry behind the aligning agent for liquid crystal of the present invention, firing process and can select arbitrary temp and time.Usually, in order fully to remove the organic solvent that contains, make its dry 1 minute～10 minutes in 50 ℃～120 ℃, burnt till 5 minutes～120 minutes in 150 ℃～300 ℃ afterwards.The thickness of filming after burning till is not particularly limited, if but excessively thin, then the reliability of liquid crystal display cells can reduce sometimes, better is 5～300nm therefore, is more preferably 10～200nm.
As the method for the liquid crystal orientation film that makes being carried out orientation process, can exemplify rubbing manipulation, light orientation process method etc., but particularly useful in the situation of aligning agent for liquid crystal of the present invention employing light orientation process method.
As the concrete example of light orientation process method, can exemplify the radioactive ray of aforementioned film coated surface irradiation towards the certain orientation deflection, according to circumstances further under 150～250 ℃ temperature, carry out heat treated, give the method for liquid crystal aligning ability.Can use ultraviolet ray and the visible light of the wavelength with 100nm～800nm as radioactive ray.Wherein, better be the ultraviolet ray with 100nm～400nm wavelength, the spy is well the ultraviolet ray with 200nm～400nm wavelength.In addition, in order to improve liquid crystal aligning, can be to shine when substrate is filmed in 50～250 ℃ of lower heating radioactive ray.The exposure of aforementioned radioactive ray better is 1～10000mJ/cm
2, the spy is 100～5000mJ/cm well
2The liquid crystal orientation film that makes as mentioned above can make liquid crystal molecule stably be orientated towards certain orientation.
＜liquid crystal display cells 〉
Liquid crystal display cells of the present invention is to obtain with the substrate of liquid crystal orientation film by aligning agent for liquid crystal of the present invention and after carrying out orientation process, make the liquid crystal display cells that the liquid crystal structure cell forms by known method by said method.
Manufacture method to the liquid crystal structure cell is not particularly limited, as enumerating an example, normally adopt 1 pair of substrate will being formed with liquid crystal orientation film with the liquid crystal aligning face as the mode clamping of inboard better be 1～30 μ m, after the sept that is more preferably 2～10 μ m arranges, around fixing with sealant, and inject liquid crystal and the method that seals.The method of enclosing liquid crystal is had no particular limits, can exemplify the method etc. of dripping that seals behind the vacuum method that injects liquid crystal after in to the liquid crystal structure cell that makes, reducing pressure, the liquid crystal that drips.
Embodiment
The below enumerates embodiment, further specifies the present invention.But the present invention is not interpreted as and is subject to these embodiment.
The abbreviation of using in embodiment and the comparative example and the assay method of each characteristic are as described below.
1,3DMCBDE-Cl:1, two (chlorocarbonyl)-1 of 3-, 3-dimethyl cyclo-butane-2,4-dimethyl dicarboxylate
ODA:4,4 '-diaminodiphenyl ether
BDA:1,2,3,4-butane tetracarboxylic acid dianhydride
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
The NMP:N-N-methyl-2-2-pyrrolidone N-
γ-BL: gamma-butyrolacton
BCS: butyl cellosolve
PAE: poly amic acid ester
PAA: polyamic acid
[changing 32]
[viscosity]
In synthesis example, poly amic acid ester and polyamic acid solution viscosity are utilized E type viscosity meter TVE-22H ((East Machine industry society of Toki Sangyo Co., Ltd.) system), under the condition of 25 ℃ of sample size 1.1mL, coniform rotor (コ one Application ロ one タ) TE-1 (1 ° 34 ', R24), temperature, measure.
[molecular weight]
In addition, the molecular weight of poly amic acid ester is to adopt GPC(normal temperature gel permeation chromatography) device measures, and calculates number-average molecular weight (below, be also referred to as Mn) and weight-average molecular weight (below, be also referred to as Mw) with polyglycol, polyethylene oxide scaled value.
GPC device: Shodex (Showa Denko K. K) company's system (GPC-101)
Post: Showa Denko K. K's system (series connection of KD803, KD805)
Column temperature: 50 ℃
Eluent: N, and the N'-dimethyl formamide (as adjuvant, lithium bromide-hydrate (LiBrH
2O) be that 30mmol/L, phosphoric acid anhydrous crystal (ortho-, meta-or p-phosphoric acid) are 10ml/L for 30mmol/L, tetrahydrofuran (THF))
Flow velocity: 1.0ml/ minute
Calibration curve is made and to be used standard sample: (East ソ ー society of eastern Cao company) TSK standard polyethylene oxide processed (weight-average molecular weight (Mw) about 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) polyglycol processed (peak molecular weight (Mp) about 12000,4000,1000).Repeat for fear of peak value, measured respectively 2 samples, namely mixed 900000,100000,12000,1000 these samples of 4 kinds and mixed 150000,30000,4000 these samples of 3 kinds.
[center line average roughness mensuration]
To in the heated air circulation type stove of 250 ℃ of temperature, burn till 1 hour after 5 minutes in drying on 80 ℃ the heating plate through the filming of aligning agent for liquid crystal that rotary coating makes, obtain filming of thickness 100nm.Observe this film surface of filming with atomic force microscope (AFM), and measured the center line average roughness (Ra) on film surface, the flatness on evaluated for film surface.
Determinator: L-trace probe microscope (SII technology Co., Ltd. (エ ス ア イ ア イ テ Network ノ ロ ジ one society) system)
[voltage retention]
Aligning agent for liquid crystal is spun on the glass substrate with transparency electrode, through 60 minutes burn till and obtain the polyimide film of thickness 100nm in the drying of heating plate upper 5 minute of 80 ℃ of temperature, heated air circulation type stove at 250 ℃.Across the ultraviolet 100mJ/cm of polarization plates to this coated surface irradiation 254nm
2, obtain the substrate with liquid crystal orientation film.Prepare 2 this substrates with liquid crystal orientation film, after the liquid crystal aligning face of a substrate scatters the sept of 6 μ m, with the antiparallel condition of the orientation of 2 substrates with 2 substrate in combination, sealing on every side, but stay liquid crystal injecting port, making structure cell opening (cell gap) is the negative crystal born of the same parents of 6 μ m.Vacuum is injected liquid crystal (MLC-2041, Merck ﹠ Co., Inc. (メ Le Network society) system) in this structure cell at normal temperatures, with the inlet sealing, makes the liquid crystal structure cell.
The voltage retention of the above-mentioned liquid crystal structure cell of following mensuration.
Measure voltage after applying voltage 60 μ s, the 16.67ms of 4V, calculate by this variation with respect to initial value, with this as voltage retention.During mensuration, the temperature of liquid crystal structure cell is made as 23 ℃, 60 ℃, 90 ℃, under these temperature, measures respectively.
[ion concentration]
The ion concentration of the above-mentioned liquid crystal structure cell of following mensuration.
The use Dongyang (East Yang テ of technology Co., Ltd. Network ニ カ society) 6254 type liquid crystal evaluation of physical property devices of system are measured.Apply the triangular wave of 10V, 0.01Hz, calculate the area suitable with ion concentration of gained waveform by the triangle method of approximation, with it as ion concentration.During mensuration, the temperature of liquid crystal structure cell is made as 23 ℃, 60 ℃, under these temperature, measures respectively.
[interchange that FFS drives the liquid crystal structure cell drives sintering]
On the glass substrate that is formed with fringe field conversion (Fringe Field Switching, hereinafter referred to as FFS) driving electrode, be coated with aligning agent for liquid crystal by spin-coating method, the described glass substrate that is formed with fringe field conversion driving electrode for the ground floor on glass substrate have ITO electrode as the thickness 50nm of electrode, have silicon nitride as the thickness 500nm of dielectric film at the second layer, at the 3rd layer of zigzag ITO electrode (electrode width: 3 μ m, electrode gap: 6 μ m, electrode height: 50nm) that has as electrode.After 80 ℃ heating plates make its dry 5 minutes, in 250 ℃ heated air circulation type stove, burnt till 60 minutes, forming thickness is filming of 100nm.Across the ultraviolet 100mJ/cm of polarization plates to this coated surface irradiation 254nm
2, obtain the substrate with liquid crystal orientation film.In addition, as not being formed with electrode and having to form too on the glass substrate of column spacer of height 4 μ m and film of counter substrate, implementation orientation is processed.
Above-mentioned 2 plate bases as one group, behind 1 plate base of fitting as 0 ° condition in printing and sealing agent on the substrate and take the relative orientation direction of liquid crystal orientation film in addition, are made sealant cures and make the negative crystal born of the same parents.Inject liquid crystal MLC-2041 (Merck ﹠ Co., Inc. (メ Le Network society) system) by the decompression injection method in the negative crystal born of the same parents, the sealing inlet obtains FFS and drives the liquid crystal structure cell.
After measuring the V-T characteristic (voltage-transmission characteristics) under 58 ℃ of temperature that this FFS drives the liquid crystal structure cell, apply 4 hours ± the 4V/120Hz square wave.After 4 hours, cut off voltage, after placing 60 minutes under 58 ℃ the temperature, again measure the V-T characteristic, calculate the transmissivity that applies before and after the square wave and be 50% voltage difference.
[evaluation of electric charge Accumulation]
Above-mentioned FFS is driven the liquid crystal structure cell is positioned on the light source, measure V-T characteristic (voltage-transmission characteristics) after, measured and applied ± transmissivity (T under the state of 1.5V/60Hz square wave
a).Afterwards, apply ± square wave of 1.5V/60Hz is after 10 minutes, repeats to apply to make it drive 30 minutes under the direct current 1V.Cut off DC voltage, measure through exchanging the transmissivity (T after driving 10 minutes
b), based on T
bAnd T
aDifference calculate the poor of the transmissivity that produced by the voltage that remains in the liquid crystal display cells.
Two (chlorocarbonyl)-1 of 1,3-, 3-dimethyl cyclo-butane-2, the 4-dimethyl dicarboxylate (1,3DMCBDE-Cl) synthetic
A-1: tetrabasic carboxylic acid dialkyl group ester synthesis
[changing 33]
In stream of nitrogen gas, in the 3L four-hole boiling flask, add 220g(0.981mol) 1,3-dimethyl cyclo-butane-1,2,3,4-tetracarboxylic dianhydride (the compound of formula (5-1), hereinafter to be referred as 1,3-DM-CBDA), 2200g(68.7mol, with respect to 1,3-DM-CBDA be 10wt doubly) methyl alcohol, under 65 ℃, add hot reflux, become uniform solution after 30 minutes.Reaction solution directly adds hot reflux 4 hours 30 minutes and stirs.(hereinafter to be referred as HPLC) measured this reactant liquor by high performance liquid chromatography.Analysis to this measurement result is set forth below.
After removing solvent in this reactant liquor with evaporator distillation, the ethyl acetate that adds 1301g is heated to 80 ℃, and it was refluxed 30 minutes.Afterwards, be cooled to interior temperature with per 10 minutes 2～3 ℃ speed and reach 25 ℃, keep intact and under 25 ℃, stirred 30 minutes.By filter taking out the white crystals of having separated out, and after washing this crystallization 2 times with the ethyl acetate of 141g, by the white crystals of drying under reduced pressure acquisition 103.97g.
According to the result that 1HNMR analyzes and X ray crystalline texture is analyzed, confirming this crystallization is compound (1-1) (the HPLC relative area is 97.5%) (yield is 36.8%).
1H NMR(DMSO-d6，δppm);12.82(s，2H)，3.60(s，6H)，3.39(s，2H)，1.40(s，6H)。
A-2.1,3-DM-CBDE-Cl's is synthetic
[changing 34]
Under stream of nitrogen gas, in the four-hole boiling flask of 3L, add 234.15g(0.81mol) compound (1-1), 1170.77g(11.68mol, 5wt is doubly) normal heptane after, add 0.64g(0.01mol) pyridine, be stirred to 75 ℃ with heating under the magnetic stirrer.Then, dripped 289.93g(2.44mol through 1 hour) thionyl chloride.Begin immediately foaming after the dropping, drip 30 minutes afterreaction solution becomes of end and get evenly, stopped foaming.Then, directly 75 ℃ lower stir 1 hour 30 minutes after, the inner capacities of utilizing evaporator that the solvent distillation is removed to 40 ℃ of water-baths reaches 924.41g.Be heated to 60 ℃, make the dissolving crystallized of separating out when distilling desolventizing, and behind the filtration insolubles, with per 10 minutes 1 ℃ speed filtrate is cooled to 25 ℃ carrying out thermosol to filter under 60 ℃.Keep intact and, the white crystals of separating out is taken out after filtration, and wash this crystallization with the normal heptane of 264.21g after 30 minutes 25 ℃ of lower stirrings.By with its drying under reduced pressure, obtain the white crystals of 226.09g.
Then, under stream of nitrogen gas, after the normal heptane of the adding above-mentioned white crystals that makes of 226.09g and 452.18g, heating is stirred to 60 ℃, makes dissolving crystallized in the four-hole boiling flask of 3L.Afterwards, with per 10 minutes speed cooling and stirring to 25 of 1 ℃ ℃, make crystallization.Keep intact 25 ℃ lower stir 1 hour after, the white crystals of separating out is taken out after filtration, and after washing this crystallization with the normal heptane of 113.04g, by the white crystals of drying under reduced pressure acquisition 203.91g.Confirming this crystallization by 1H NMR analysis result is compound (3-1), namely 1, two (chlorocarbonyl)-1 of 3-, 3-dimethyl cyclo-butane-2, and the 4-dimethyl dicarboxylate (1,3-DM-CBDE-C1) (the HPLC relative area is 99.5%) (yield 77.2%).
1H NMR (CDCl 3，δppm)：3.78(s，6H)，3.72(s，2H)，1.69(s，6H)。
(synthesis example 1)
To be made as nitrogen atmosphere with the four-hole boiling flask of the 300ml of stirring apparatus, add 8.0129g(40.02mmol) ODA, add NMP and the 7.13g(90.13mmol of 157.25g) the pyridine as alkali, make its dissolving through stirring.Then 1 of this two amine aqueous solutions limit interpolation 12.2295g (37.61mmol) is stirred on the limit, and 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.The polyamic acid ester solution that makes is added in the water of 1747g while stirring, filters and take out the white precipitate of separating out, then, with the water washing of 1747g 1 time, ethanol with 1747g washs 1 time, uses the ethanol of 437g to wash 3 times, and drying obtains the white poly amic acid ester toner of 16.65g.Yield is 95.3%.In addition, the molecular weight of this poly amic acid ester is Mn=13104, Mw=29112.
The poly amic acid ester toner that 1.8731g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 16.89g, at room temperature stirs 24 hours and makes its dissolving, makes polyamic acid ester solution (A-1).
(synthesis example 2)
To be made as nitrogen atmosphere with the four-hole boiling flask of the 300ml of stirring apparatus, add 7.0154g(35.03mmol) ODA, add NMP and the 6.50g(82.22mmol of 140.77g) the pyridine as alkali, make its dissolving through stirring.Then 1 of this two amine aqueous solutions limit interpolation 11.1392g (34.26mmol) is stirred on the limit, and 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.The polyamic acid ester solution that makes is added in the water of 1564g while stirring, filters and take out the white precipitate of separating out, then, with the water washing of 1564g 1 time, ethanol with 1564g washs 1 time, uses the ethanol of 391g to wash 3 times, and drying obtains the white poly amic acid ester toner of 14.33g.Yield is 91.6%.In addition, the molecular weight of this poly amic acid ester is Mn=24228, Mw=61076.
The poly amic acid ester toner that 1.7324g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 15.65g, at room temperature stirs 24 hours and makes its dissolving, makes polyamic acid ester solution (A-2).
(synthesis example 3)
With 4.583g(23.0mmol) 4,4 '-diamino-diphenylamine is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, adds the NMP of 62.9g, the limit is supplied with the nitrogen limit and is stirred and make its dissolving.CBDA while stirring this two amine aqueous solution and add 4.335g (22.10mmol) adds NMP again and makes solid component concentration reach 10 quality %, at room temperature stirs 24 hours, obtains polyamic acid (B-1) solution.The viscosity of this polyamic acid solution under 25 ℃ of temperature is 165.1mPas.In addition, the molecular weight of this polyamic acid is Mn=17171, Mw=35201.
(embodiment 1)
The polyamic acid solution (B-1) that makes in the polyamic acid ester solution (A-1) that makes in the synthesis example 1 with 1.5114g and the synthesis example 3 of 1.5048g is taken in the there-necked flask, add NMP, the BCS of 1.0016g of 1.028g, obtained aligning agent for liquid crystal (I) in 30 minutes with magnetic stirrer.
(comparative example 1)
The polyamic acid solution (B-1) that makes in the polyamic acid ester solution (A-2) that makes in the synthesis example 2 with 1.5145g and the synthesis example 3 of 1.5241g is taken in the there-necked flask, add NMP, the BCS of 1.0012g of 1.0331g, obtain aligning agent for liquid crystal (II) with magnetic stirrer 30 minutes.
(comparative example 2)
The polyamic acid ester solution (A-1) that makes in the synthesis example 1 with 4.2010g was taken in the there-necked flask, adds NMP, the BCS of 1.2519g of 0.5993g, obtained aligning agent for liquid crystal (III) with magnetic stirrer 30 minutes.
(embodiment 2)
Behind the aligning agent for liquid crystal (I) that makes among the filtrator filtration embodiment 1 with 1.0 μ m, be spun on the glass substrate with transparency electrode, through the drying of heating plate upper 5 minute of 80 ℃ of temperature, in the heated air circulation type stove of 250 ℃ of temperature 60 minutes burn till, obtained the film of the imidizate of thickness 100nm.Measured center line average roughness (Ra) for this imidizate film.Measurement result is shown in table 1 described later.
(comparative example 3)
The aligning agent for liquid crystal that in usage comparison example 1, makes (II), use the method identical with embodiment 2 to make the film of imidizate.Measured center line average roughness (Ra) for this imidizate film.Measurement result is shown in table 1 described later.
[table 1]
According to the result of embodiment 2 and comparative example 3, confirm weight-average molecular weight by making PAE less than PAA, will small concavo-convexly suppress littlely by what being separated of poly amic acid ester and polyamic acid caused, can obtain more level and smooth film.
(embodiment 3)
Behind the aligning agent for liquid crystal (I) that makes among the filtrator filtration embodiment 1 with 1.0 μ m, be spun on the glass substrate with transparency electrode, through 60 minutes burn till in the drying of heating plate upper 5 minute of 80 ℃ of temperature, heated air circulation type stove at 250 ℃, obtained the film of the imidizate of thickness 100nm.Across the ultraviolet 100mJ/cm of polarization plates to this coated surface irradiation 254nm
2, obtain the substrate with liquid crystal orientation film.Prepare 2 this substrates with liquid crystal orientation film, after the liquid crystal aligning face of a substrate scatters the sept of 6 μ m, with the antiparallel condition of the orientation of 2 substrates with 2 substrate in combination, sealing on every side, but stay liquid crystal injecting port, making structure cell opening (cell gap) is the negative crystal born of the same parents of 6 μ m.Vacuum is injected liquid crystal (MLC-2041, Merck ﹠ Co., Inc. (メ Le Network society) system) in this negative crystal born of the same parents at normal temperatures, with the inlet sealing, makes the liquid crystal structure cell.This liquid crystal structure cell is measured voltage retention, then carried out the mensuration of ion concentration.The measurement result of voltage retention and ion concentration is shown in table 2 described later.
(comparative example 4)
The aligning agent for liquid crystal that in usage comparison example 1, makes (II), made the liquid crystal structure cell with method similarly to Example 3.This liquid crystal structure cell is measured voltage retention, then carried out the mensuration of ion concentration.The measurement result of voltage retention and ion concentration is shown in table 2 described later.
(comparative example 5)
The aligning agent for liquid crystal that in usage comparison example 2, makes (III), made the liquid crystal structure cell with method similarly to Example 3.This liquid crystal structure cell is measured voltage retention, then carried out the mensuration of ion concentration.The measurement result of voltage retention and ion concentration is shown in table 2 described later.
[table 2]
According to the result of embodiment 3 and comparative example 4, voltage retention and ion concentration when confirming the more level and smooth film of acquisition during high temperature are good.In addition, result according to embodiment 3 and comparative example 5, confirm and mixed poly amic acid ester and polyamic acid and make in the situation of level and smooth film, compare with independent use poly amic acid ester, voltage retention during high temperature and ion concentration become better, can obtain the high liquid crystal orientation film of reliability.
(embodiment 4)
Behind the aligning agent for liquid crystal (I) that makes among the filtrator filtration embodiment 1 with 1.0 μ m, coat the glass substrate that is formed with fringe field conversion (Fringe Field Switching, hereinafter referred to as FFS) driving electrode by spin-coating method, the described glass substrate that is formed with fringe field conversion driving electrode has ITO electrode as the thickness 50nm of ground floor at glass substrate, as the silicon nitride of the thickness 500nm of the second layer, as the 3rd layer zigzag ITO electrode (electrode width: 3 μ m, electrode gap: 6 μ m, electrode height: 50nm).After 80 ℃ heating plates make its dry 5 minutes, in 250 ℃ heated air circulation type stove, burnt till 60 minutes, forming thickness is filming of 130nm.Across the ultraviolet 100mJ/cm of polarization plates to this coated surface irradiation 254nm
2, obtain the substrate with liquid crystal orientation film.In addition, as not being formed with electrode and having to form too on the glass substrate of column spacer of height 4 μ m and film of counter substrate, implementation orientation is processed.
Above-mentioned 2 plate bases as one group, behind 1 plate base of fitting as 0 ° condition in printing and sealing agent on the substrate and take the relative orientation direction of liquid crystal orientation film in addition, are made sealant cures and make the negative crystal born of the same parents.Inject liquid crystal MLC-2041 (Merck ﹠ Co., Inc. (メ Le Network society) system) by the decompression injection method in the negative crystal born of the same parents, the sealing inlet obtains FFS and drives the liquid crystal structure cell.
This FFS is driven the liquid crystal structure cell carried out the mensuration of liquid crystal aligning restraint and the evaluation of electric charge Accumulation.The results are shown in table 3 described later.
(comparative example 6)
The aligning agent for liquid crystal that in usage comparison example 1, makes (II), made FFS with method similarly to Example 4 and driven the liquid crystal structure cell.This FFS is driven the liquid crystal structure cell carried out the mensuration of liquid crystal aligning restraint and the evaluation of electric charge Accumulation.The results are shown in table 3 described later.
[table 3]
According to the result of embodiment 4 and comparative example 6, confirm the liquid crystal orientation film of the application of the invention, can make and exchange the few liquid crystal orientation film of the driving little and residual electric industry of sintering degree.
Synthesizing (AD-4)
[changing 35]
In the reaction vessel of 500ml, add compound (b) (50.00g, 229mmol), pyridine (0.500g, 0.632mmol), compound (c) (63.02,504mmol), acetonitrile (300g), under nitrogen atmosphere, react through adding hot reflux.After reaction finishes, be cooled to 20 ℃ after, filter, wash with acetonitrile (100g), the acquisition crude product.Then, in crude product, add 2-propyl alcohol (300g), distilled water (100g), and add hot reflux.Afterwards, be cooled to 20 ℃, cross filter solid, with 2-propyl alcohol (100g) washing, dry compound (d) (receipts amount: 37.8g, the yield: 37%) of obtaining.
1H-NMR (
1The light splitting of H nuclear magnetic resonance) (400MHz, DMSO-d
6, σ (ppm)): 8.07 (2H, s), 5.15-5.14 (2H, m), 4.62 (2H, t), 4.59-4.49 (4H, m), 4.38 (2H,, q).
In the 500mL reaction vessel, add compound (d) (20.00g, 44.0mmol), thionyl chloride (120.0g, 1.01mol), add hot reflux.After 30 minutes, be cooled to 20 ℃ after, append thionyl chloride (120.0g, 1.01mol), further carry out 2 hours the hot reflux that adds.After reaction finished, superfluous thionyl chloride was removed in decompression distillation, with hexane (200g) washing.Then, in crude product, add methylene chloride (200g) in 20 ℃ and stir, add compound (c) (12.1g, 96.8mmol), pyridine (13.93g, 176mmol), methylene chloride (100g) solution to wherein slowly dripping down.Stir after 1 hour, further add compound (c) (12.1g, 96.8mmol), pyridine (13.93g, 176mmol).After reaction finished, the distillation desolventizing obtained crude product with distilled water (144g) washing.In this crude product, add tetrahydrofuran (144g), and in 23 ℃ of dispersion washings, filtration, it is rear, dry to use respectively tetrahydrofuran (130g), distilled water (170g), methyl alcohol (150g) to wash, and obtains (AD-4) (receipts amount: 17.72g, yield: 62%).
1H-NMR (
1The light splitting of H nuclear magnetic resonance) (400MHz, DMSO-d
6, σ (ppm)): 8.17 (2H, s), 5.18-5.13 (2H, m), 4.64-4.53 (6H, m), 4.37 (2H, q).
(synthesis example 4)
To be made as nitrogen atmosphere with the four-hole boiling flask of the 300ml of stirring apparatus, add 5.0284g(25.11mmol) ODA, add NMP and the 4.72g(59.63mmol of 202.80g) the pyridine as alkali, make its dissolving through stirring.Then 1 of this two amine aqueous solutions limit interpolation 8.0794g (24.85mmol) is stirred on the limit, and 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.The polyamic acid ester solution that makes is added in the water of 1127g while stirring, filters and take out the white precipitate of separating out, then, with the water washing of 1127g 1 time, ethanol with 1127g washs 1 time, uses the ethanol of 282g to wash 3 times, and drying obtains white poly amic acid ester toner.The molecular weight of this poly amic acid ester is Mn=6394, Mw=13794.
The poly amic acid ester toner that 4.5796g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 41.20g, at room temperature stirs 24 hours and makes its dissolving, makes polyamic acid ester solution (A-3).
(synthesis example 5)
With 2 of 5.1584g (19.82mmol), two (methoxycarbonyl) cyclo-butane-1 of 4-, 3-dicarboxylic acid are taken in the 100ml four-hole boiling flask with stirring apparatus, add the NMP of 68.12g, stir and make its dissolving.Then, add triethylamine, the 1.7315g (16.01mmol) of 4.45g (43.98mmol) p-phenylenediamine (PPD), 0.7922g (3.99mmol) 4,4 '-diaminodiphenyl-methane makes its dissolving through stirring.When stirring this solution, add (2,3-dihydroxy-2-sulfo--3-benzoxazolyl) phosphonic acid diphenyl ester of 16.90g (44.08mmol), add the NMP of 9.67g again, under water-cooled, make its reaction 4 hours.The polyamic acid ester solution that makes while stirring in the 2-propyl alcohol that drops into 650g, and is filtered and takes out the sediment of separating out, and then 2-propyl alcohol washing 5 times, the drying with 210g obtains the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=3860, Mw=5384.
The poly amic acid ester toner that 2.0332g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 18.4708g, at room temperature stirs 24 hours and makes its dissolving, makes polyamic acid ester solution (A-4).
(synthesis example 6)
To be made as nitrogen atmosphere with the 100mL four-hole boiling flask of stirring apparatus, add 4 of 2.01g (10.09mmol), the 3-amino of 4 '-diaminodiphenyl-methane, 0.92g (6.73mmol)-N-methylbenzylamine, add the triethylamine as alkali of NMP, the 3.83g (37.93mmol) of 131.14g, make its dissolving through stirring.Then 1 of this two amine aqueous solutions limit interpolation 5.1407g (15.81mmol) is stirred on the limit, and 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.The polyamic acid ester solution that makes while stirring in the 2-propyl alcohol that drops into 690g, and is filtered and takes out the white precipitate of separating out, then with the 2-propyl alcohol washing 5 times of 220g, the poly amic acid ester toner that drying obtains white.In addition, the molecular weight of this poly amic acid ester is Mn=5064, Mw=11348.
The poly amic acid ester toner that 2.0014g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 18.2912g, at room temperature stirs 24 hours and makes its dissolving, makes polyamic acid ester solution (A-5).
(synthesis example 7)
To be made as nitrogen atmosphere with the 100mL four-hole boiling flask of stirring apparatus, add 4 of 2.01g (10.09mmol), the 3-amino of 4 '-diaminodiphenyl-methane, 0.92g (6.73mmol)-N-methylbenzylamine, add the triethylamine as alkali of NMP, the 4.04g (39.95mmol) of 135.18g, make its dissolving through stirring.Then 1 of this two amine aqueous solutions limit interpolation 5.4260g (16.69mmol) is stirred on the limit, and 3DM-CBDE-Cl makes its reaction 4 hours under water-cooled.The polyamic acid ester solution that makes while stirring in the 2-propyl alcohol that drops into 711g, and is filtered and takes out the white precipitate of separating out, then with the 2-propyl alcohol washing 5 times of 230g, the poly amic acid ester toner that drying obtains white.In addition, the molecular weight of this poly amic acid ester is Mn=11820, Mw=28719.
The poly amic acid ester toner that 2.4381g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 21.4224g, at room temperature stirs 24 hours and makes its dissolving, makes polyamic acid ester solution (A-6).
(synthesis example 8)
With 2 of 2.2617g (8.01mmol), 2 of two (methoxycarbonyl) terephthalic acid (TPA)s of 5-, 2.7808g (10.61mmol), two (methoxycarbonyl) cyclo-butane-1 of 4-, the 3-dicarboxylic acid is taken in the 300ml four-hole boiling flask with stirring apparatus, add the NMP of 102.82g, stir and make its dissolving.Then, 1 of the triethylamine of interpolation 4.45g (43.98mmol), 3.4396g (12.01mmol), 1 of two (4-amino-benzene oxygen) heptane of 5-, 2.3914g (8.01mmol), two (the 4-aminobenzene ethyl) ureas of 3-make its dissolving through stirring.Add the 4-(4,6-dimethoxy-1,3,5-triazines-2-yl) of 16.60g-4-methyl morpholine chloride (15 ± 2 % by weight hydrate) when stirring this solution, add again the NMP of 14.12g, it was reacted 4 hours.The polyamic acid ester solution that makes while stirring in the 2-propyl alcohol that drops into 890g, and is filtered and takes out the sediment of separating out, and then 2-propyl alcohol washing 5 times, the drying with 300g obtains the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=9450, Mw=22588.
The poly amic acid ester toner that 1.1487g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 19.1544g, at room temperature stirs 24 hours and makes its dissolving, makes polyamic acid ester solution (A-7).
(synthesis example 9)
With 2 of 2.2589g (8.00mmol), 2 of two (methoxycarbonyl) terephthalic acid (TPA)s of 5-, 3.0710g (11.80mmol), two (methoxycarbonyl) cyclo-butane-1 of 4-, the 3-dicarboxylic acid is taken in the 300ml four-hole boiling flask with stirring apparatus, add the NMP of 105.54g, stir and make its dissolving.Then, 1 of the triethylamine of interpolation 4.45g (43.98mmol), 3.4376g (12.00mmol), 1 of two (4-amino-benzene oxygen) heptane of 5-, 2.3862g (8.00mmol), two (the 4-aminobenzene ethyl) ureas of 3-make its dissolving through stirring.Add the 4-(4,6-dimethoxy-1,3,5-triazines-2-yl) of 16.73g-4-methyl morpholine chloride (15 ± 2 % by weight hydrate) when stirring this solution, add again the NMP of 14.50g, it was reacted 4 hours.The polyamic acid ester solution that makes while stirring in the 2-propyl alcohol that drops into 910g, and is filtered and takes out the sediment of separating out, and then 2-propyl alcohol washing 5 times, the drying with 300g obtains the poly amic acid ester toner.
The molecular weight of this poly amic acid ester is Mn=18067, Mw=46973.
The poly amic acid ester toner that 1.3221g is obtained is taken in the Erlenmeyer flask of 50ml, adds the NMP of 24.8708g, at room temperature stirs 24 hours and makes its dissolving, makes polyamic acid ester solution (A-8).
(synthesis example 10)
With 20.0838g(132.0mmol) 3, the 5-diaminobenzoic acid is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add DA-1, the NMP of 268.48g of 21.3254 (88.0mmol) g, the limit is supplied with the stirring of nitrogen limit and is made its dissolving.The limit is stirred this two amine aqueous solutions limit and is added 1,2,3 of 42.4946g (216.7mmol), and 4-cyclo-butane tetracarboxylic dianhydride adds NMP again and makes solid component concentration reach 20 quality %, at room temperature stirs 24 hours, obtains polyamic acid (B-2) solution.The viscosity of this polyamic acid solution under 25 ℃ of temperature is 2156mPas.In addition, the molecular weight of this polyamic acid is Mn=18794, Mw=63387.
(synthesis example 11)
With 6.0854g(40.0mmol) 3, the 5-diaminobenzoic acid is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, adds the NMP of 65.56g, the limit is supplied with the nitrogen limit and is stirred and make its dissolving.The limit is stirred this two amine aqueous solutions limit and is added 8.5449g(39.18mmol) pyromellitic acid anhydride, and add NMP and make the concentration of solid constituent reach 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that makes under 25 ℃ of temperature is 523mPas.In addition, the molecular weight of this polyamic acid is Mn=20565, Mw=47912.
The nmp solution of the 3-glycidoxy propyl group methyldiethoxysilane of the 0.3 quality % of interpolation 13.79g obtains polyamic acid solution (B-3) in solution.
(synthesis example 12)
With 3.6541g(24.02mmol) 3,5-diaminobenzoic acid, 4.2931g(16.00mmol) 1, two (4-aminophenyl) piperazines of 4-are taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 36.48g, and the limit is supplied with the nitrogen limit and stirred and make its dissolving.When stirring this two amine aqueous solution, add 4.7522g(23.99mmol) BDA, at room temperature stirred 2 hours.Then, add the NMP of 36.50g, add 3.4084g(15.63mmol) pyromellitic acid anhydride.Further add NMP so that the concentration of solid constituent reaches 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that makes under 25 ℃ of temperature is 1166mPas.In addition, the molecular weight of this polyamic acid is Mn=19307, Mw=42980.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0483g, at room temperature stirred 24 hours, obtain polyamic acid solution (B-4).
(synthesis example 13)
With 3 of 3.6516g (24.0mmol), the 4-of 5-diaminobenzoic acid, 2.4070g (16.02mmol) ((2-methylamino) ethyl) aniline is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 66.21g, the limit is supplied with the stirring of nitrogen limit and is made its dissolving.When stirring this two amine aqueous solution, add 8.5972g(39.42mmol) pyromellitic acid anhydride.Further add NMP so that the concentration of solid constituent reaches 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that makes under 25 ℃ of temperature is 488mPas.In addition, the molecular weight of this polyamic acid is Mn=13205, Mw=33511.
In solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0438g, at room temperature stirred 24 hours, obtain polyamic acid solution (B-5).
(synthesis example 14)
With 0.6123g(4.00mmol) 3,4 of 5-diaminobenzoic acid, 3.199g (16.06mmol), the 4-diamino-diphenylamine is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, adds the NMP of 19.64g, and the limit is supplied with the nitrogen limit and stirred and make its dissolving.When stirring this two amine aqueous solution, add 3.1780g(16.04mmol) BDA, at room temperature stirred 2 hours.Then, add the NMP of 8.93g, add 0.8736g(4.01mmol) pyromellitic acid anhydride.Further add NMP so that the concentration of solid constituent reaches 18 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that makes under 25 ℃ of temperature is 8100mPas.In addition, the molecular weight of this polyamic acid is Mn=22537, Mw=72601.
In solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0235g, at room temperature stirred 24 hours, obtain polyamic acid solution (B-6).
(synthesis example 15)
With 3.6603g(24.06mmol) 3,5-diaminobenzoic acid, 4.7740g(16.0mmol) 1, two (the 4-aminobenzene ethyl) ureas of 3-are taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 28.59g, and the limit is supplied with the nitrogen limit and stirred and make its dissolving.When stirring this two amine aqueous solution, add 2.3782g(12.0mmol) BDA, at room temperature stirred 2 hours.Then, add the NMP of 38.13g, add 6.0903g(27.92mmol) pyromellitic acid anhydride.Further add NMP so that the concentration of solid constituent reaches 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that makes under 25 ℃ of temperature is 744mPas.In addition, the molecular weight of this polyamic acid is Mn=17771, Mw=38991.
In solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0505g, at room temperature stirred 24 hours, obtain polyamic acid solution (B-7).
(synthesis example 16)
With 3.6536g(24.01mmol) 3,5-diaminobenzoic acid, 3.8715g(15.98mmol) DA-1 be taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 31.75g, the limit is supplied with the nitrogen limit and is stirred and make its dissolving.When stirring this two amine aqueous solution, add 3.9621g(20.0mmol) BDA, at room temperature stirred 2 hours.Then, add the NMP of 25.42g, add 1,2,4 of 4.4776g (19.97mmol), 5-cyclohexane tetracarboxylic dianhydride.Further add NMP so that the concentration of solid constituent reaches 20 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that makes under 25 ℃ of temperature is 417mPas.In addition, the molecular weight of this polyamic acid is Mn=13291, Mw=54029.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0476g, at room temperature stirred 24 hours, obtain polyamic acid solution (B-8).
(synthesis example 17)
With 3 of 1.2133g (7.97mmol), 4 of 5-diaminobenzoic acid, 6.8216g (31.98mmol), 4 '-diamino-diphenyl-N-methyl-amine is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 44.03g, the limit is supplied with the stirring of nitrogen limit and is made its dissolving.When stirring this two amine aqueous solution, add the BDA of 7.1310g (36.0mmol), at room temperature stirred 2 hours.Then, add the NMP of 14.62g, add the pyromellitic acid anhydride of 0.8713g (3.99mmol).Further add NMP so that the concentration of solid constituent reaches 18 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that makes under 25 ℃ of temperature is 577mPas.In addition, the molecular weight of this polyamic acid is Mn=12656, Mw=28487.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0480g, at room temperature stirred 24 hours, obtain polyamic acid solution (B-9).
(synthesis example 18)
With 3 of 2.7365g (17.99mmol), 2 of 5-diaminobenzoic acid, 2.5471g (12.0mmol), 2 '-dimethyl-4,4 '-benzidine is taken in the four-hole boiling flask with the 100ml of stirring apparatus and nitrogen ingress pipe, add the NMP of 27.32g, the limit is supplied with the stirring of nitrogen limit and is made its dissolving.When stirring this two amine aqueous solution, add dicyclo [3.3.0] octane-2,4,6 of 2.2562g (902mmol), 8-tetracarboxylic dianhydride, in 80 ℃ of lower stirrings 3 hours.After reaction solution is cooled to room temperature, add the NMP of 27.32g, add 4.5715g(20.96mmol) pyromellitic acid anhydride.Further add NMP so that the concentration of solid constituent reaches 15 quality %, at room temperature stirred 24 hours.The viscosity of the polyamic acid solution that makes under 25 ℃ of temperature is 2190mPas.In addition, the molecular weight of this polyamic acid is Mn=23632, Mw=56881.
In this solution, further add the 3-glycidoxy propyl group methyldiethoxysilane of 0.0360g, at room temperature stirred 24 hours, obtain polyamic acid solution (B-10).
(embodiment 5)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (B-1) that makes in the synthesis example 3 of the polyamic acid ester solution (A-3) that makes in the synthesis example 4 of 3.0443g, 3.0126g, add NMP, the BCS of 2.0083g of 1.7670g, further add the multi-functional epoxy compound's as crosslinking chemical (AD-1) of 0.2380g 5 quality %NMP solution, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (I-1).
(embodiment 6)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (B-1) that makes in the synthesis example 3 of the polyamic acid ester solution (A-3) that makes in the synthesis example 4 of 3.0160g, 3.1312g, add NMP, the BCS of 2.0099g of 2.0339g, further add the compound that contains multifunctional hydroxyl (AD-2) as crosslinking chemical of 0.0274g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (I-2).
(embodiment 7)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (B-1) that makes in the synthesis example 3 of the polyamic acid ester solution (A-3) that makes in the synthesis example 4 of 3.0328g, 3.0058g, add NMP, the BCS of 2.0125g of 2.0417g, further add the multifunctional cyclic carbonate compound (AD-4) as crosslinking chemical of 0.0366g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal ((I-3).
(embodiment 8)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (B-1) that makes in the synthesis example 3 of the polyamic acid ester solution (A-3) that makes in the synthesis example 4 of 3.0463g, 3.0433g, add NMP, the BCS of 2.0367g of 2.0306g, further add the multifunctional oxetane compound (AD-3) as crosslinking chemical of 0.0454g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (I-4).
(embodiment 9)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (B-1) that makes in the synthesis example 3 of the polyamic acid ester solution (A-3) that makes in the synthesis example 4 of 3.0073g, 3.0197g, add NMP, the BCS of 2.0364g of 2.0436g, the N-α as imidizate promoter of further interpolation 0.0701g-(9-fluorenylidene methoxycarbonyl)-N-tert-butoxycarbonyl-L-Histidine, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (I-5).
(embodiment 10)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (B-1) that makes in the synthesis example 3 of the polyamic acid ester solution (A-3) that makes in the synthesis example 4 of 3.0210g, 3.0105g, add NMP, the BCS of 2.0246g of 2.0140g, further add the 4-as imidizate promoter (tert-butoxycarbonyl the is amino) pyridine of 0.0341g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (I-6).
(embodiment 11)
In the Erlenmeyer flask of 50ml, put into stirrer, be taken into the polyamic acid solution (B-1) that makes in the synthesis example 3 of the polyamic acid ester solution (A-3) that makes in the synthesis example 4 of 3.0021g, 3.1795g, add NMP, the BCS of 2.0062g of 2.0480g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (I-7).
(embodiment 12)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-2) that makes in the synthesis example 10 of the polyamic acid ester solution (A-3) that makes in the synthesis example 4 of 1.8064g, 2.1642g, add NMP, the BCS of 2.0388g of 4.1032g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (II-1).
(comparative example 7)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-2) that makes in the synthesis example 10 of the polyamic acid ester solution (A-2) that makes in the synthesis example 2 of 1.8510g, 2.1257g, add NMP, the BCS of 2.0012g of 6.1321g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (II-2).
(embodiment 13)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-3) that makes in the synthesis example 11 of the polyamic acid ester solution (A-4) that makes in the synthesis example 5 of 1.8212g, 2.8206g, add NMP, the BCS of 2.0629g of 3.4198g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (III-1).
(embodiment 14)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-4) that makes in the synthesis example 12 of the polyamic acid ester solution (A-4) that makes in the synthesis example 5 of 4.2276g, 1.2331g, add NMP, the BCS of 2.0189g of 2.6302g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (III-2).
(embodiment 15)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-5) that makes in the synthesis example 13 of the polyamic acid ester solution (A-4) that makes in the synthesis example 5 of 3.0022g, 2.3359g, add NMP, the BCS of 2.0168g of 2.9918g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (III-3).
(embodiment 16)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-6) that makes in the synthesis example 14 of the polyamic acid ester solution (A-5) that makes in the synthesis example 6 of 3.0145g, 1.7284g, add NMP, the BCS of 2.0155g of 3.3210g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (IV-1).
(embodiment 17)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-6) that makes in the synthesis example 14 of the polyamic acid ester solution (A-6) that makes in the synthesis example 7 of 3.0186g, 1.7640g, add NMP, the BCS of 2.0344g of 3.3171g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (IV-2).
(embodiment 18)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-7) that makes in the synthesis example 15 of the polyamic acid ester solution (A-5) that makes in the synthesis example 6 of 3.0250g, 2.1211g, add NMP, the BCS of 2.0720g of 3.0711g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (IV-3).
(embodiment 19)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-7) that makes in the synthesis example 15 of the polyamic acid ester solution (A-6) that makes in the synthesis example 7 of 3.0026g, 2.0594g, add NMP, the BCS of 2.0030g of 3.0194g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (IV-4).
(embodiment 20)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-8) that makes in the synthesis example 16 of the polyamic acid ester solution (A-5) that makes in the synthesis example 6 of 1.2318g, 3.2286g, add NMP, the BCS of 2.0178g of 3.6275g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (IV-5).
(embodiment 21)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-9) that makes in the synthesis example 17 of the polyamic acid ester solution (A-7) that makes in the synthesis example 8 of 4.8328g, 2.1984g, add NMP, the BCS of 2.0307g of 1.2268g, with magnetic stirrer 30 minutes, and make aligning agent for liquid crystal (V-1).
(comparative example 8)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-9) that makes in the synthesis example 17 of the polyamic acid ester solution (A-8) that makes in the synthesis example 9 of 4.8426g, 2.0480g, add NMP, the BCS of 2.0380g of 1.2241g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (V-2).
(embodiment 22)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-5) that makes in the synthesis example 14 of the polyamic acid ester solution (A-7) that makes in the synthesis example 8 of 4.8210g, 2.4526g, add NMP, the BCS of 2.0452g of 0.8197g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (V-3).
(comparative example 9)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-5) that makes in the synthesis example 14 of the polyamic acid ester solution (A-8) that makes in the synthesis example 9 of 4.7940g, 2.5558g, add NMP, the BCS of 2.0254g of 0.8545g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (V-4).
(embodiment 23)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-10) that makes in the synthesis example 18 of the polyamic acid ester solution (A-7) that makes in the synthesis example 8 of 3.6281g, 2.8751g, add NMP, the BCS of 2.0514g of 1.6002g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (V-5).
(embodiment 24)
In the Erlenmeyer flask of 50mL, put into stirrer, be taken into the polyamic acid solution (B-10) that makes in the synthesis example 18 of the polyamic acid ester solution (A-8) that makes in the synthesis example 9 of 3.6507g, 2.8195g, add NMP, the BCS of 1.9982g of 1.6288g, with magnetic stirrer 30 minutes, make aligning agent for liquid crystal (V-6).
(embodiment 25)
Behind the aligning agent for liquid crystal (I-1) that makes among the filtrator filtration embodiment 5 with 1.0 μ m, be spun on the glass substrate with transparency electrode, and through the drying of heating plate upper 5 minute of 80 ℃ of temperature, in the heated air circulation type stove of 230 ℃ of temperature 20 minutes burn till, obtained the film of the imidizate of thickness 100nm.Measured center line average roughness (Ra) for this imidizate film.Measurement result is shown in table 4 described later.
(embodiment 26～45 and comparative example 10～12)
Each aligning agent for liquid crystal that in using above-described embodiment 6～24, comparative example 7～9, makes, use the method identical with embodiment 25 to form respectively and film.Observed the film surface of respectively filming with AFM.In addition, measured center line average roughness (Ra) to respectively filming.These measurement results are shown in table 4.
[table 4]
The possibility of utilizing on the industry
Aligning agent for liquid crystal of the present invention, surface by can reducing the liquid crystal orientation film that makes trickle concavo-convex, the electrical characteristics such as residual of voltage retention, ion concentration, the ghost that is caused by alternating current, DC voltage also are improved in the liquid crystal aligning raising.Its result can be widely used in TN element, STN element, TFT liquid crystal cell, and the liquid crystal display cells of vertical orientating type etc.
Quote the full content of Japanese patent application 2010-058554 number instructions, claims and the specification digest of filing an application on March 15th, 2010 here as the announcement of instructions of the present invention.
Claims (9)
1. aligning agent for liquid crystal, it is characterized in that, contain the poly amic acid ester with the repetitive that is represented by following formula (1), polyamic acid and the organic solvent with the repetitive that is represented by following formula (2), the weight-average molecular weight of described poly amic acid ester is less than the weight-average molecular weight of described polyamic acid
[changing 1]
In formula (1) and formula (2), X
1And X
2Be respectively the organic group of 4 valencys independently, Y
1And Y
2Be the organic group of divalent independently respectively, R
1Be the alkyl of carbon number 1～5, A
1And A
2Alkyl, alkenyl or the alkynyl that maybe can have independently respectively substituent carbon number 1～10 for hydrogen atom.
2. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, in the mass ratio of the content of the content/polyamic acid of poly amic acid ester, the content of described poly amic acid ester and the content of polyamic acid are 1/9～9/1.
3. as described claim 1 or 2 described aligning agent for liquid crystal is characterized in that the total content of described poly amic acid ester and polyamic acid is 0.5～15 quality % with respect to organic solvent.
4. such as each described aligning agent for liquid crystal in the claim 1～3, it is characterized in that the weight-average molecular weight of described poly amic acid ester is less by 1000～100000 than the weight-average molecular weight of described polyamic acid.
5. such as each described aligning agent for liquid crystal in the claim 1～4, it is characterized in that the X in formula (1) and the formula (2)
1And X
2Respectively independently for being selected from least a kind of the structure that represented by following formula,
[changing 2]
6. such as each described aligning agent for liquid crystal in the claim 1～5, it is characterized in that the Y in the described formula (1)
1For being selected from least a kind of the structure that represented by following formula,
[changing 3]
7. such as each described aligning agent for liquid crystal in the claim 1～6, it is characterized in that, in the formula (2), Y
2For being selected from least a kind of the structure that represented by following formula,
[changing 4]
8. liquid crystal orientation film is coated with each described aligning agent for liquid crystal in the claim 1～7 and burn till and makes.
9. liquid crystal orientation film is to each described aligning agent for liquid crystal coating in the claim 1～7 and burn till and the tunicle irradiation that obtains makes through the radioactive ray of polarization.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-058554 | 2010-03-15 | ||
| JP2010058554 | 2010-03-15 | ||
| PCT/JP2011/055973 WO2011115078A1 (en) | 2010-03-15 | 2011-03-14 | Liquid crystal alignment agent containing polyamic acid ester and polyamic acid, and liquid crystal alignment film |
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| Publication Number | Publication Date |
|---|---|
| CN102893208A true CN102893208A (en) | 2013-01-23 |
| CN102893208B CN102893208B (en) | 2015-07-08 |
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| Country | Link |
|---|---|
| JP (1) | JP6048143B2 (en) |
| KR (1) | KR101818788B1 (en) |
| CN (1) | CN102893208B (en) |
| TW (1) | TWI515227B (en) |
| WO (1) | WO2011115078A1 (en) |
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Also Published As
| Publication number | Publication date |
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| KR101818788B1 (en) | 2018-01-15 |
| TW201200541A (en) | 2012-01-01 |
| KR20130016275A (en) | 2013-02-14 |
| WO2011115078A1 (en) | 2011-09-22 |
| CN102893208B (en) | 2015-07-08 |
| JPWO2011115078A1 (en) | 2013-06-27 |
| JP6048143B2 (en) | 2016-12-21 |
| TWI515227B (en) | 2016-01-01 |
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