JP4900560B2 - Novel diamine compound, polymer and liquid crystal aligning agent - Google Patents
Novel diamine compound, polymer and liquid crystal aligning agent Download PDFInfo
- Publication number
- JP4900560B2 JP4900560B2 JP2005284989A JP2005284989A JP4900560B2 JP 4900560 B2 JP4900560 B2 JP 4900560B2 JP 2005284989 A JP2005284989 A JP 2005284989A JP 2005284989 A JP2005284989 A JP 2005284989A JP 4900560 B2 JP4900560 B2 JP 4900560B2
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- JP
- Japan
- Prior art keywords
- liquid crystal
- dianhydride
- polyamic acid
- diamine compound
- mol
- 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.)
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 121
- -1 diamine compound Chemical class 0.000 title claims description 76
- 229920000642 polymer Polymers 0.000 title claims description 60
- 239000003795 chemical substances by application Substances 0.000 title description 31
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 52
- 229920005575 poly(amic acid) Polymers 0.000 claims description 52
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 20
- 239000004642 Polyimide Substances 0.000 claims description 18
- 229920001721 polyimide Polymers 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 150000001875 compounds Chemical class 0.000 description 43
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 36
- 239000000758 substrate Substances 0.000 description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 25
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 230000018044 dehydration Effects 0.000 description 13
- 238000006297 dehydration reaction Methods 0.000 description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- RHRNYXVSZLSRRP-UHFFFAOYSA-N 3-(carboxymethyl)cyclopentane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CC1C(C(O)=O)CC(C(O)=O)C1C(O)=O RHRNYXVSZLSRRP-UHFFFAOYSA-N 0.000 description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 125000000962 organic group Chemical group 0.000 description 7
- DMFZUPUWYGUECI-UHFFFAOYSA-N 4-(2,5-dioxooxolan-3-yl)benzo[e][2]benzofuran-1,3-dione Chemical compound O=C1OC(=O)CC1C1=CC2=CC=CC=C2C2=C1C(=O)OC2=O DMFZUPUWYGUECI-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000004988 Nematic liquid crystal Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 210000002858 crystal cell Anatomy 0.000 description 5
- 239000012024 dehydrating agents Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006358 imidation reaction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 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 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 3
- JYCTWJFSRDBYJX-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3a,4,5,9b-tetrahydrobenzo[e][2]benzofuran-1,3-dione Chemical compound O=C1OC(=O)CC1C1C2=CC=CC=C2C(C(=O)OC2=O)C2C1 JYCTWJFSRDBYJX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000005591 trimellitate group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 2
- JEAQJTYJUMGUCD-UHFFFAOYSA-N 3,4,5-triphenylphthalic acid Chemical compound C=1C=CC=CC=1C=1C(C=2C=CC=CC=2)=C(C(O)=O)C(C(=O)O)=CC=1C1=CC=CC=C1 JEAQJTYJUMGUCD-UHFFFAOYSA-N 0.000 description 2
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 2
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 2
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 2
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 2
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- ITCGQBAPLXQYCA-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-8-methyl-3a,4,5,9b-tetrahydrobenzo[e][2]benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C2=CC(C)=CC=C2C1C1CC(=O)OC1=O ITCGQBAPLXQYCA-UHFFFAOYSA-N 0.000 description 2
- SNCJAJRILVFXAE-UHFFFAOYSA-N 9h-fluorene-2,7-diamine Chemical compound NC1=CC=C2C3=CC=C(N)C=C3CC2=C1 SNCJAJRILVFXAE-UHFFFAOYSA-N 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WDVSHHCDHLJJJR-UHFFFAOYSA-N Proflavine Chemical compound C1=CC(N)=CC2=NC3=CC(N)=CC=C3C=C21 WDVSHHCDHLJJJR-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- OYTKINVCDFNREN-UHFFFAOYSA-N amifampridine Chemical compound NC1=CC=NC=C1N OYTKINVCDFNREN-UHFFFAOYSA-N 0.000 description 2
- 229960004012 amifampridine Drugs 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
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- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- YAAWASYJIRZXSZ-UHFFFAOYSA-N pyrimidine-2,4-diamine Chemical compound NC1=CC=NC(N)=N1 YAAWASYJIRZXSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 150000003431 steroids Chemical group 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/53—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having the nitrogen atom of at least one of the amino groups further bound to a hydrocarbon radical substituted by amino groups
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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Description
本発明は、新規ジアミン化合物、ポリアミック酸、そのイミド化重合体、液晶配向剤および液晶表示素子に関する。さらに詳しくは、新規ジアミン化合物、それを用いたポリアミック酸、そのイミド化重合体、これらの少なくとも一方の重合体を含有する液晶配向剤および当該液晶配向剤から得られる液晶配向膜を具備する液晶表示素子に関する。 The present invention relates to a novel diamine compound, a polyamic acid, an imidized polymer thereof, a liquid crystal aligning agent, and a liquid crystal display element. More specifically, a liquid crystal display comprising a novel diamine compound, a polyamic acid using the same, an imidized polymer thereof, a liquid crystal alignment agent containing at least one of these polymers, and a liquid crystal alignment film obtained from the liquid crystal alignment agent It relates to an element.
従来、透明導電膜を介して液晶配向膜が表面に形成されている2枚の基板の間に、正の誘電異方性を有するネマティック型液晶の層を形成してサンドイッチ構造のセルとし、前記液晶分子の長軸が一方の基板から他方の基板に向かって連続的に90度捻れるようにしたTN(Twisted Nematic)型液晶セルを有するTN型液晶表示素子が知られている。
また、カイラル剤の添加によって当該液晶分子の長軸が基板間で180度以上にわたって連続的に捻れる状態を達成させ、これにより生じる複屈折効果を利用したSTN(Super Twisted Nematic)型液晶表示素子も存在する。さらに最近においては、対向する基板間に負の誘電異方性を有するホメオトロピック配向状態のネマチック液晶層や螺旋軸が基板法線と平行状態にあるコレステリック液晶層を形成させ、それらの液晶層中に色素を添加したゲスト−ホスト型の反射型液晶表示素子も開発されている。これらの液晶表示素子における液晶の配向は、通常、ラビング処理が施された液晶配向膜により発現される。ここに、液晶表示素子を構成する液晶配向膜の材料としては、従来よりポリイミド、ポリアミドおよびポリエステルなどが知られている。特にポリイミドは、耐熱性、液晶との親和性、機械的強度などに優れているため多くの液晶表示素子に使用されている。
Conventionally, a cell of a sandwich structure is formed by forming a nematic liquid crystal layer having positive dielectric anisotropy between two substrates having a liquid crystal alignment film formed on the surface via a transparent conductive film, There is known a TN liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell in which the major axis of liquid crystal molecules is continuously twisted by 90 degrees from one substrate toward the other substrate.
Further, the addition of a chiral agent achieves a state in which the major axis of the liquid crystal molecules is continuously twisted between the substrates by 180 degrees or more, and an STN (Super Twisted Nematic) type liquid crystal display element utilizing the birefringence effect generated thereby. Is also present. More recently, a homeotropically aligned nematic liquid crystal layer having negative dielectric anisotropy between opposing substrates and a cholesteric liquid crystal layer in which the helical axis is parallel to the substrate normal are formed. A guest-host type reflective liquid crystal display element in which a dye is added to the above has also been developed. The alignment of the liquid crystal in these liquid crystal display elements is usually expressed by a liquid crystal alignment film subjected to a rubbing treatment. Here, as a material for the liquid crystal alignment film constituting the liquid crystal display element, polyimide, polyamide, polyester, and the like are conventionally known. In particular, polyimide is used in many liquid crystal display elements because of its excellent heat resistance, affinity with liquid crystals, mechanical strength, and the like.
これまで液晶表示素子の高精細化を始めとする表示品位向上、低消費電力化等の検討が進み、高性能な表示素子としてめざましい発展を遂げ、特許文献1に示されているような高電圧保持率、高信頼性を持つ液晶表示素子が開発されている。しかし近年、従来の透過型に加え反射型、半透過型というような液晶表示素子の利用範囲の拡大、基板の大型化に伴う装置、製造ラインの巨大化が大きく進み、それに伴い高電圧保持率、高信頼性とともにプレチルト角のプロセス条件依存性に対する要求性能も厳しくなってきている。これまでのポリイミドの前駆体であるポリアミック酸や、それを脱水閉環させて得られる構造を有するイミド系重合体などからなる液晶配向膜の中には、その液晶配向膜を用いて液晶表示素子を作成した場合、たとえ高電圧保持率、高信頼性が得られたとしてもプロセス条件に対するプレチルト角の安定性に問題を有するものが数多く存在した。
本発明の目的は、液晶配向膜の製造に用いられるポリアミック酸の製造に好適な新規ジアミン化合物を提供することにある。 The objective of this invention is providing the novel diamine compound suitable for manufacture of the polyamic acid used for manufacture of a liquid crystal aligning film.
本発明の他の目的は、本発明の新規ジアミン化合物を用いたポリアミック酸およびそのイミド化重合体を提供することにある。 Another object of the present invention is to provide a polyamic acid and an imidized polymer thereof using the novel diamine compound of the present invention.
本発明のさらに他の目的は、ポリアミック酸および/またはそのイミド化重合体からなり、そして高電圧保持率、高信頼性を保ちつつも、プレチルト角のプロセス条件依存性が良好である液晶配向膜を提供することにある。 Still another object of the present invention is a liquid crystal alignment film comprising a polyamic acid and / or an imidized polymer thereof, and having a good pretilt angle dependency on process conditions while maintaining a high voltage holding ratio and high reliability. Is to provide.
本発明のさらに他の目的は、本発明の液晶配向膜を備え且上記の如き高電圧保持率の優れた持性を示す液晶配向剤を提供することにある。 Still another object of the present invention is to provide a liquid crystal aligning agent comprising the liquid crystal aligning film of the present invention and having excellent high voltage holding ratio as described above.
本発明のさらに他の目的はおよび利点は以下の説明から明らかになろう。 Still other objects and advantages of the present invention will become apparent from the following description.
本発明によれば、本発明の上記目的および利点は、
第1に下記式(I)
According to the present invention, the above objects and advantages of the present invention are:
First, the following formula (I)
(式中、R1およびR2は、それぞれ独立に、炭素数1〜12のアルキル基、炭素数1〜12のハロアルキル基またはハロゲン原子であり、XおよびYは、互いに独立に、下記式(a)〜(d) (In the formula, R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, or a halogen atom, and X and Y are each independently represented by the following formula ( a) to (d)
のそれぞれで表される2価の結合基のいずれかであり、Zは上記(a)〜(d)のそれぞれで表示される基または酸素原子でありそしてaは0〜4の整数である。)で表されるジアミン化合物(以下、「特定ジアミン化合物」という)によって達成される。 Z is a group represented by each of the above (a) to (d) or an oxygen atom, and a is an integer of 0 to 4. ) (Hereinafter referred to as “specific diamine compound”).
本発明によれば、本発明の上記目的および利点は、
第2に特定ジアミン化合物とテトラカルボン酸二無水物とを反応させて得られるポリアミック酸(以下、「特定重合体I」という)およびそれを脱水閉環させて得られるイミド化重合体(以下、「特定重合体II」という)によって達成される。
According to the present invention, the above objects and advantages of the present invention are:
Secondly, a polyamic acid obtained by reacting a specific diamine compound and tetracarboxylic dianhydride (hereinafter referred to as “specific polymer I”) and an imidized polymer obtained by subjecting it to dehydration and ring closure (hereinafter referred to as “ A specific polymer II ”).
また、本発明によれば、本発明の上記目的および利点は、
第3にポリアミック酸(特定重合体I)および/またはイミド化重合体(特定重合体II)を含有する液晶配向剤によって達成される。
According to the present invention, the above object and advantage of the present invention are as follows.
Thirdly, it is achieved by a liquid crystal aligning agent containing a polyamic acid (specific polymer I) and / or an imidized polymer (specific polymer II).
さらに、本発明によれば、本発明の上記目的および利点は、
第4に、本発明の液晶配向剤から得られる液晶配向膜を備えた液晶表示素子によって達成される。
Furthermore, according to the present invention, the above objects and advantages of the present invention are as follows:
Fourthly, it is achieved by a liquid crystal display device provided with a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.
本発明のジアミン化合物を用いて合成されたポリアミック酸および/またはイミド化重合体より形成される配向膜は、従来の配向膜と比べ高電圧保持率を保ちながらも優れたプレチルト角のプロセスマージン依存性をもち、TN型液晶表示素子、STN型液晶表示素子、反射型液晶表示素子および半透過型液晶表示素子など種々の液晶表示素子を構成するために好適に使用することができる。
本発明の液晶表示素子は、種々の装置に有効に使用することができ、例えば、卓上計算機、腕時計、置時計、携帯電話、計数表示板、ワードプロセッサ、パーソナルコンピュータ、液晶テレビなどの表示装置として好適に用いることができる。
The alignment film formed from the polyamic acid and / or imidized polymer synthesized by using the diamine compound of the present invention has an excellent pretilt angle dependency on the process margin while maintaining a high voltage holding ratio as compared with the conventional alignment film. And can be suitably used to construct various liquid crystal display elements such as a TN liquid crystal display element, an STN liquid crystal display element, a reflective liquid crystal display element, and a transflective liquid crystal display element.
The liquid crystal display element of the present invention can be effectively used in various devices, and is suitable for display devices such as desk calculators, watches, table clocks, mobile phones, counting display boards, word processors, personal computers, and liquid crystal televisions. Can be used.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
特定ジアミン化合物
本発明で用いられる特定ジアミン化合物は、上記式(I)で表される化合物である。式(I)中、R1、R2は、互に独立に、炭素数1〜12のアルキル基、炭素数1〜12のハロアルキル基またはハロゲン原子であり、X、Yは互いに独立に上記式(a)〜(d)のそれぞれで表れされるエステル基またはアミド基であり、Zは上記式(a)〜(d)のそれぞれで表わされる基または酸素原子であり、aは0〜4の整数である。また、aが2〜4の整数のとき、複数のR1は同一でも異なっていてもよい。
R1、R2を表す炭素数1〜12のアルキル基としては、炭素数1〜4の低級アルキル基が好ましく、その例としては、メチル基、エチル基、n−プロピル基、iso−プロピル基、n−ブチル基、tert−ブチル基などを挙げることができる。R1、R2を表す炭素数1〜12のハルアルキル基としては、例えばトリフルオロメチル基を好ましいものとして挙げることができる。また、R1を表すハロゲン原子としては、例えばフッ素原子を挙げることができる。
上記式(I)で示される特定ジアミン化合物は、例えば次に示す方法によって得られる。
[Xが上記式(a)で表わされる基でありそして、Yが上記式(b)で表される基である化合物]
工程(i).下記式(II)
Specific diamine compound The specific diamine compound used in the present invention is a compound represented by the above formula (I). In the formula (I), R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, or a halogen atom, and X and Y are independently selected from the above formulae. It is an ester group or an amide group represented by each of (a) to (d), Z is a group or oxygen atom represented by each of the above formulas (a) to (d), and a is 0 to 4 It is an integer. Also, when a is an integer from 2 to 4, a plurality of R 1 may be the same or different.
The alkyl group having 1 to 12 carbon atoms representing R 1 and R 2 is preferably a lower alkyl group having 1 to 4 carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. , N-butyl group, tert-butyl group and the like. The hull alkyl group having 1 to 12 carbon atoms representing the R 1, R 2, can be cited as an example preferred the trifluoromethyl group. Examples of the halogen atom representing R 1 include a fluorine atom.
The specific diamine compound represented by the above formula (I) can be obtained by, for example, the following method.
[Compound wherein X is a group represented by the above formula (a) and Y is a group represented by the above formula (b)]
Step (i). Following formula (II)
(ここでAはハロゲン原子である)で表されるジニトロ安息香酸ハライド化合物に、ジヒドロキシシクロヘキサンを反応させて、下記式(III) (Wherein A is a halogen atom) a dinitrobenzoic acid halide compound is reacted with dihydroxycyclohexane to give the following formula (III)
で表される水酸基を含有する化合物を得る。
工程(ii).工程(i)で生成した水酸基を有する化合物(III)に、下記式(IV)
The compound containing the hydroxyl group represented by this is obtained.
Step (ii). In the compound (III) having a hydroxyl group produced in the step (i), the following formula (IV)
(ここで、R1、R2、Z、Aおよびaの定義は上記に同じである)で表される化合物を反応させて、下記式(V) (Wherein the definitions of R 1 , R 2 , Z, A and a are the same as above) are reacted to give the following formula (V)
(ここで、R1、R2、Zおよびaの定義は上記に同じである)で表されるジニトロ化合物を得る。
工程(iii).工程(ii)で得られたジニトロ化合物(V)を還元し、下記式(VI)
(Wherein the definitions of R 1 , R 2 , Z and a are the same as above).
Step (iii). The dinitro compound (V) obtained in step (ii) is reduced, and the following formula (VI)
(ここで、R1、R2、Zおよびaの定義は上記に同じである)で表される特定ジアミン化合物を得る。 (Here, the definition of R < 1 >, R < 2 >, Z, and a is the same as above.) The specific diamine compound represented by this is obtained.
[Xが上記式(c)で表わされる基でありそしてYが上記式(d)で表される場合]
工程(i).上記式(II)で表されるジニトロ安息香酸ハライドにジアミノシクロヘキサンを反応させて、下記式(VII)
[When X is a group represented by the above formula (c) and Y is represented by the above formula (d)]
Step (i). The dinitrocyclohexane halide represented by the above formula (II) is reacted with diaminocyclohexane to give the following formula (VII)
で表されるアミノ基を有する化合物を得る。
工程(ii).工程(i)で生成したアミノ基を有する化合物(VII)に、上記式(IV)で表される化合物を反応させて、下記式(VIII)
The compound which has an amino group represented by these is obtained.
Step (ii). The compound represented by the above formula (IV) is reacted with the compound (VII) having an amino group produced in the step (i), and the following formula (VIII)
(ここで、R1、R2、Zおよびaの定義は上記に同じである。)で表されるジニトロ化合物を得る。
工程(iii).工程(ii)で得られたジニトロ化合物(VIII)を還元し、下記式(IX)
(Here, the definitions of R 1 , R 2 , Z and a are the same as above.) Are obtained.
Step (iii). The dinitro compound (VIII) obtained in step (ii) is reduced, and the following formula (IX)
(ここで、R1、R2、Zおよびaの定義は上記に同じである。)で表される特定ジアミン化合物を得る。 (Here, the definitions of R 1 , R 2 , Z and a are the same as above.) Are obtained.
特定ジアミン化合物の合成反応には、必要に応じて溶媒を用いることができる。上記溶媒としては、特定ジアミン化合物を溶解させることができ、かつ反応を阻害しないものであれば特に限定されない。例えばベンゼン、トルエンなどの芳香族炭化水素;ジエチルエーテル、テトラヒドロフラン、ジオキサンなどのエーテル類;アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン類;その他ジメチルスルフォオキシド、ジメチルホルムアミド、ジメチルアセトアミドなどを挙げることができる。上記反応に用いられる塩基性触媒としては、例えば水酸化ナトリウム、水酸化カリウム、ピリジン、トリエチルアミンなどを挙げることができる。
上記工程(i)における上記式(II)で表されるジニトロ安息香酸ハライド化合物とシクロヘキサン構造を有する化合物との使用割合は、ジニトロ安息香酸ハライド化合物1モルに対し、シクロヘキサン構造を有する化合物が2〜20モルが好ましい。上記工程(ii)における工程(i)で得られた化合物(III)または(VII)の1モルに対する上記式(IV)または(VIII)で表される化合物の使用割合は1〜1.2モルが好ましい。
In the synthesis reaction of the specific diamine compound, a solvent can be used as necessary. The solvent is not particularly limited as long as it can dissolve the specific diamine compound and does not inhibit the reaction. For example, aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and other dimethylsulfoxide, dimethylformamide and dimethylacetamide it can. Examples of the basic catalyst used in the above reaction include sodium hydroxide, potassium hydroxide, pyridine, triethylamine and the like.
The ratio of the dinitrobenzoic acid halide compound represented by the above formula (II) in the step (i) and the compound having a cyclohexane structure is such that the compound having a cyclohexane structure is 2 to 1 mol of the dinitrobenzoic acid halide compound. 20 moles are preferred. The ratio of the compound represented by the above formula (IV) or (VIII) to 1 mol of the compound (III) or (VII) obtained in the step (i) in the above step (ii) is 1 to 1.2 mol. Is preferred.
上記工程(iii)におけるジニトロ化合物の還元には、水素ガス、ヒドラジン、塩酸などの還元剤を周知の触媒の存在化に行うことができる。上記触媒としては、たとえばVIII族金属、すなわち鉄、コバルト、ニッケル、ルテニウム、ロジウム、パラジウム、オスミウム、インジウム、白金などの金属を活性主体とする金属触媒、具体的には担体に上記金属が担時された触媒、上記金属の錯体触媒を挙げることができる。上記還元反応は均一系でも不均一系であってもよい。 In the reduction of the dinitro compound in the step (iii), a reducing agent such as hydrogen gas, hydrazine, or hydrochloric acid can be used in the presence of a known catalyst. Examples of the catalyst include a group VIII metal, that is, a metal catalyst mainly composed of a metal such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, indium and platinum, specifically, when the metal is supported on a support. And the above-mentioned metal complex catalysts. The reduction reaction may be homogeneous or heterogeneous.
上記触媒の使用量は、適宜の割合で使用でき、例えば触媒が前記VIII族の金属を活性主体とする場合、ジニトロ化合物100重量部に対して0.0001〜100重量部、特に0.001〜20重量部の範囲で用いることが好ましい。また、上記還元反応として、亜鉛、スズ、炭化スズ(II)、硫化ナトリウム、ナトリウムヒドロスルフィド、亜二チオン酸ナトリウム、硫化アンモニウムなどの還元剤を用いる方法も使用できる。この場合、還元剤はジニトロ化合物のニトロ基1モルに対して0.001〜10モルの範囲で使用することが好ましい。
上記還元反応に用いる溶媒としては、ジニトロ化合物とジアミン化合物とをともに溶解し、還元反応によって変質しないものが好ましく、例えばメタノール、エタノール、プロパノール、ブタノールなどのアルコール類;ジエチルエーテル、1,2−ジメトキシエタン、テトラヒドロフラン、ジオキサン、アニソールなどのエーテル類をあげることができる。
特定ジアミン化合物は、単独でまたは2種類以上を組み合わせて使用でき、下記式(X)〜(XVII)の化合物が好ましいものとして例示される。
The amount of the catalyst used can be used at an appropriate ratio. For example, when the catalyst is mainly composed of the group VIII metal, the catalyst is used in an amount of 0.0001 to 100 parts by weight, particularly 0.001 to 100 parts by weight based on 100 parts by weight of the dinitro compound. It is preferably used in the range of 20 parts by weight. In addition, as the reduction reaction, a method using a reducing agent such as zinc, tin, tin (II) carbide, sodium sulfide, sodium hydrosulfide, sodium dithionite, or ammonium sulfide can be used. In this case, the reducing agent is preferably used in the range of 0.001 to 10 mol with respect to 1 mol of the nitro group of the dinitro compound.
As the solvent used in the reduction reaction, those which dissolve both the dinitro compound and the diamine compound and are not altered by the reduction reaction are preferable. For example, alcohols such as methanol, ethanol, propanol and butanol; diethyl ether, 1,2-dimethoxy Examples include ethers such as ethane, tetrahydrofuran, dioxane, and anisole.
A specific diamine compound can be used individually or in combination of 2 or more types, The compound of following formula (X)-(XVII) is illustrated as a preferable thing.
また、本発明に使用されるジアミン化合物には、特定ジアミン化合物の他に、本発明の効果を損なわない範囲で他のジアミン化合物を併用することができる。 In addition to the specific diamine compound, other diamine compounds can be used in combination with the diamine compound used in the present invention as long as the effects of the present invention are not impaired.
他のジアミン化合物としては、以下に示す化合物が例示される。p−フェニレンジアミン、m−フェニレンジアミン、4,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルエタン、4,4’−ジアミノジフェニルスルフィド、4,4’−ジアミノジフェニルスルホン、3,3’−ジメチル−4,4’−ジアミノビフェニル、4,4’−ジアミノベンズアニリド、4,4’−ジアミノジフェニルエーテル、1,5−ジアミノナフタレン、2,2’−ジメチル−4,4’−ジアミノビフェニル、5−アミノ−1−(4’−アミノフェニル)−1,3,3−トリメチルインダン、6−アミノ−1−(4’−アミノフェニル)−1,3,3−トリメチルインダン、3,4’−ジアミノジフェニルエーテル、3,3’−ジアミノベンゾフェノン、3,4’−ジアミノベンゾフェノン、4,4’−ジアミノベンゾフェノン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2−ビス(4−アミノフェニル)ヘキサフルオロプロパン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]スルホン、1,4−ビス(4−アミノフェノキシ)ベンゼン、1,3−ビス(4−アミノフェノキシ)ベンゼン、1,3−ビス(3−アミノフェノキシ)ベンゼン、9,9−ビス(4−アミノフェニル)−10−ヒドロアントラセン、2,7−ジアミノフルオレン、9,9−ビス(4−アミノフェニル)フルオレン、4,4’−メチレン−ビス(2−クロロアニリン)、2,2’,5,5’−テトラクロロ−4,4’−ジアミノビフェニル、2,2’−ジクロロ−4,4’−ジアミノ−5,5’−ジメトキシビフェニル、3,3’−ジメトキシ−4,4’−ジアミノビフェニル、1,4,4’−(p−フェニレンイソプロピリデン)ビスアニリン、4,4’−(m−フェニレンイソプロピリデン)ビスアニリン、2,2’−ビス[4−(4−アミノ−2−トリフルオロメチルフェノキシ)フェニル]ヘキサフルオロプロパン、4,4’−ジアミノ−2,2’−ビス(トリフルオロメチル)ビフェニル、4,4’−ビス[(4−アミノ−2−トリフルオロメチル)フェノキシ]−オクタフルオロビフェニルなどの芳香族ジアミン;
1,1−メタキシリレンジアミン、1,3−プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、4,4−ジアミノヘプタメチレンジアミン、1,4−ジアミノシクロヘキサン、イソホロンジアミン、テトラヒドロジシクロペンタジエニレンジアミン、トリシクロ[6.2.1.02,7]−ウンデシレンジメチルジアミン、4,4’−メチレンビス(シクロヘキシルアミン)などの脂肪族および脂環式ジアミン;
2,3−ジアミノピリジン、2,6−ジアミノピリジン、3,4−ジアミノピリジン、2,4−ジアミノピリミジン、5,6−ジアミノ−2,3−ジシアノピラジン、5,6−ジアミノ−2,4−ジヒドロキシピリミジン、2,4−ジアミノ−6−ジメチルアミノ−1,3,5−トリアジン、1,4−ビス(3−アミノプロピル)ピペラジン、2,4−ジアミノ−6−イソプロポキシ−1,3,5−トリアジン、2,4−ジアミノ−6−メトキシ−1,3,5−トリアジン、2,4−ジアミノ−6−フェニル−1,3,5−トリアジン、2,4−ジアミノ−6−メチル−s−トリアジン、2,4−ジアミノ−1,3,5−トリアジン、4,6−ジアミノ−2−ビニル−s−トリアジン、2,4−ジアミノ−5−フェニルチアゾール、2,6−ジアミノプリン、5,6−ジアミノ−1,3−ジメチルウラシル、3,5−ジアミノ−1,2,4−トリアゾール、6,9−ジアミノ−2−エトキシアクリジンラクテート、3,8−ジアミノ−6−フェニルフェナントリジン、1,4−ジアミノピペラジン、3,6−ジアミノアクリジン、ビス(4−アミノフェニル)フェニルアミンおよび下記式(XVIII)および(XIX)のそれぞれで表される化合物などの、分子内に2つの1級アミノ基および該1級アミノ基以外の窒素原子を有するジアミン;
Examples of other diamine compounds include the compounds shown below. p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfone, 3,3′- Dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 5 -Amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'- Diaminodiphenyl ether, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3- Bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′ -Methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-di Mino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 1,4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenylene) Isopropylidene) bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) Aromatic diamines such as biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;
1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1 , 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, tricyclo [6.2.1.0 2,7 ] -undecylenedimethyldiamine, aliphatic such as 4,4′-methylenebis (cyclohexylamine) And alicyclic diamines;
2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4 -Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3 , 5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl -S-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6- Aminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6 Intramolecular such as phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and compounds represented by the following formulas (XVIII) and (XIX) A diamine having two primary amino groups and a nitrogen atom other than the primary amino group;
(式中、R3は、ピリジン、ピリミジン、トリアジン、ピペリジンおよびピペラジンから選ばれる窒素原子を含む環構造を有する1価の有機基を示し、X1は2価の有機基を示す。) (Wherein R 3 represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X 1 represents a divalent organic group.)
(式中、X2は、ピリジン、ピリミジン、トリアジン、ピペリジンおよびピペラジンから選ばれる窒素原子を含む環構造を有する2価の有機基を示し、R4は2価の有機基を示し、複数存在するX2は、同一でも異なっていてもよい。)
下記式(XX)で表されるモノ置換フェニレンジアミン類;下記式(XXI)で表されるジアミノオルガノシロキサン;
(Wherein X 2 represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, R 4 represents a divalent organic group, and there are a plurality of them. X 2 may be the same or different.)
Mono-substituted phenylenediamines represented by the following formula (XX); diaminoorganosiloxanes represented by the following formula (XXI);
(式中、R5は、−O−、−COO−、−OCO−、−NHCO−、−CONH−および−CO−から選ばれる2価の有機基を示し、R6は、ステロイド骨格、トリフルオロメチル基およびフルオロ基から選ばれる基を有する1価の有機基または炭素数6〜30のアルキル基を示す。) (Wherein R 5 represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R 6 represents a steroid skeleton, A monovalent organic group having a group selected from a fluoromethyl group and a fluoro group or an alkyl group having 6 to 30 carbon atoms is shown.)
(式中、R7は炭素数1〜12の炭化水素基を示し、複数存在するR7は、それぞれ同一でも異なっていてもよく、pは1〜3の整数であり、qは1〜20の整数である。)
および下記式(XXII)〜(XXVI)のそれぞれで表される化合物などを挙げることができる。これらのジアミン化合物は、単独でまたは2種以上組み合わせて用いることができる。
(Wherein R 7 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R 7 may be the same or different, p is an integer of 1 to 3, and q is 1 to 20) Is an integer.)
And compounds represented by the following formulas (XXII) to (XXVI). These diamine compounds can be used alone or in combination of two or more.
(式中、yは2〜12の整数であり、zは1〜5の整数である。)
これらのうち、p−フェニレンジアミン、4,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルスルフィド、1,5−ジアミノナフタレン、2,7−ジアミノフルオレン、4,4’−ジアミノジフェニルエーテル、2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン、9,9−ビス(4−アミノフェニル)フルオレン、2,2−ビス[4−(4−アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2−ビス(4−アミノフェニル)ヘキサフルオロプロパン、4,4’−(p−フェニレンジイソプロピリデン)ビスアニリン、4,4’−(m−フェニレンジイソプロピリデン)ビスアニリン、1,4−シクロヘキサンジアミン、4,4’−メチレンビス(シクロヘキシルアミン)、1,4−ビス(4−アミノフェノキシ)ベンゼン、4,4’−ビス(4−アミノフェノキシ)ビフェニル、上記式(XXII)〜(XXVI)のそれぞれで表される化合物、2,6−ジアミノピリジン、3,4−ジアミノピリジン、2,4−ジアミノピリミジン、3,6−ジアミノアクリジン、上記式(XVIII)で表される化合物のうち下記式(XXVII)で表される化合物、上記式(XIX)で表される化合物のうち下記式(XXVIII)で表される化合物および上記式(XX)で表される化合物のうち下記式(XXIX)〜(XXXIV)のそれぞれで表される化合物が好ましい。
(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5.)
Among these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2 , 2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine 4,4′-methylenebis (cyclohexylamine), 1,4-bis (4-amino) Enoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, compounds represented by the above formulas (XXII) to (XXVI), 2,6-diaminopyridine, 3,4-diaminopyridine, 2 1,4-diaminopyrimidine, 3,6-diaminoacridine, a compound represented by the following formula (XXVII) among the compounds represented by the above formula (XVIII), and the following formula among the compounds represented by the above formula (XIX) Of the compounds represented by (XXVIII) and the compounds represented by the above formula (XX), compounds represented by the following formulas (XXIX) to (XXXIV) are preferred.
テトラカルボン酸二無水物
本発明に使用されるテトラカルボン酸二無水物としては、以下に示す化合物が例示される。ブタンテトラカルボン酸二無水物、1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジクロロ−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2,3,4−テトラメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2,3,4−シクロペンタンテトラカルボン酸二無水物、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物、3,3’,4,4’−ジシクロヘキシルテトラカルボン酸二無水物、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、3,5,6−トリカルボキシノルボルナン−2−酢酸二無水物、2,3,4,5−テトラヒドロフランテトラカルボン酸二無水物、1,3,3a,4,5,9b−ヘキサヒドロ−5(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−5−メチル−5(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−5−エチル−5(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−7−メチル−5(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−7−エチル−5(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−エチル−5(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−5,8−ジメチル−5(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]−フラン−1,3−ジオン、5−(2,5−ジオキソテトラヒドロフラル)−3−メチル−3−シクロヘキセン−1,2−ジカルボン酸二無水物、ビシクロ[2.2.2]−オクト−7−エン−2,3,5,6−テトラカルボン酸二無水物、3−オキサビシクロ[3.2.1]オクタン−2,4−ジオン−6−スピロ−3’−(テトラヒドロフラン−2’,5’−ジオン)、下記式(1)および(2)で表される化合物などの脂肪族および脂環式テトラカルボン酸二無水物;
Tetracarboxylic dianhydride Examples of the tetracarboxylic dianhydride used in the present invention include the compounds shown below. Butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3 3a, 4,5,9b-Hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3 3a, 4,5,9b-Hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3 3a, 4,5,9b-Hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3 3a, 4,5,9b-Hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3- Chlohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2 .1] Aliphatics and fats such as octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), compounds represented by the following formulas (1) and (2) Cyclic tetracarboxylic dianhydrides;
(式中、R8およびR10は、芳香環を有する2価の有機基を示し、R9およびR11は、水素原子またはアルキル基を示し、複数存在するR9およびR11は、それぞれ同一でも異なっていてもよい。)
ピロメリット酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’−ビフェニルスルホンテトラカルボン酸二無水物、1,4,5,8−ナフタレンテトラカルボン酸二無水物、2,3,6,7−ナフタレンテトラカルボン酸二無水物、3,3’,4,4’−ビフェニルエーテルテトラカルボン酸二無水物、3,3’,4,4’−ジメチルジフェニルシランテトラカルボン酸二無水物、3,3’,4,4’−テトラフェニルシランテトラカルボン酸二無水物、1,2,3,4−フランテトラカルボン酸二無水物、4,4’−ビス(3,4−ジカルボキシフェノキシ)ジフェニルスルフィド二無水物、4,4’−ビス(3,4−ジカルボキシフェノキシ)ジフェニルスルホン二無水物、4,4’−ビス(3,4−ジカルボキシフェノキシ)ジフェニルプロパン二無水物、3,3’,4,4’−パーフルオロイソプロピリデンジフタル酸二無水物、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、ビス(フタル酸)フェニルホスフィンオキサイド二無水物、p−フェニレン−ビス(トリフェニルフタル酸)二無水物、m−フェニレン−ビス(トリフェニルフタル酸)二無水物、ビス(トリフェニルフタル酸)−4,4’−ジフェニルエーテル二無水物、ビス(トリフェニルフタル酸)−4,4’−ジフェニルメタン二無水物、エチレングリコール−ビス(アンヒドロトリメリテート)、プロピレングリコール−ビス(アンヒドロトリメリテート)、1,4−ブタンジオール−ビス(アンヒドロトリメリテート)、1,6−ヘキサンジオール−ビス(アンヒドロトリメリテート)、1,8−オクタンジオール−ビス(アンヒドロトリメリテート)、2,2−ビス(4−ヒドロキシフェニル)プロパン−ビス(アンヒドロトリメリテート)、下記式(3)〜(6)のそれぞれで表される化合物などの芳香族テトラカルボン酸二無水物を挙げることができる。これらは1種単独でまたは2種以上組み合わせて用いられる。
(Wherein R 8 and R 10 represent a divalent organic group having an aromatic ring, R 9 and R 11 represent a hydrogen atom or an alkyl group, and a plurality of R 9 and R 11 are the same. But it may be different.)
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicar Boxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (Phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4 , 4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, ethylene glycol-bis (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate) 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydride) Trimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), the following formulas (3) to (6) An aromatic tetracarboxylic dianhydride such as a compound represented by each of the above can be exemplified. These may be used alone or in combination of two or more.
これらのうち、ブタンテトラカルボン酸二無水物、1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2,3,4−シクロペンタンテトラカルボン酸二無水物、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、5−(2,5−ジオキソテトラヒドロフラル)−3−メチル−3−シクロヘキセン−1,2−ジカルボン酸二無水物、1,3,3a,4,5,9b−ヘキサヒドロ−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−5,8−ジメチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、ビシクロ[2.2.2]−オクト−7−エン−2,3,5,6−テトラカルボン酸二無水物、3−オキサビシクロ[3.2.1]オクタン−2,4−ジオン−6−スピロ−3’−(テトラヒドロフラン−2’,5’−ジオン)、ピロメリット酸二無水物、3,3’,4,4’−ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’−ビフェニルスルホンテトラカルボン酸二無水物、1,4,5,8−ナフタレンテトラカルボン酸二無水物、上記式(1)で表される化合物のうち下記式(7)〜(9)のそれぞれで表される化合物および上記式(2)で表される化合物のうち下記式(10)で表される化合物が、良好な液晶配向性を発現させることができる観点から好ましく、特に好ましいものとして、1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,3−ジメチル−1,2,3,4−シクロブタンテトラカルボン酸二無水物、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物、2,3,5−トリカルボキシシクロペンチル酢酸二無水物、1,3,3a,4,5,9b−ヘキサヒドロ−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)−ナフト[1,2−c]フラン−1,3−ジオン、3−オキサビシクロ[3.2.1]オクタン−2,4−ジオン−6−スピロ−3’−(テトラヒドロフラン−2’,5’−ジオン)、ピロメリット酸二無水物および下記式(7)〜(10)で表される化合物を挙げることができる。 Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- ( 2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5 − Oxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic Acid dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Of the anhydrides, compounds represented by the above formula (1) Of the compounds represented by the formulas (7) to (9) and the compound represented by the above formula (2), the compound represented by the following formula (10) exhibits good liquid crystal orientation. Are preferable from the viewpoint of being capable of producing 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, , 2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2, 5-Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2, 5-Dioxo -3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran) -2 ', 5'-dione), pyromellitic dianhydride and compounds represented by the following formulas (7) to (10).
[ポリアミック酸の合成反応]
本発明に用いられる特定重合体I(ポリアミック酸)は特定ジアミン化合物を含有するジアミン化合物とテトラカルボン酸二無水物とを反応させて得られる。特定ジアミン化合物の使用割合は、全ジアミン化合物中、0.1〜100モル%を占めるのが好ましく、5〜30モル%を占めるのがより好ましい。ポリアミック酸の合成反応に供されるテトラカルボン酸二無水物とジアミン化合物の使用割合は、ジアミン化合物に含まれるアミノ基1当量に対して、テトラカルボン酸二無水物の酸無水物基が0.2〜2当量となる割合が好ましく、さらに好ましくは0.3〜1.2当量となる割合である。
[Synthetic reaction of polyamic acid]
The specific polymer I (polyamic acid) used in the present invention is obtained by reacting a diamine compound containing a specific diamine compound with tetracarboxylic dianhydride. The use ratio of the specific diamine compound preferably occupies 0.1 to 100 mol%, and more preferably 5 to 30 mol% in all diamine compounds. The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
ポリアミック酸の合成反応は、有機溶媒中において、好ましくは−20〜150℃、より好ましくは0〜100℃の温度条件下で行われる。ここで、有機溶媒としては、合成される特定重合体Iを溶解できるものであれば特に制限はなく、例えばN−メチル−2−ピロリドン、N,N−ジメチルアセトアミド、N,N−ジメチルホルムアミド、ジメチルスルホキシド、γ−ブチロラクトン、テトラメチル尿素、ヘキサメチルホスホルトリアミドなどの非プロトン系極性溶媒;m−クレゾール、キシレノール、フェノール、ハロゲン化フェノールなどのフェノール系溶媒を例示することができる。また、有機溶媒の使用量(a)は、テトラカルボン酸二無水物およびジアミン化合物の総量(b)が、反応溶液の全量(a+b)に対して0.1〜30重量%になるような量であることが好ましい。 The synthetic reaction of polyamic acid is preferably carried out in an organic solvent under a temperature condition of -20 to 150 ° C, more preferably 0 to 100 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the specific polymer I to be synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Examples include aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount of the organic solvent used (a) is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight with respect to the total amount (a + b) of the reaction solution. It is preferable that
[貧溶媒]
なお、前記有機溶媒には、ポリアミック酸の貧溶媒であるアルコール類、ケトン類、エステル類、エーテル類、ハロゲン化炭化水素類、炭化水素類などを、生成するポリアミック酸が析出しない範囲で併用することができる。かかる貧溶媒の具体例としては、例えばメチルアルコール、エチルアルコール、イソプロピルアルコール、シクロヘキサノール、エチレングリコール、プロピレングリコール、1,4−ブタンジオール、トリエチレングリコール、エチレングリコールモノメチルエーテル、乳酸エチル、乳酸ブチル、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、酢酸メチル、酢酸エチル、酢酸ブチル、メチルメトキシプロピオネ−ト、エチルエトキシプロピオネ−ト、シュウ酸ジエチル、マロン酸ジエチル、ジエチルエーテル、エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコール−n−プロピルエーテル、エチレングリコール−i−プロピルエーテル、エチレングリコール−n−ブチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、テトラヒドロフラン、ジクロロメタン、1,2−ジクロロエタン、1,4−ジクロロブタン、トリクロロエタン、クロルベンゼン、o−ジクロルベンゼン、ヘキサン、ヘプタン、オクタン、ベンゼン、トルエン、キシレンなどを挙げることができる。
以上のようにして、特定重合体Iを溶解してなる反応溶液が得られる。そして、この反応溶液を大量の貧溶媒中に注いで析出物を得、この析出物を減圧下乾燥することにより特定重合体Iを得ることができる。また、この特定重合体Iを再び有機溶媒に溶解させ、次いで貧溶媒で析出させる工程を1回または数回行うことにより、特定重合体Iを精製することができる。
かくして得られる本発明の特定重合体Iは、下記式(11)
[Poor solvent]
For the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for polyamic acid, are used in combination as long as the polyamic acid to be produced does not precipitate. be able to. Specific examples of the poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene Glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n- Chill ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1 , 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.
As described above, a reaction solution obtained by dissolving the specific polymer I is obtained. And the specific polymer I can be obtained by pouring this reaction solution in a lot of poor solvents, obtaining a deposit, and drying this deposit under reduced pressure. Further, the specific polymer I can be purified by dissolving the specific polymer I in an organic solvent and then precipitating with a poor solvent once or several times.
The specific polymer I of the present invention thus obtained has the following formula (11)
(ここで、R1、R2、X、Y、Zおよびaの定義は上記に同じであり、Aはテトラカルボン酸二無水物から二つの酸無水物基を除いた残基である)で表される繰り返し単位を有する。 Where R 1 , R 2 , X, Y, Z and a are the same as defined above, and A is a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Having repeating units represented.
イミド化重合体
本発明に用いられる特定重合体II(イミド化重合体)は、上記の特定重合体Iを脱水閉環することにより合成することができる。本発明で用いるイミド化重合体は、イミド化率100%未満の、部分的に脱水閉環されたものであってもよい。ここでいう「イミド化率」とは、ポリマーの全繰り返し単位中、イミド環またはイソイミド環を有する繰り返し単位の割合つまりイミド結合単位とアミック酸結合単位の合計単位数に対するイミド結合単位数の割合を、百分率で表した値である。イミド化率が30〜100%からなるイミド化重合体からなる配向膜は、特にTFT型素子に用いられる場合、焼き付きおよび信頼性が高いという評価を得ることができる。ポリアミック酸の脱水閉環は、(i)ポリアミック酸を加熱する方法により、または(ii)ポリアミック酸を有機溶媒に溶解し、この溶液中に脱水剤および脱水閉環触媒を添加し必要に応じて加熱する方法により行われる。
上記(i)のポリアミック酸を加熱する方法における反応温度は、好ましくは50〜200℃であり、より好ましくは60〜170℃である。反応温度が50℃未満では脱水閉環反応が十分に進行し難く、反応温度が200℃を超えると得られるイミド化重合体の分子量が低下することがある。
Imidized polymer The specific polymer II (imidized polymer) used in the present invention can be synthesized by dehydrating and ring-closing the specific polymer I described above. The imidized polymer used in the present invention may be partially dehydrated and ring-closed with an imidation rate of less than 100%. The “imidation rate” as used herein means the ratio of the number of imide bond units to the total number of units of imide bond units and amic acid bond units, that is, the ratio of repeat units having an imide ring or an isoimide ring in all repeating units of the polymer. The value is expressed as a percentage. An alignment film made of an imidized polymer having an imidization ratio of 30 to 100% can be evaluated to have high image sticking and high reliability, particularly when used in a TFT type device. The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.
The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C., the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease.
一方、上記(ii)のポリアミック酸の溶液中に脱水剤および脱水閉環触媒を添加する方法において、脱水剤としては、例えば無水酢酸、無水プロピオン酸、無水トリフルオロ酢酸などの酸無水物を用いることができる。脱水剤の使用量は、ポリアミック酸の繰り返し単位1モルに対して0.01〜20モルとするのが好ましい。また、脱水閉環触媒としては、例えばピリジン、コリジン、ルチジン、トリエチルアミンなどの3級アミンを用いることができる。しかし、これらに限定されるものではない。脱水閉環触媒の使用量は、使用する脱水剤1モルに対して0.01〜10モルとするのが好ましい。なお、脱水閉環反応に用いられる有機溶媒としては、ポリアミック酸の合成に用いられるものとして例示した有機溶媒を挙げることができる。そして、脱水閉環反応の反応温度は、好ましくは0〜180℃、より好ましくは10〜150℃である。また、このようにして得られる反応溶液に対し、ポリアミック酸の精製方法と同様の操作を行うことにより、イミド化重合体を精製することができる。
かくして得られる本発明の特定重合体IIは、下記式(12)
On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol relative to 1 mol of the polyamic acid repeating unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. In addition, the imidized polymer can be purified by performing the same operation as the polyamic acid purification method on the reaction solution thus obtained.
The specific polymer II of the present invention thus obtained has the following formula (12)
(ここで、R1、R2、X、Y、Z、Aおよびaの定義は上記に同じである)で表される繰り返し単位を有する。 (Wherein R 1 , R 2 , X, Y, Z, A and a have the same definition as above).
<末端修飾型の重合体>
上記特定重合体Iおよび特定重合体IIは、分子量が調節された末端修飾型のものであってもよい。この末端修飾型の重合体を用いることにより、本発明の効果が損われることなく液晶配向剤の塗布特性などを改善することができる。このような末端修飾型のものは、ポリアミック酸を合成する際に、酸一無水物、モノアミン化合物、モノイソシアネート化合物などを反応系に添加することにより合成することができる。ここで、酸一無水物としては、例えば無水マレイン酸、無水フタル酸、無水イタコン酸、n−デシルサクシニック酸無水物、n−ドデシルサクシニック酸無水物、n−テトラデシルサクシニック酸無水物、n−ヘキサデシルサクシニック酸無水物などを挙げることができる。また、モノアミン化合物としては、例えばアニリン、シクロヘキシルアミン、n−ブチルアミン、n−ペンチルアミン、n−ヘキシルアミン、n−ヘプチルアミン、n−オクチルアミン、n−ノニルアミン、n−デシルアミン、n−ウンデシルアミン、n−ドデシルアミン、n−トリデシルアミン、n−テトラデシルアミン、n−ペンタデシルアミン、n−ヘキサデシルアミン、n−ヘプタデシルアミン、n−オクタデシルアミン、n−エイコシルアミンなどを挙げることができる。また、モノイソシアネート化合物としては、例えばフェニルイソシアネート、ナフチルイソシアネートなどを挙げることができる。
<End-modified polymer>
The specific polymer I and the specific polymer II may be of a terminal modified type with a controlled molecular weight. By using this terminal-modified polymer, the coating characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention. Such a terminal-modified type can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when synthesizing the polyamic acid. Here, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride , N-hexadecyl succinic anhydride and the like. Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and n-undecylamine. N-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. Can do. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
[対数粘度]
<重合体の対数粘度>
以上のようにして得られるポリアミック酸およびイミド基含有ポリアミック酸は、その対数粘度(ηln)の値が好ましくは0.05〜10dl/g、より好ましくは0.05〜5dl/gである。
本発明における対数粘度(ηln)の値は、N−メチル−2−ピロリドンを溶媒として用い、濃度が0.5g/100ミリリットルである溶液について30℃で粘度の測定を行い、下記式(i)によって求められるものである。
[Logarithmic viscosity]
<Logarithmic viscosity of polymer>
The polyamic acid and imide group-containing polyamic acid obtained as described above preferably have a logarithmic viscosity (η ln ) of 0.05 to 10 dl / g, more preferably 0.05 to 5 dl / g.
The value of the logarithmic viscosity (η ln ) in the present invention is determined by measuring the viscosity at 30 ° C. for a solution having a concentration of 0.5 g / 100 ml using N-methyl-2-pyrrolidone as a solvent. ).
<液晶配向剤>
本発明の液晶配向剤は、本発明のポリアミック酸および/またはイミド化重合体よりなる有効成分が有機溶媒中に溶解含有されて構成される。
本発明の液晶配向剤を構成する有機溶媒としては、ポリアミック酸の合成反応に用いられるものとして例示した溶媒を挙げることができる。また、ポリアミック酸の合成反応の際に併用することができるものとして例示した貧溶媒も適宜選択して併用することができる。
<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention is constituted by dissolving and containing an active ingredient comprising the polyamic acid and / or imidized polymer of the present invention in an organic solvent.
As an organic solvent which comprises the liquid crystal aligning agent of this invention, the solvent illustrated as what is used for the synthesis reaction of a polyamic acid can be mentioned. Moreover, the poor solvent illustrated as what can be used together in the case of the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together.
本発明の液晶配向剤における固形分濃度は、粘性、揮発性などを考慮して選択されるが、好ましくは1〜10重量%の範囲とされる。すなわち、本発明の液晶配向剤は、基板表面に塗布され、液晶配向膜となる塗膜が形成されるが、固形分濃度が1重量%未満である場合には、この塗膜の膜厚が過小となって良好な液晶配向膜を得難い。固形分濃度が10重量%を超える場合には、塗膜の膜厚が過大となって良好な液晶配向膜を得難く、また、液晶配向剤の粘性が増大して塗布特性が劣化し易くなる。また、本発明の液晶配向剤を調製する際の温度は、好ましくは、0℃〜200℃、より好ましくは20℃〜60℃である。
本発明の液晶配向膜を形成する液晶配向剤は、基板表面に対する接着性を向上させる観点から、分子内に少なくとも一つのエポキシ基を有する化合物(以下「エポキシ基含有化合物」ともいう)を含有してもよい。
The solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the coating film thickness is It is too small to obtain a good liquid crystal alignment film. When the solid content concentration exceeds 10% by weight, it is difficult to obtain a good liquid crystal alignment film because the film thickness is excessive, and the viscosity of the liquid crystal aligning agent increases to easily deteriorate the coating characteristics. . Moreover, the temperature at the time of preparing the liquid crystal aligning agent of this invention, Preferably, it is 0 to 200 degreeC, More preferably, it is 20 to 60 degreeC.
The liquid crystal aligning agent that forms the liquid crystal alignment film of the present invention contains a compound having at least one epoxy group in the molecule (hereinafter also referred to as “epoxy group-containing compound”) from the viewpoint of improving the adhesion to the substrate surface. May be.
エポキシ基含有化合物としては、例えばエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、2,2−ジブロモネオペンチルグリコールジグリシジルエーテル、1,3,5,6−テトラグリシジル−2,4−ヘキサンジオール、N,N,N’,N’−テトラグリシジル−m−キシレンジアミン、1,3−ビス(N,N−ジグリシジルアミノメチル)シクロヘキサン、N,N,N’,N’−テトラグリシジル−4、4’−ジアミノジフェニルメタンなどを好ましいものとして挙げることができる。これらエポキシ基含有化合物の配合割合は、特定重合体100重量部に対して、好ましくは、40重量部以下である。
Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′ - tetraglycidyl -m- xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N ', N' - -4,4'- tetraglycidyl Gia Minodiphenylmethane and the like can be mentioned as preferable ones. The blending ratio of these epoxy group-containing compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the specific polymer.
また、本発明の液晶配向剤は、官能性シラン含有化合物を含有していてもよい。斯かる官能性シラン含有化合物としては、例えば3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、2−アミノプロピルトリメトキシシラン、2−アミノプロピルトリエトキシシラン、N−(2−アミノエチル)−3−アミノプロピルトリメトキシシラン、N−(2−アミノエチル)−3−アミノプロピルメチルジメトキシシラン、3−ウレイドプロピルトリメトキシシラン、3−ウレイドプロピルトリエトキシシラン、N−エトキシカルボニル−3−アミノプロピルトリメトキシシラン、N−エトキシカルボニル−3−アミノプロピルトリエトキシシラン、N−トリエトキシシリルプロピルトリエチレントリアミン、N−トリメトキシシリルプロピルトリエチレントリアミン、10−トリメトキシシリル−1,4,7−トリアザデカン、10−トリエトキシシリル−1,4,7−トリアザデカン、9−トリメトキシシリル−3,6−ジアザノニルアセテート、9−トリエトキシシリル−3,6−ジアザノニルアセテート、N−ベンジル−3−アミノプロピルトリメトキシシラン、N−ベンジル−3−アミノプロピルトリエトキシシラン、N−フェニル−3−アミノプロピルトリメトキシシラン、N−フェニル−3−アミノプロピルトリエトキシシラン、N−ビス(オキシエチレン)−3−アミノプロピルトリメトキシシラン、N−ビス(オキシエチレン)−3−アミノプロピルトリエトキシシランなどを挙げることができる。
これら官能性シラン含有化合物の配合割合は、特定重合体100重量部に対して、好ましくは40重量部以下である。
Moreover, the liquid crystal aligning agent of this invention may contain the functional silane containing compound. Examples of such functional silane-containing compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- , 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N -Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. can be mentioned.
The blending ratio of these functional silane-containing compounds is preferably 40 parts by weight or less with respect to 100 parts by weight of the specific polymer.
<液晶表示素子>
本発明の液晶配向剤を用いて得られる液晶表示素子は、例えば次の方法によって製造することができる。
<Liquid crystal display element>
The liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured, for example with the following method.
(1)パターニングされた透明導電膜が設けられている基板の一面に、本発明の液晶配向剤を例えばロールコーター法、スピンナー法、印刷法、インクジェット法などの方法によって塗布し、次いで、塗布面を加熱することにより塗膜を形成する。ここに、基板としては、例えばフロートガラス、ソーダガラスなどのガラス;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルスルホン、ポリカーボネートなどのプラスチックからなる透明基板を用いることができる。基板の一面に設けられる透明導電膜としては、酸化スズ(SnO2)からなるNESA膜(米国PPG社登録商標)、酸化インジウム−酸化スズ(In2O3−SnO2)からなるITO膜などを用いることができる。これらの透明導電膜のパターニングには、フォト・エッチング法や予めマスクを用いる方法が用いられる。液晶配向剤の塗布に際しては、基板表面および透明導電膜と塗膜との接着性をさらに良好にするために、基板の該表面に、官能性シラン含有化合物、官能性チタン含有化合物などを予め塗布することもできる。液晶配向剤塗布後の加熱温度は好ましくは80〜300℃であり、より好ましくは120〜250℃である。なお、ポリアミック酸を含有する本発明の液晶配向剤は、塗布後に有機溶媒を除去することによって配向膜となる塗膜を形成するが、さらに加熱することによって脱水閉環を進行させ、よりイミド化された塗膜とすることもできる。形成される塗膜の膜厚は、好ましくは0.001〜1μmであり、より好ましくは0.005〜0.5μmである。 (1) The liquid crystal aligning agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film by a method such as a roll coater method, a spinner method, a printing method, an ink jet method, etc. Is heated to form a coating film. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO 2 ), an ITO film made of indium oxide-tin oxide (In 2 O 3 —SnO 2 ), etc. Can be used. For patterning these transparent conductive films, a photo-etching method or a method using a mask in advance is used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane-containing compound, a functional titanium-containing compound, or the like is previously applied to the surface of the substrate. You can also The heating temperature after application of the liquid crystal aligning agent is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. In addition, the liquid crystal aligning agent of the present invention containing a polyamic acid forms a coating film that becomes an alignment film by removing the organic solvent after coating, but further proceeds with dehydration ring closure by further heating, and is further imidized. It can also be set as a coating film. The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.
(2)形成された塗膜面を、例えばナイロン、レーヨン、コットンなどの繊維からなる布を巻き付けたロールで一定方向に擦るラビング処理を行う。これにより、液晶分子の配向能が塗膜に付与されて液晶配向膜となる。
また、本発明の液晶配向剤により形成された液晶配向膜に、例えば特開平6−222366号公報や特開平6−281937号公報に示されているような、紫外線を部分的に照射することによってプレチルト角を変化させるような処理、あるいは特開平5−107544号公報に示されているような、ラビング処理を施した液晶配向膜表面にレジスト膜を部分的に形成し、先のラビング処理と異なる方向にラビング処理を行った後にレジスト膜を除去して、液晶配向膜の液晶配向能を変化させるような処理を行うことによって、液晶表示素子の視界特性を改善することが可能である。
(2) A rubbing process is performed in which the formed coating film surface is rubbed in a certain direction with a roll wound with a cloth made of a fiber such as nylon, rayon, or cotton. Thereby, the orientation ability of liquid crystal molecules is imparted to the coating film to form a liquid crystal orientation film.
Further, by partially irradiating the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention with ultraviolet rays as disclosed in, for example, JP-A-6-222366 and JP-A-6-281937. A resist film is partially formed on the surface of the liquid crystal alignment film that has been subjected to a treatment for changing the pretilt angle or a rubbing treatment as disclosed in JP-A-5-107544, which is different from the previous rubbing treatment. The visibility characteristics of the liquid crystal display element can be improved by removing the resist film after performing the rubbing treatment in the direction and changing the liquid crystal alignment ability of the liquid crystal alignment film.
(3)上記のようにして液晶配向膜が形成された基板を2枚作製し、それぞれの液晶配向膜におけるラビング方向が直交または逆平行となるように、2枚の基板を、間隙(セルギャップ)を介して対向配置し、2枚の基板の周辺部をシール剤を用いて貼り合わせ、基板表面およびシール剤により区画されたセルギャップ内に液晶を注入充填し、注入孔を封止して液晶セルを構成する。そして、液晶セルの外表面、すなわち、液晶セルを構成する透明基板側に、偏光板を配することにより、液晶表示素子が得られる。
ここに、シール剤としては、例えば硬化剤およびスペーサーとしての酸化アルミニウム球を含有するエポキシ樹脂などを用いることができる。
(3) Two substrates on which the liquid crystal alignment film is formed as described above are manufactured, and the two substrates are separated by a gap (cell gap) so that the rubbing directions in the respective liquid crystal alignment films are orthogonal or antiparallel. ), And the periphery of the two substrates are bonded together using a sealant, and liquid crystal is injected and filled in the cell gap defined by the substrate surface and the sealant, and the injection hole is sealed. A liquid crystal cell is constructed. And a liquid crystal display element is obtained by arrange | positioning a polarizing plate to the outer surface of a liquid crystal cell, ie, the transparent substrate side which comprises a liquid crystal cell.
Here, as the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
液晶としては、ネマティック型液晶およびスメクティック型液晶を挙げることができ、その中でもネマティック型液晶が好ましく、例えばシッフベース系液晶、アゾキシ系液晶、ビフェニル系液晶、フェニルシクロヘキサン系液晶、エステル系液晶、ターフェニル系液晶、ビフェニルシクロヘキサン系液晶、ピリミジン系液晶、ジオキサン系液晶、ビシクロオクタン系液晶、キュバン系液晶などを用いることができる。また、これらの液晶に、例えばコレスチルクロライド、コレステリルノナエート、コレステリルカーボネートなどのコレステリック型液晶や商品名「C−15」「CB−15」(メルク社製)として販売されているようなカイラル剤などを添加して使用することもできる。さらに、p−デシロキシベンジリデン−p−アミノ−2−メチルブチルシンナメートなどの強誘電性液晶も使用することができる。
また、液晶セルの外表面に貼り合わされる偏光板としては、ポリビニルアルコールを延伸配向させながら、ヨウ素を吸収させたH膜と称される偏光膜を酢酸セルロース保護膜で挟んだ偏光板またはH膜そのものからなる偏光板を挙げることができる。
Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable. For example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal. Liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.
Further, as a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an H film that absorbs iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films. The polarizing plate which consists of itself can be mentioned.
以下、本発明を実施例によりさらに具体的に説明するが、本発明はこれらの実施例に制限されるものではない。実施例および比較例における電圧保持率は以下の方法により評価した。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The voltage holding ratios in the examples and comparative examples were evaluated by the following methods.
[イミド化率]
FT−IR測定における1381cm−1付近の吸収(C−N−C変角振動=イミド結合の吸収)と、1503cm−1付近の吸収(アミック酸結合の吸収)とのピーク面積比から、下記式によりイミド化率を算出した、
イミド化率={α1/(α1+α2)}×100(%)
α1:1381cm−1付近の吸収のピーク面積
α2:1503cm−1付近の吸収のピーク面積
なお、α2は塗膜を300℃のホットプレートで10分間加熱したものの1303cm−1付近の吸収を0として、ピーク面積を求めた値である。
[Imidation rate]
From the peak area ratio of absorption near 1381 cm −1 (C—N—C bending vibration = absorption of imide bond) and absorption near 1503 cm −1 (absorption of amic acid bond) in FT-IR measurement, The imidization rate was calculated by
Imidation ratio = {α 1 / (α 1 + α 2 )} × 100 (%)
α 1: 1381cm -1 vicinity of the absorption peak area alpha 2: peak area of absorption around 1503cm -1 Incidentally, alpha 2 is the absorption in the vicinity of 1303cm -1 but was heated for 10 minutes on a hot plate at 300 ° C. The coating The value obtained by calculating the peak area as 0.
[電圧保持率]
液晶表示素子に5Vの電圧を60マイクロ秒の印加時間、167ミリ秒のスパンで印加した後、印加解除から167ミリ秒後の電圧保持率を測定した。測定装置は(株)東陽テクニカ製VHR−1を使用した。電圧保持率が90%以上の場合を良、それ以外の場合を不良と判断した。
[Voltage holding ratio]
A voltage of 5 V was applied to the liquid crystal display element with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from release of application was measured. The measuring apparatus used was VHR-1 manufactured by Toyo Corporation. The case where the voltage holding ratio was 90% or more was judged as good, and the other cases were judged as bad.
[信頼性試験]
100℃の恒温槽中に液晶表示素子を入れ、駆動波形発生装置「Function /arbitrary waveform generator」(Hewlett Packard社製)にて24hr連続駆動させた後、コントラストムラ、表示欠損の有無を確認する。
[Reliability test]
A liquid crystal display element is placed in a constant temperature bath at 100 ° C., and continuously driven for 24 hours with a drive waveform generator “Function / arbitrary waveform generator” (manufactured by Hewlett Packard).
実施例1(特定ジアミン化合物の合成)
工程(i):3,5−ジニトロ安息香酸クロリド23.06g(100ミリモル)および1,4−ジヒドロキシシクロヘキサン34.85g(300ミリモル)を、テトラヒドロフラン400gに溶解した。次いで、攪拌氷冷を行いながら、ピリジン7.91g(100ミリモル)を徐々に滴下した。6時間反応を行った後反応液を大過剰の水中にあけ、析出物を濾別し、メチルエチルケトンより再結晶を行い、白色のジニトロ化合物を得た。
工程(ii):工程(i)で得られたジニトロ化合物24.82g(80ミリモル)およびp−トリフルオロメトキシ安息香酸クロリド19.6g(80ミリモル)を、テトラヒドロフラン400gに溶解した。次いで、攪拌氷冷を行いながら、ピリジン6.33g(80ミリモル)を徐々に滴下した。6時間反応を行った後反応液を大過剰の水中にあけ、析出物を濾別し、メチルエチルケトンより再結晶を行い、白色のジニトロ化合物を得た。
工程(iii):工程(ii)で得られたジニトロ化合物37.35g(72ミリモル)をエタノール400gに溶解させて、5重量%パラジウム−炭素触媒0.30およびヒドラジン一水和物5.6g(100ミリモル)を加え、6時間還流反応した。反応液を大過剰の水中にあけ、析出物を濾別し、エタノールより再結晶を行い、上記式(X)で表される白色の特定ジアミン(I)24.44gを得た。得られた特定ジアミン化合物のNMRスペクトルを図1に示す。元素分析(C21H21N2O5F3、分子量 438.4):計算値C:57.48%、H:4.79%、N:6.39%、O:18.25%、F:13.09%。実測値C:57.39%、H:4.74%、N:6.45%、O:18.32%、F:13.10%。
Example 1 ( Synthesis of specific diamine compound)
Step (i): 23.06 g (100 mmol) of 3,5-dinitrobenzoyl chloride and 34.85 g (300 mmol) of 1,4-dihydroxycyclohexane were dissolved in 400 g of tetrahydrofuran. Next, 7.91 g (100 mmol) of pyridine was gradually added dropwise while stirring and cooling with ice. After reacting for 6 hours, the reaction solution was poured into a large excess of water, and the precipitate was filtered off and recrystallized from methyl ethyl ketone to obtain a white dinitro compound.
Step (ii): 24.82 g (80 mmol) of the dinitro compound obtained in step (i) and 19.6 g (80 mmol) of p-trifluoromethoxybenzoyl chloride were dissolved in 400 g of tetrahydrofuran. Next, 6.33 g (80 mmol) of pyridine was gradually added dropwise while stirring and cooling with ice. After reacting for 6 hours, the reaction solution was poured into a large excess of water, and the precipitate was filtered off and recrystallized from methyl ethyl ketone to obtain a white dinitro compound.
Step (iii): 37.35 g (72 mmol) of the dinitro compound obtained in step (ii) was dissolved in 400 g of ethanol, and 0.3 g of a 5 wt% palladium-carbon catalyst and 5.6 g of hydrazine monohydrate ( 100 mmol) was added and the reaction was refluxed for 6 hours. The reaction solution was poured into a large excess of water, and the precipitate was filtered off and recrystallized from ethanol to obtain 24.44 g of a white specific diamine (I) represented by the above formula (X). The NMR spectrum of the obtained specific diamine compound is shown in FIG. Elemental analysis (C 21 H 21 N 2 O 5
実施例2(特定重合体IIaの合成)
テトラカルボン酸二無水物として2,3,5−トリカルボキシシクロペンチル酢酸二無水物112.09g(0.5モル)および1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)ナフト[1,2−c]フラン−1,3−ジオン157.15g(0.5モル)、ジアミン化合物としてp−フェニレンジアミン90.03g(0.8325モル)、ビスアミノプロピルテトラメチルジシロキサン24.85g(0.1モル)および特定ジアミン化合物(I)26.3g(0.06モル)、モノアミンとしてアニリン1.396g(0.015モル)をN−メチル−2−ピロリドン4500gに溶解させ、60℃で6時間反応させた。次いで、反応溶液を大過剰のメチルアルコールに注いで反応生成物を沈澱させた。その後、メチルアルコールで洗滌し、減圧下40℃で15時間乾燥させることにより、対数粘度0.81dl/gの特定重合体Iaを400g得た。得られた特定重合体Ia30gをN−メチル−2−ピロリドン570gに溶解させ、ピリジン23.4gおよび無水酢酸18.1gを添加し110℃で4時間脱水閉環させ、上記と同様にして沈殿、洗滌、減圧を行い、対数粘度0.75dl/gの特定重合体IIa18.2gを得た。得られた特定重合体IIaのNMRスペクトルを図2に示す。
Example 2 (Synthesis of specific polymer IIa)
2,3,5-tricarboxycyclopentylacetic acid dianhydride 112.09 g (0.5 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157.15 g (0.5 mol), p-phenylenediamine as a diamine compound 90.03 g (0 8325 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane and 26.3 g (0.06 mol) of the specific diamine compound (I), 1.396 g (0.015 mol) of aniline as a monoamine Was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 400 g of a specific polymer Ia having a logarithmic viscosity of 0.81 dl / g. 30 g of the obtained specific polymer Ia was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, dehydrating and ring-closing at 110 ° C. for 4 hours, and precipitation and washing were performed in the same manner as above. The pressure was reduced to obtain 18.2 g of the specific polymer IIa having a logarithmic viscosity of 0.75 dl / g. The NMR spectrum of the obtained specific polymer IIa is shown in FIG.
実施例3(特定重合体IIbの合成)
テトラカルボン酸二無水物として2,3,5−トリカルボキシシクロペンチル酢酸二無水物224.17g(1.0モル)、ジアミン化合物としてp−フェニレンジアミン95.16g(0.88モル)および特定ジアミン化合物(I)52.61g(0.12モル)をN−メチル−2−ピロリドン4,500gに溶解させ、60℃で6時間反応させた。次いで、反応溶液を大過剰のメチルアルコールに注いで反応生成物を沈澱させた。その後、メチルアルコールで洗滌し、減圧下40℃で15時間乾燥させることにより、対数粘度0.78dl/gの特定重合体Ibを380g得た。得られた特定重合体Ib30gをN−メチル−2−ピロリドン570gに溶解させ、ピリジン23.4gおよび無水酢酸18.1gを添加し110℃で4時間脱水閉環させ、上記と同様にして沈殿、洗滌、減圧を行い、対数粘度0.76dl/gの特定重合体IIb20.1gを得た。得られた特定重合体IIbのNMRスペクトルを図3に示す。
Example 3 (Synthesis of specific polymer IIb)
224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 95.16 g (0.88 mol) of p-phenylenediamine as a diamine compound and a specific diamine compound (I) 52.61 g (0.12 mol) was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 380 g of a specific polymer Ib having a logarithmic viscosity of 0.78 dl / g. 30 g of the obtained specific polymer Ib was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours. The pressure was reduced to obtain 20.1 g of a specific polymer IIb having a logarithmic viscosity of 0.76 dl / g. The NMR spectrum of the obtained specific polymer IIb is shown in FIG.
実施例4(特定重合体IIcの合成)
テトラカルボン酸二無水物として2,3,5−トリカルボキシシクロペンチル酢酸二無水物112.09g(0.5モル)および1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)ナフト[1,2−c]フラン−1,3−ジオン157.15g(0.5モル)、ジアミン化合物としてp−フェニレンジアミン82.46g(0.7625モル)、ビスアミノプロピルテトラメチルジシロキサン24.85g(0.1モル)、式(X)で表される特定ジアミン化合物(i)35.07g(0.08モル)、および4,4’−ジアミノジフェニルメタン9.91g(0.05モル)、モノアミンとしてアニリン1.396g(0.015モル)をN−メチル−2−ピロリドン4500gに溶解させ、60℃で6時間反応させた。次いで、反応溶液を大過剰のメチルアルコールに注いで反応生成物を沈澱させた。その後、メチルアルコールで洗浄し、減圧下40℃で15時間乾燥させることにより、対数粘度0.79dl/gの特定重合体Icを350g得た。得られた特定重合体Ic30gをN−メチル−2−ピロリドン570gに溶解させ、ピリジン23.4gおよび無水酢酸18.1gを添加し110℃で4時間脱水閉環させ、上記と同様にして沈殿、洗浄、減圧を行い、対数粘度0.78dl/gの特定重合体IIc18.8gを得た。得られた特定重合体IIcのNMRスペクトルを図4に示す。
Example 4 (Synthesis of specific polymer IIc)
1,2.09 g (0.5 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157.15 g (0.5 mol), p-phenylenediamine 82.46 g (0 as diamine compound) 7625 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane, 35.07 g (0.08 mol) of the specific diamine compound (i) represented by formula (X), and 4,4 9.91 g (0.05 mol) of '-diaminodiphenylmethane and 1.396 g (0.015 mol) of aniline as a monoamine were added to N-methyl-2-pyrrolidone 4500 Dissolved in, and reacted for 6 hours at 60 ° C.. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Then washed with methyl alcohol, and dried 15 hours in vacuo at 40 ° C., a specific polymer I c logarithmic viscosity 0.79 dl / g was obtained 350 g. 30 g of the obtained specific polymer Ic was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation and washing in the same manner as above. The pressure was reduced to obtain 18.8 g of a specific polymer IIc having a logarithmic viscosity of 0.78 dl / g. The NMR spectrum of the obtained specific polymer IIc is shown in FIG.
合成例1(ポリアミック酸(A−1)の合成)
テトラカルボン酸二無水物として1,2,3,4−シクロブタンテトラカルボン酸二無水物196.12g(1.0モル)、ジアミン化合物として2,2’−ジメチル−4,4’−ジアミノビフェニル212.3g(1.0モル)をN−メチル−2−ピロリドン4,500gに溶解させ、40℃で3時間反応させた。次いで、反応溶液を大過剰のメチルアルコール中に注いで反応生成物を沈澱させた。その後、メチルアルコールで洗浄し、減圧下40℃で15時間乾燥させることにより、対数粘度0.91dl/gのポリアミック酸(これを「ポリアミック酸(A−1)」とする)390gを得た。
Synthesis Example 1 (Synthesis of polyamic acid (A-1))
196.12 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 2,2′-dimethyl-4,4′-diaminobiphenyl 212 as diamine compound .3 g (1.0 mol) was dissolved in 4,500 g of N-methyl-2-pyrrolidone and reacted at 40 ° C. for 3 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 390 g of a polyamic acid having a logarithmic viscosity of 0.91 dl / g (referred to as “polyamic acid (A-1)”).
合成例2(ポリイミドB−1の合成)
テトラカルボン酸二無水物として2,3,5−トリカルボキシシクロペンチル酢酸二無水物224.17g(1.0モル)、ジアミン化合物としてp−フェニレンジアミン95.16g(0.88モル)および4−(4’−トリフルオロメチルベンゾイロキシ)シクロヘキシルー3,5−ジアミノベンゾエート50.69g(0.12モル)をN−メチル−2−ピロリドン4500gに溶解させ、60℃で6時間反応させた。次いで、反応溶液を大過剰のメチルアルコールに注いで反応生成物を沈澱させた。その後、メチルアルコールで洗滌し、減圧下40℃で15時間乾燥させることにより、対数粘度0.79dl/gのポリアミック酸を390g得た。得られたポリアミック酸30gをN−メチル−2−ピロリドン570gに溶解させ、ピリジン23.4gおよび無水酢酸18.1gを添加し110℃で4時間脱水閉環させ、上記と同様にして沈殿、洗滌、減圧を行い、対数粘度0.77dl/gのポリイミド(これを「ポリイミドB−1」とする)18.7gを得た。
Synthesis Example 2 (Synthesis of polyimide B-1)
224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 95.16 g (0.88 mol) of p-phenylenediamine as a diamine compound and 4- ( 4'-trifluoromethyl-acetoxyphenyl)
合成例3(ポリアミック酸A-2、ポリイミドB−2の合成)
テトラカルボン酸二無水物として2,3,5−トリカルボキシシクロペンチル酢酸二無水物224.17g(1.0モル)、ジアミン化合物としてp−フェニレンジアミン95.16g(0・88モル)、および4−(4’−トリフルオロメチルベンゾイロキシ)シクロヘキシルー3,5−ジアミノベンゾエート50.69g(0.12モル)をN−メチル−2−ピロリドン4500gに溶解させ、60℃で6時間反応させた。次いで、反応溶液を大過剰のメチルアルコールに注いで反応生成物を沈澱させた。その後、メチルアルコールで洗浄し、減圧下40℃で15時間乾燥させることにより、対数粘度0.79dl/gのポリアミック酸(これを「ポリアミック酸A−2」とする)を390g得た。得られたポリアミック酸30gをN−メチル−2−ピロリドン570gに溶解させ、ピリジン23.4gおよび無水酢酸18.1gを添加し110℃で4時間脱水閉環させ、上記と同様にして沈殿、洗浄、減圧を行い、対数粘度0.77dl/gのポリイミド(これを「ポリイミドB−2」とする)18.7gを得た。
Synthesis Example 3 (Synthesis of polyamic acid A-2 and polyimide B-2)
224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 95.16 g (0.88 mol) of p-phenylenediamine as a diamine compound, and 4- 50.69 g (0.12 mol) of (4′-trifluoromethylbenziloxy)
合成例4
テトラカルボン酸二無水物として2,3,5−トリカルボキシシクロペンチル酢酸二無水物224.17g(1.0モル)、ジアミン化合物としてp−フェニレンジアミン95.16g(0.88モル)、およびコレスタニル−3,5−ジアミノベンゾエート7.842g(0.015モル)をN−メチル−2−ピロリドン4500gに溶解させ、60℃で6時間反応させた。次いで、反応溶液を大過剰のメチルアルコールに注いで反応生成物を沈澱させた。その後、メチルアルコールで洗滌し、減圧下40℃で15時間乾燥させることにより、対数粘度0.75dl/gのポリアミック酸(これを「ポリアミック酸A−3」とする)を400g得た。得られたポリアミック酸30gをN−メチル−2−ピロリドン570gに溶解させ、ピリジン23.4gおよび無水酢酸18.1gを添加し110℃で4時間脱水閉環させ、上記と同様にして沈殿、洗滌、減圧を行い、対数粘度0.78dl/gのポリイミド(これを「ポリイミドB−3」とする)19.2gを得た。
Synthesis example 4
224.17 g (1.0 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 95.16 g (0.88 mol) of p-phenylenediamine as a diamine compound, and cholestanyl- 7.842 g (0.015 mol) of 3,5-diaminobenzoate was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 400 g of a polyamic acid having a logarithmic viscosity of 0.75 dl / g (referred to as “polyamic acid A-3”). 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 19.2 g of polyimide having a logarithmic viscosity of 0.78 dl / g (referred to as “polyimide B-3”).
合成例5
テトラカルボン酸二無水物として2,3,5−トリカルボキシシクロペンチル酢酸二無水物112.08g(0.5モル)および1,3,3a,4,5,9b−ヘキサヒドロ−8−メチル−5−(テトラヒドロ−2,5−ジオキソ−3−フラニル)ナフト[1,2−c]フラン−1,3−ジオン157.15g(0.5モル)、ジアミン化合物としてp−フェニレンジアミン95.71g(0.865モル)、ビスアミノプロピルテトラメチルジシロキサン24.85g(0.1モル)、および3,6−ビス(4−アミノベンゾイルオキシ)コレスタン12.86g(0.02モル)、モノアミンとしてN−オクタデシルアミン8.09g(0.03モル)をN−メチル−2−ピロリドン4500gに溶解させ、60℃で6時間反応させた。次いで、反応溶液を大過剰のメチルアルコールに注いで反応生成物を沈澱させた。その後、メチルアルコールで洗滌し、減圧下40℃で15時間乾燥させることにより、対数粘度0.84dl/gのポリアミック酸340gを得た。得られたポリアミック酸30gをN−メチル−2−ピロリドン570gに溶解させ、ピリジン23.4gおよび無水酢酸18.1gを添加し110℃で4時間脱水閉環させ、上記と同様にして沈殿、洗滌、減圧を行い、対数粘度0.65dl/gのポリイミド(これを「ポリイミド(B−4)」とする)17.4gを得た。
Synthesis example 5
2,3,5-tricarboxycyclopentylacetic acid dianhydride 112.08 g (0.5 mol) and 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 as tetracarboxylic dianhydride (Tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 157.15 g (0.5 mol), p-phenylenediamine 95.71 g (0 mol) as the diamine compound 865 mol), 24.85 g (0.1 mol) of bisaminopropyltetramethyldisiloxane, and 12.86 g (0.02 mol) of 3,6-bis (4-aminobenzoyloxy) cholestane, N- 8.09 g (0.03 mol) of octadecylamine was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 340 g of polyamic acid having a logarithmic viscosity of 0.84 dl / g. 30 g of the obtained polyamic acid was dissolved in 570 g of N-methyl-2-pyrrolidone, 23.4 g of pyridine and 18.1 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours, followed by precipitation, washing, The pressure was reduced to obtain 17.4 g of a polyimide having a logarithmic viscosity of 0.65 dl / g (referred to as “polyimide (B-4)”).
実施例5
実施例2で得られた特定重合体IIaおよび合成例1で得られたポリアミック酸(A−1)を、特定重合体IIa:ポリアミック酸=20:80(重量比)になるように、γ−ブチロラクトン/N−メチル−2−ピロリドン/ブチルセロソルブ混合溶剤(重量比72/15/13)に溶解させて、固形分濃度4重量%の溶液とし、十分な攪拌後、この溶液を孔径1μmのフィルターを用いて濾過し、本発明の液晶配向剤を調製した。上記液晶配向剤を、厚さ1mmのガラス基板の一面に設けられたITO膜からなる透明導電膜上に、スピンナーを用いて塗布(回転数:2,500rpm,塗布時間:1分間)し、200℃で1時間乾燥することにより乾燥膜厚0.08μmの被膜を形成した。この被膜のイミド化率を測定したところ、イミド化率は52%であった。この被膜にレーヨン製の布を巻き付けたロールを有するラビングマシーンにより、ロールの回転数400rpm、ステージの移動速度3cm/秒、毛足押し込み長さ0.4mmでラビング処理を行った。上記液晶配向膜塗布基板を、イソプロピルアルコール中に1分間浸漬した後、100℃のホットプレート上で5分間乾燥した。次に、一対の透明電極/透明電極基板の上記液晶配向膜塗布基板の液晶配向膜を有するそれぞれの外縁に、直径5.5μmの酸化アルミニウム球入りエポキシ樹脂接着剤を塗布した後、液晶配向膜面が相対するように重ね合わせて圧着し、接着剤を硬化させた。次いで、液晶注入口より基板間に、ネマティック型液晶(メルク社製、MLC−6221)を充填した後、アクリル系光硬化接着剤で液晶注入口を封止し、基板の外側の両面に偏光板を張り合わせ、液晶表示素子を作製した。得られた液晶表示素子の電圧保持率を評価した。電圧保持率は99%と高い値を示し、コントラストムラ、表示欠損は見られなかった。
Example 5
The specific polymer IIa obtained in Example 2 and the polyamic acid (A-1) obtained in Synthesis Example 1 were converted into γ− so that the specific polymer IIa: polyamic acid = 20: 80 (weight ratio). Dissolve in butyrolactone / N-methyl-2-pyrrolidone / butyl cellosolve mixed solvent (weight ratio 72/15/13) to make a solution with a solid content concentration of 4% by weight, and after thorough stirring, filter the solution with a pore size of 1 μm. It filtered using, and the liquid crystal aligning agent of this invention was prepared. The liquid crystal aligning agent was applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spinner (rotation speed: 2500 rpm, application time: 1 minute), and 200 A film having a dry film thickness of 0.08 μm was formed by drying at 0 ° C. for 1 hour. When the imidization rate of this film was measured, the imidation rate was 52%. A rubbing machine having a roll in which a rayon cloth was wound around this film was subjected to a rubbing treatment at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / second, and a hair foot pushing length of 0.4 mm. The liquid crystal alignment film-coated substrate was dipped in isopropyl alcohol for 1 minute and then dried on a hot plate at 100 ° C. for 5 minutes. Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of transparent electrodes / transparent electrode substrates having the liquid crystal alignment film of the liquid crystal alignment film coated substrate, the liquid crystal alignment film The adhesive was cured by overlapping and pressing so that the surfaces were opposed. Next, a nematic liquid crystal (MLC-6221, manufactured by Merck & Co., Inc.) is filled between the substrates through the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and polarizing plates are formed on both sides of the substrate. Were laminated to prepare a liquid crystal display element. The voltage holding ratio of the obtained liquid crystal display element was evaluated. The voltage holding ratio was as high as 99%, and contrast unevenness and display defects were not observed.
また、上記液晶配向剤を、厚さ1mmのガラス基板の一面に設けられたITO膜からなる透明導電膜上に、スピンナーを用いて塗布(塗布時間:1分間)し、表1記載のセル作成条件1〜5のそれぞれの乾燥温度で1時間乾燥することにより表1記載の乾燥膜厚の被膜を形成した。被膜形成後、上記と同様な方法でラビング処理を行ったのち、一対の透明電極/透明電極基板の上記液晶配向膜塗布基板の外縁に、直径17μmの酸化アルミニウム球入りエポキシ樹脂接着剤を塗布した後、液晶配向膜面が相対するように重ね合わせて圧着し、接着剤を硬化させた。次いで、液晶注入口より基板間に、ネマティック型液晶(メルク社製、MLC−5081)を充填した後、アクリル系光硬化接着剤で液晶注入口を封止し、基板の外側の両面に偏光板を張り合わせ、液晶表示素子を作製した。得られた液晶表示素子のプレチルト角を評価し、プレチルト角のプロセス条件依存性を判断した。結果を表2に示した。
Further, the liquid crystal aligning agent was applied on a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spinner (application time: 1 minute). A film having a dry film thickness shown in Table 1 was formed by drying for 1 hour at each drying temperature under
実施例6、7および比較例1〜6
合成例1〜5で得られたポリイミドとポリアミック酸とをγ―ブチルラクトンを主成分とする混合溶剤に溶解させ固形分濃度4.0%の溶液を得、この溶液を孔径1μmのフィルターでろ過することにより、液晶配向剤を調製した。このようにして調整された液晶配向剤の各々を用い、実施例5と同様にして、基板表面上に被膜を形成し、被膜のイミド化率を測定。当該液晶配向膜が形成された基板を用いて液晶表示素子を作製した。そして、電圧保持率、プレチルト角を評価した。結果を表2に示す。なお、実施例7および比較例6においてポリアミック酸とポリイミドは、ポリアミック酸:ポリイミド=4:1(重量比)となるような割合で用いた。
Examples 6 and 7 and Comparative Examples 1 to 6
The polyimide and polyamic acid obtained in Synthesis Examples 1 to 5 are dissolved in a mixed solvent containing γ-butyllactone as a main component to obtain a solution having a solid content concentration of 4.0%, and this solution is filtered through a filter having a pore size of 1 μm. By doing so, a liquid crystal aligning agent was prepared. Using each of the liquid crystal aligning agents thus adjusted, a film was formed on the substrate surface in the same manner as in Example 5, and the imidization ratio of the film was measured. A liquid crystal display element was produced using the substrate on which the liquid crystal alignment film was formed. Then, the voltage holding ratio and the pretilt angle were evaluated. The results are shown in Table 2. In Example 7 and Comparative Example 6, polyamic acid and polyimide were used in such a ratio that polyamic acid: polyimide = 4: 1 (weight ratio).
Claims (7)
The following formula (II) or (III)
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