JP2007279691A - Photo alignment film and liquid crystal display element - Google Patents
Photo alignment film and liquid crystal display element Download PDFInfo
- Publication number
- JP2007279691A JP2007279691A JP2007029477A JP2007029477A JP2007279691A JP 2007279691 A JP2007279691 A JP 2007279691A JP 2007029477 A JP2007029477 A JP 2007029477A JP 2007029477 A JP2007029477 A JP 2007029477A JP 2007279691 A JP2007279691 A JP 2007279691A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- alignment film
- photo
- liquid crystal
- diamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 182
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 53
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 14
- 150000004985 diamines Chemical class 0.000 claims description 95
- 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 75
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 71
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 239000004642 Polyimide Substances 0.000 claims description 24
- 229920001721 polyimide Polymers 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 230000010287 polarization Effects 0.000 claims description 15
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 125000002723 alicyclic group Chemical group 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002835 absorbance Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000005462 imide group Chemical group 0.000 claims description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 3
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 22
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000008016 vaporization Effects 0.000 abstract 2
- 238000009834 vaporization Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 155
- 210000002858 crystal cell Anatomy 0.000 description 55
- 239000002966 varnish Substances 0.000 description 52
- 239000000203 mixture Substances 0.000 description 42
- 150000001875 compounds Chemical class 0.000 description 33
- 238000011282 treatment Methods 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
- 150000002500 ions Chemical class 0.000 description 19
- 230000007547 defect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- OMHYGQBGFWWXJK-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid;dihydrate Chemical compound O.O.OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O OMHYGQBGFWWXJK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 229920002959 polymer blend Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- RHLMOYPJGYMFAJ-UHFFFAOYSA-N 1-iodo-4-(2-iodoethynyl)benzene Chemical compound IC#CC1=CC=C(I)C=C1 RHLMOYPJGYMFAJ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- KFUSEUYYWQURPO-UPHRSURJSA-N cis-1,2-dichloroethene Chemical group Cl\C=C/Cl KFUSEUYYWQURPO-UPHRSURJSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 125000006159 dianhydride group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- JNFBOWNNNAHVNZ-UHFFFAOYSA-N 1,2-dibromoethyne Chemical group BrC#CBr JNFBOWNNNAHVNZ-UHFFFAOYSA-N 0.000 description 2
- XANKMCMFEJCODV-UHFFFAOYSA-N 1,2-diiodoethyne Chemical group IC#CI XANKMCMFEJCODV-UHFFFAOYSA-N 0.000 description 2
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- IUAZAEWSGCXPPS-UHFFFAOYSA-N diethyl 4-ethynylbenzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C#C)C=C1C(=O)OCC IUAZAEWSGCXPPS-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000012306 spectroscopic technique Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KFUSEUYYWQURPO-OWOJBTEDSA-N trans-1,2-dichloroethene Chemical group Cl\C=C\Cl KFUSEUYYWQURPO-OWOJBTEDSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LCWVSNGGGAEKPU-UHFFFAOYSA-N (4-nitrophenyl) prop-2-ynoate Chemical compound [O-][N+](=O)C1=CC=C(OC(=O)C#C)C=C1 LCWVSNGGGAEKPU-UHFFFAOYSA-N 0.000 description 1
- LKFKFNXPGMGBIS-XCVCLJGOSA-N (e)-1,3-bis(4-aminophenyl)prop-2-en-1-one Chemical compound C1=CC(N)=CC=C1\C=C\C(=O)C1=CC=C(N)C=C1 LKFKFNXPGMGBIS-XCVCLJGOSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical compound NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- KOGDFDWINXIWHI-OWOJBTEDSA-N 4-[(e)-2-(4-aminophenyl)ethenyl]aniline Chemical compound C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1 KOGDFDWINXIWHI-OWOJBTEDSA-N 0.000 description 1
- WAUKJWLKPXRNKT-UHFFFAOYSA-N 4-[2-(4-aminophenyl)ethynyl]aniline Chemical compound C1=CC(N)=CC=C1C#CC1=CC=C(N)C=C1 WAUKJWLKPXRNKT-UHFFFAOYSA-N 0.000 description 1
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical compound NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 240000008168 Ficus benjamina Species 0.000 description 1
- 240000001973 Ficus microcarpa Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MCMSPRNYOJJPIZ-UHFFFAOYSA-N cadmium;mercury;tellurium Chemical compound [Cd]=[Te]=[Hg] MCMSPRNYOJJPIZ-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- YWWARDMVSMPOLR-UHFFFAOYSA-M oxolane;tetrabutylazanium;fluoride Chemical compound [F-].C1CCOC1.CCCC[N+](CCCC)(CCCC)CCCC YWWARDMVSMPOLR-UHFFFAOYSA-M 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000843 phenylene group Chemical class C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Abstract
Description
本発明は光配向膜、その製造法、及び該光配向膜を有する液晶表示素子に関する。 The present invention relates to a photo-alignment film, a manufacturing method thereof, and a liquid crystal display element having the photo-alignment film.
液晶表示素子は画面の拡大化やカラー化、コントラストや発色等の表示品位や応答速度向上の要求に伴い、ツイステッドネマチック（Ｔｗｉｓｔｅｄ Ｎｅｍａｔｉｃ：ＴＮ）から、スーパーツイステッドネマチック（Ｓｕｐｅｒ Ｔｗｉｓｔｅｄ Ｎｅｍａｔｉｃ：ＳＴＮ）へ、さらに画素一つ一つに薄膜トランジスタ（Ｔｈｉｎ Ｆｉｌｍｅｄ Ｔｒａｎｓｉｓｔｏｒ：ＴＦＴ）を取り付けたＴＦＴ型表示素子へと発展してきている。近年ではＴＦＴ型表示素子の駆動方式の改良が進み、例えば視野角をさらに拡大するため、イン−プレーン−スイッチング（Ｉｎ Ｐｌａｉｎ Ｓｗｉｔｃｈｉｎｇ：ＩＰＳ）方式や垂直配向（Ｖｅｒｔｉｃａｌ Ａｌｉｍｅｎｔ、以下、ＶＡと略す）方式が開発され、さらに動画対応可能な応答速度を持つ光学補償ベンド（Ｏｐｔｉｃａｌｌｙ Ｃｏｍｐｅｎｓａｔｅｄ Ｂｅｎｄ：ＯＣＢ）方式が開発されている。 Liquid crystal display elements have been changed from Twisted Nematic (TN) to Super Twisted Nematic (STN) in response to demands for screen enlargement, colorization, display quality such as contrast and color development, and response speed improvement. Furthermore, it has been developed into a TFT type display element in which a thin film transistor (TFT) is attached to each pixel. In recent years, improvements in driving methods of TFT display devices have progressed. For example, in order to further increase the viewing angle, an in-plane switching (IPS) method or a vertical alignment (hereinafter abbreviated as VA) method is used. In addition, an optically compensated bend (OCB) system having a response speed capable of moving images has been developed.
用途の面から眺めると、現在液晶ディスプレイはパソコン用モニターからテレビへと適用範囲が広がっている。このためより大きな画面のディスプレイが求められることとなったが、これに伴い画質を均一に保つことが非常に難しくなっている。またモニター用途に比べテレビ用途においては、ユーザーがこれを使用する時間が長くなるため、長時間駆動させても画像に不具合を生じさせない（高信頼性を持つ）ことが求められている。 From the viewpoint of usage, the range of applications for LCDs has expanded from PC monitors to televisions. For this reason, a display with a larger screen has been demanded, but it is very difficult to keep the image quality uniform. Further, in television applications as compared with monitor applications, the user spends a longer time using it, and therefore, it is required that the image is not defective even when driven for a long time (has high reliability).
液晶配向膜は、液晶表示素子において液晶組成物を一定方向に配向させること、基板平面に対して液晶組成物を傾けること（プレチルト角を付与する）の２つの役割を果たしている。基板平面に対する液晶組成物の傾きはプレチルト角と呼ばれる。本明細書中でも以降この名称を使用する。液晶配向膜には、分子配向の経時的な、化学的な、及び熱的な劣化を最小限に抑えるため、ガラス転移点（Ｔｇ）が高く耐薬品性や耐熱性に優れたポリイミド薄膜がその材料として主に使用されている。液晶配向膜は、通常ポリアミック酸又は可溶性ポリイミドの溶液（以下、ワニスと略す）をスピナー法や印刷法等により電極付ガラス基板に塗布し、その基板を加熱してポリアミック酸を脱水、閉環するか、又は可溶性ポリイミド溶液の溶媒を蒸発させることによってポリイミドの薄膜を得る。さらにローラーに巻き付けた布でこの薄膜を擦る（ラビングする）ことにより、液晶組成物に対する均一な配向特性を液晶配向膜に与えることができる。 The liquid crystal alignment film plays two roles of aligning the liquid crystal composition in a certain direction in the liquid crystal display element and tilting the liquid crystal composition with respect to the substrate plane (giving a pretilt angle). The inclination of the liquid crystal composition with respect to the substrate plane is called a pretilt angle. This name will be used hereinafter in this specification. The liquid crystal alignment film is made of a polyimide thin film with a high glass transition point (Tg) and excellent chemical resistance and heat resistance in order to minimize the temporal and chemical and thermal degradation of molecular alignment. It is mainly used as a material. The liquid crystal alignment film is usually prepared by applying a solution of polyamic acid or soluble polyimide (hereinafter abbreviated as varnish) to a glass substrate with an electrode by a spinner method or a printing method, and heating the substrate to dehydrate and ring-close the polyamic acid. Alternatively, a polyimide thin film is obtained by evaporating the solvent of the soluble polyimide solution. Further, by rubbing (rubbing) the thin film with a cloth wound around a roller, uniform alignment characteristics for the liquid crystal composition can be imparted to the liquid crystal alignment film.
しかしながら上記のラビングによる配向処理は、液晶表示素子を製造する上で、以下のいくつかの問題を惹起している。まずラビング操作によって生じる静電気、それにより配向膜表面に吸着されるごみ、又はラビングにより布から溶出する不純物資により、電圧保持率（Ｖｏｌｔａｇｅ Ｈｏｌｄｉｎｇ Ｒａｔｉｏ、ＶＨＲ）等の液晶表示素子における特性が悪化し、ディスプレイの信頼性が低下することがある。また画面の大型化により、ラビング時に基板が変形し、ラビング布が液晶配向膜と接触しない領域が発生することがある。また逆に高精細なディスプレイでは画素が小さくなることにより、電極とその間の高低差が大きくなるため、均一な配向処理が難しく表示ムラの原因となる場合がある。 However, the alignment treatment by rubbing raises the following problems in manufacturing a liquid crystal display element. First, due to static electricity generated by the rubbing operation, dust adsorbed on the alignment film surface, or impurities that are eluted from the cloth by rubbing, the characteristics of the liquid crystal display element such as voltage holding ratio (VHR) deteriorate. Display reliability may be reduced. Further, due to the enlargement of the screen, the substrate may be deformed during rubbing, and an area where the rubbing cloth does not contact the liquid crystal alignment film may occur. On the other hand, in a high-definition display, since the pixels become small, the difference in height between the electrodes becomes large, so that uniform alignment processing is difficult and may cause display unevenness.
このようなラビングの問題点を解決するため、光や荷電粒子を用いた非接触の配向処理（いわゆるラビングレス）を行う方法が模索されている。しかしながらこれらの方法では、液晶の配向性が実用上十分でないことがある。また材料又は処理上の理由からＶＨＲ等の特性が悪化する場合がある。 In order to solve such problems of rubbing, a method of performing non-contact alignment treatment (so-called rubbing-less) using light or charged particles is being sought. However, in these methods, the orientation of the liquid crystal may not be practically sufficient. Moreover, characteristics such as VHR may deteriorate due to material or processing reasons.
非接触の配向処理については、例えば主鎖に二重結合や三重結合を持つ高分子からなる光配向膜が知られている（例えば、特許文献１参照。）。しかしながらこの光配向膜は、耐熱性については検討されているものの、この文献には作製された配向膜の電気的な特性に関する記載がなく、ＶＨＲ等の、液晶表示素子の信頼性に係る他の特性については検討の余地が残されている。 For non-contact alignment treatment, for example, a photo-alignment film made of a polymer having a double bond or a triple bond in the main chain is known (for example, see Patent Document 1). However, although this photo-alignment film has been studied for heat resistance, this document does not describe the electrical characteristics of the prepared alignment film, and other related to the reliability of liquid crystal display elements such as VHR. There is still room for studying characteristics.
また非接触の配向処理については、ポリアミック酸主鎖にアゾベンゼンを有するポリアミック酸を用い、イミド化前に光照射を行い、続いてこれをイミド化させることにより、非常に良好な配向性を有する膜が得られることが知られている（例えば、非特許文献１参照。）。しかしながらこの文献には作製された配向膜の電気的な特性に関する記載がない。
本発明の目的は、配向性が良好でＶＨＲ等の電気的な特性も実用に耐えうる光配向膜を提供することである。 An object of the present invention is to provide a photo-alignment film that has good orientation and can withstand electrical characteristics such as VHR in practical use.
本発明者らは鋭意研究開発を進めた結果、少なくともテトラカルボン酸二無水物及びジアミンを原料として形成されたポリアミック酸であって、テトラカルボン酸二無水物及びジアミンの少なくともいずれか一方又は両方に、Ａ成分である１〜３個の炭素−炭素二重結合又は１〜４個の三重結合等の不飽和結合含有基を有する化合物を用い、不飽和結合含有基が主鎖に導入されたポリアミック酸の膜に光照射を行い、続いてこれをイミド化させることにより、液晶配向膜に用いたときに液晶組成物の配向安定性に優れ、電圧保持率が高い光配向膜を提供出来ることを見出し、本発明を完成させた。 As a result of intensive research and development, the inventors of the present invention are polyamic acids formed using at least tetracarboxylic dianhydride and diamine as raw materials, and at least one of or both of tetracarboxylic dianhydride and diamine. , A compound having an unsaturated bond-containing group such as 1 to 3 carbon-carbon double bonds or 1 to 4 triple bonds as the component A, and a polyamic in which the unsaturated bond-containing group is introduced into the main chain By irradiating the acid film with light and subsequently imidizing it, it is possible to provide a photo-alignment film that has excellent alignment stability of the liquid crystal composition and a high voltage holding ratio when used in the liquid crystal alignment film. The headline and the present invention were completed.
本発明は以下から構成される。 The present invention comprises the following.
[１] 少なくともジアミン及びテトラカルボン酸二無水物を原料として生成されたポリ
アミック酸を光の照射によって所定の方向に配向させた後、イミド化することによって形成された光配向膜において、前記ジアミンがＡ成分である下記一般式（１）で表される不飽和結合含有ジアミンの一又は二以上を含むか、又は前記テトラカルボン酸二無水物がＡ成分である下記一般式（２）で表される不飽和結合含有テトラカルボン酸二無水物の一又は二以上を含むか、又は前記ジアミンがＡ成分である前記不飽和結合含有ジアミンの一又は二以上を含みかつ前記テトラカルボン酸二無水物がＡ成分である前記不飽和結合含有テトラカルボン酸二無水物の一又は二以上を含むことを特徴とする光配向膜。
[1] In a photo-alignment film formed by orienting a polyamic acid produced from at least a diamine and tetracarboxylic dianhydride as a raw material in a predetermined direction by light irradiation and then imidizing, the diamine contains One or two or more unsaturated bond-containing diamines represented by the following general formula (1), which is the A component, are included, or the tetracarboxylic dianhydride is represented by the following general formula (2), which is the A component. One or more unsaturated bond-containing tetracarboxylic dianhydrides, or one or more of the unsaturated bond-containing diamines, wherein the diamine is component A, and the tetracarboxylic dianhydride is A photo-alignment film comprising one or more of the unsaturated bond-containing tetracarboxylic dianhydrides as component A.
一般式（１）中、Ａ1及びＡ2は、それぞれ独立して二価の有機基を表し、Ｔは１〜３個の炭素−炭素二重結合又は１〜４個の三重結合を含む二価の不飽和結合含有基を表す。また一般式（２）中、Ａ3及びＡ4は、それぞれ独立して三価の有機基を表し、Ｔは１〜３個の炭素−炭素二重結合又は１〜４個の三重結合を含む二価の不飽和結合含有基を表す。 In general formula (1), A 1 and A 2 each independently represent a divalent organic group, and T represents a group having 1 to 3 carbon-carbon double bonds or 1 to 4 triple bonds. Represents a valent unsaturated bond-containing group. In general formula (2), A 3 and A 4 each independently represent a trivalent organic group, and T contains 1 to 3 carbon-carbon double bonds or 1 to 4 triple bonds. Represents a divalent unsaturated bond-containing group.
［２］ 前記不飽和結合含有ジアミンが、前記一般式（１）中、Ａ1及びＡ2はそれぞれ独立して炭素数６から２０の芳香環、炭素数１から１０の脂環、又は炭素数１から１０のアルキレンを表し、それぞれオキシ及びカルボニルを含んでいてもよく、Ｔは以下の（Ａ）から（Ｇ）の群から選ばれる不飽和結合含有基のいずれかを表すジアミンであることを特徴とする［１］記載の光配向膜。 [2] In the general formula (1), in the unsaturated bond-containing diamine, A 1 and A 2 are each independently an aromatic ring having 6 to 20 carbon atoms, an alicyclic ring having 1 to 10 carbon atoms, or a carbon number. 1 to 10 alkylene, each of which may contain oxy and carbonyl, and T is a diamine representing any one of unsaturated bond-containing groups selected from the following groups (A) to (G): The photo-alignment film according to [1], which is characterized.
［３］ 前記不飽和結合含有テトラカルボン酸二無水物が、前記一般式（２）中、Ａ3及びＡ4は、それぞれ独立して炭素数６から２０の芳香環又は炭素数１から２０の脂肪族基を表し、それぞれオキシ及びカルボニルを含んでいてもよく、Ｔは前記（Ａ）から（Ｇ）の群から選ばれる不飽和結合含有基のいずれかを表すテトラカルボン酸二無水物であることを特徴とする［１］又は［２］に記載の光配向膜。 [3] In the general formula (2), the unsaturated bond-containing tetracarboxylic dianhydride has A 6 and A 4 each independently an aromatic ring having 6 to 20 carbon atoms or 1 to 20 carbon atoms. Represents an aliphatic group, each of which may contain oxy and carbonyl, and T is a tetracarboxylic dianhydride representing any of the unsaturated bond-containing groups selected from the groups (A) to (G). The photo-alignment film according to [1] or [2], wherein
［４］ 前記ジアミンは、下記一般式（３）で表されるジアミンの一又は二以上をＢ成分としてさらに含むことを特徴とする［１］〜［３］のいずれか一項に記載の光配向膜。 [4] The light according to any one of [1] to [3], wherein the diamine further includes one or more diamines represented by the following general formula (3) as a B component. Alignment film.
一般式（３）中、Ｒ1は下記一般式（５）〜（８）で表される基から選ばれる二価の有
機基を表す。
In general formula (3), R 1 represents a divalent organic group selected from the groups represented by the following general formulas (5) to (8).
一般式（５）中、Ｒ4はＨ又は炭素数１〜１２のアルキルを表し、環Ａはそれぞれ独立して１，４−フェニレン又は１，４−シクロへキシレンを表し、Ｚ1及びＺ2はそれぞれ独立して単結合、ＣＨ2、ＣＨ2ＣＨ2又はＯを表し、ｒは０〜３、ｓはそれぞれ独立して０〜５、ｔ１は０〜３、ｔ２は０〜３の整数を表す。また、１，４−フェニレン又は１，４−シクロへキシレンの任意のＨは炭素数１〜４のアルキルで置換されていてもよい。 In the general formula (5), R 4 represents H or alkyl having 1 to 12 carbon atoms, each ring A independently represents 1,4-phenylene or 1,4-cyclohexylene, and Z 1 and Z 2 Each independently represents a single bond, CH 2 , CH 2 CH 2 or O, r is 0 to 3, s is each independently 0 to 5, t1 is 0 to 3, t2 is an integer of 0 to 3. To express. Further, any H in 1,4-phenylene or 1,4-cyclohexylene may be substituted with alkyl having 1 to 4 carbon atoms.
一般式（６）中、Ｘ1及びＸ2は単結合、Ｏ、ＣＯＯ、ＯＣＯ、ＮＨ、ＣＯＮＨ又は炭素数１〜１２のアルキレンを表し、Ｇ1及びＧ2は単結合、又は芳香族環及び脂環式環から選ばれる１〜３個の環を含む二価の基を表し、Ｒ5はＨ、Ｆ、ＣＮ、ＯＨ又は炭素数１〜３０のアルキル、ペルフルオロアルキル若しくはアルコキシを表す。ベンゼン環に対する置換基の結合位置及び２個の遊離基の位置は任意の位置である。但し、Ｇ2が単結合でありＸ2が単結合でもなくアルキレンでもない場合は、Ｒ5はＨ又はアルキルであり、またＧ1及びＧ2が共に単結合である場合は、Ｘ1、Ｘ2及びＲ5の合計の炭素数が３以上である。 In General Formula (6), X 1 and X 2 represent a single bond, O, COO, OCO, NH, CONH, or alkylene having 1 to 12 carbon atoms, G 1 and G 2 represent a single bond, an aromatic ring, and A divalent group containing 1 to 3 rings selected from an alicyclic ring is represented, and R 5 represents H, F, CN, OH, or alkyl having 1 to 30 carbon atoms, perfluoroalkyl or alkoxy. The bonding position of the substituent to the benzene ring and the positions of the two free radicals are arbitrary positions. However, when G 2 is a single bond and X 2 is neither a single bond nor alkylene, R 5 is H or alkyl, and when G 1 and G 2 are both single bonds, X 1 , X The total carbon number of 2 and R 5 is 3 or more.
一般式（７）中、Ｘ3及びＸ4はそれぞれ独立して単結合、ＣＨ2、ＣＨ2ＣＨ2又はＯを表し、Ｒ6及びＲ7はＨ、炭素数１〜１２のアルキル、又は炭素数１〜１２のペルフルオロアルキルを表す。ｕ１、ｕ２、ｕ３、ｕ４、及びｕ５はそれぞれ独立して０〜３の整数を表す。また、１，４−フェニレンの任意のＨは炭素数１〜４のアルキルで置換されていてもよい。 In general formula (7), X 3 and X 4 each independently represent a single bond, CH 2 , CH 2 CH 2 or O, R 6 and R 7 are H, alkyl having 1 to 12 carbons, or carbon The perfluoroalkyl of number 1-12 is represented. u1, u2, u3, u4, and u5 each independently represent an integer of 0 to 3. Moreover, arbitrary H of 1, 4-phenylene may be substituted by the C1-C4 alkyl.
一般式（８）中、Ｘ5又はＸ6は単結合、Ｏ、又はＳを表し、ｍ１又はｍ２は０又は１の整数を表し、ｎは０〜１０の整数を表す。また、ベンゼン環に対する置換基及び遊離基の
結合位置は任意の位置である。
In General Formula (8), X 5 or X 6 represents a single bond, O, or S, m1 or m2 represents 0 or an integer of 1, and n represents an integer of 0 to 10. Moreover, the bonding position of the substituent and free radical to the benzene ring is an arbitrary position.
［５］ 前記テトラカルボン酸二無水物は、下記一般式（４）で表されるテトラカルボン酸二無水物の一又は二以上をＢ成分としてさらに含むことを特徴とする［１］〜［４］のいずれか一項に記載の光配向膜。 [5] The tetracarboxylic dianhydride further includes one or more tetracarboxylic dianhydrides represented by the following general formula (4) as a B component [1] to [4] ] The photo-alignment film as described in any one of.
一般式（４）において、Ｒ2は下記一般式（９）〜（１７）で表される基から選ばれる四価の基を表す。 In the general formula (4), R 2 represents a tetravalent group selected from the groups represented by the following general formulas (9) to (17).
一般式（９）中、Ｇ3は単結合、炭素数１〜１２のアルキレン、１，４−フェニレン、又は１，４−シクロヘキシレンを表し、Ｘ6はそれぞれ独立して単結合又はＣＨ2を表す。 In General Formula (9), G 3 represents a single bond, alkylene having 1 to 12 carbon atoms, 1,4-phenylene, or 1,4-cyclohexylene, and X 6 independently represents a single bond or CH 2 . To express.
一般式（１０）中、Ｒ32、Ｒ33、Ｒ34、及びＲ35はＨ、メチル、エチル、又はフェニルを表す。 In general formula (10), R 32 , R 33 , R 34 , and R 35 represent H, methyl, ethyl, or phenyl.
一般式（１１）中、環Ａ6はシクロヘキサン環又はベンゼン環を表す。 In general formula (11), ring A 6 represents a cyclohexane ring or a benzene ring.
一般式（１２）中、Ｇ4は単結合、ＣＨ2、ＣＨ2ＣＨ2、Ｏ、ＣＯ、Ｓ、Ｃ（ＣＨ3）2、又はＣ（ＣＦ3）2を表し、環Ａ6はそれぞれ独立してシクロヘキサン環又はベンゼン環を表す。 In General Formula (12), G 4 represents a single bond, CH 2 , CH 2 CH 2 , O, CO, S, C (CH 3 ) 2 , or C (CF 3 ) 2, and each ring A 6 is independent. Represents a cyclohexane ring or a benzene ring.
一般式（１３）中、Ｒ36はＨ、又はメチルを表す。 In the general formula (13), R 36 represents H or methyl.
一般式（１４）中、Ｘ6はそれぞれ独立して単結合又はＣＨ2を表し、ｖは１又は２を表す。 In general formula (14), X 6 each independently represents a single bond or CH 2 , and v represents 1 or 2.
一般式（１５）中、Ｘ6は単結合又はＣＨ2を表す。 In general formula (15), X 6 represents a single bond or CH 2 .
一般式（１６）中、Ｒ37はＨ、メチル、エチル、又はフェニルを表し、環Ａ6はシクロヘキサン環又はベンゼン環を表す。 In the general formula (16), R 37 represents H, methyl, ethyl, or phenyl, ring A 6 represents a cyclohexane ring or a benzene ring.
一般式（１７）中、ｗ１及びｗ２は０又は１を表す。ただしｗ１＝１でｗ２＝０であることはない。 In general formula (17), w1 and w2 represent 0 or 1. However, w1 = 1 and w2 = 0 are not satisfied.
［６］ 一般式（１）のＡ1及びＡ2が下記構造式（Ｉ）から（Ｖ）及び下記一般式（ＶＩ）、（ＶＩＩ）の群から独立して選択されることを特徴とする［２］記載の光配向膜。一般式（ＶＩ）または（ＶＩＩ）中、ｎは１〜１０の整数を表す。 [6] A 1 and A 2 in the general formula (1) are independently selected from the following structural formulas (I) to (V) and the following general formulas (VI) and (VII): [2] The photo-alignment film according to [2]. In general formula (VI) or (VII), n represents an integer of 1 to 10.
［７］ 一般式（２）のＡ3及びＡ4が下記構造式（ＶＩＩＩ）から（Ｘ）の群から独立して選択されることを特徴とする［３］記載の光配向膜。 [7] The photo-alignment film according to [3], wherein A 3 and A 4 in the general formula (2) are independently selected from the following structural formulas (VIII) to (X).
［８］ 一般式（１）のＡ1及びＡ2が前記構造式（Ｉ）、（ＩＩ）、（ＩＩＩ）及び前記一般式（ＶＩ）、（ＶＩＩ）の群から独立して選択されることを特徴とする［６］記載の光配向膜。 [8] A 1 and A 2 in the general formula (1) are independently selected from the group of the structural formulas (I), (II), (III) and the general formulas (VI), (VII). [6] The photo-alignment film according to [6].
［９］ 一般式（２）のＡ3及びＡ4が前記構造式（ＶＩＩＩ）で表されることを特徴とする［７］記載の光配向膜。 [9] The photo-alignment film according to [7], wherein A 3 and A 4 in the general formula (2) are represented by the structural formula (VIII).
［１０］ 前記ポリアミック酸の原料の総量に対する、前記不飽和結合含有テトラカルボン酸二無水物及び前記不飽和結合含有ジアミンのモル比は０．３〜１．０であることを特徴とする［１］〜［９］のいずれか一項に記載の光配向膜。 [10] The molar ratio of the unsaturated bond-containing tetracarboxylic dianhydride and the unsaturated bond-containing diamine to the total amount of the raw material of the polyamic acid is 0.3 to 1.0. ] The photo-alignment film according to any one of [9] to [9].
［１１］ 少なくともジアミン及びテトラカルボン酸二無水物を原料として生成されたポリアミック酸を光の照射によって所定の方向に配向させた後、イミド化することによって形成された光配向膜において、前記ジアミン及び前記テトラカルボン酸二無水物は、前記ジアミンとしてＡ成分である下記構造式（１−１）〜（１−１１）の群から選択される一又は二以上のジアミン、及び前記テトラカルボン酸二無水物としてＡ成分である下記構造式（２−１）〜（２−７）の群から選択される一又は二以上のテトラカルボン酸二無水物のいずれか一方又は両方を含み、さらに前記ジアミン及び前記テトラカルボン酸二無水物は、前記ジアミンとしてＢ成分である下記一般式（３−１）、（３−３）〜（３−７）及び下記構造式（３−２）の群から選択される一又は二以上のジアミン、及び前記テトラカルボン酸二無水物としてＢ成分である下記一般式（４−２）及び下記構造式（４−１）、（４−３）〜（４−７）の群から選択される一又は二以上のテトラカルボン酸二無水物のいずれか一方又は両方を含むことを特徴とする光配向膜。 [11] In a photo-alignment film formed by orienting polyamic acid produced using at least diamine and tetracarboxylic dianhydride as raw materials in a predetermined direction by light irradiation and then imidizing, the diamine and The tetracarboxylic dianhydride is one or more diamines selected from the group of the following structural formulas (1-1) to (1-11), which are A components as the diamine, and the tetracarboxylic dianhydride. Including one or both of one or two or more tetracarboxylic dianhydrides selected from the group of the following structural formulas (2-1) to (2-7) as the A component, The tetracarboxylic dianhydride is a group of the following general formulas (3-1), (3-3) to (3-7) and the following structural formula (3-2) which are B components as the diamine. And the following general formula (4-2) and the following structural formulas (4-1) and (4-3) to (4) which are B components as the tetracarboxylic dianhydride -7) A photoalignment film comprising one or both of one or more tetracarboxylic dianhydrides selected from the group of 7).
一般式（３−４）中、Ｘ40は−Ｏ−又は−Ｓ−を表し、一般式（３−７）中、Ｘ41は独立して−ＣＨ2−、−ＣＨ2ＣＨ2−、又は−Ｏ−を表し、一般式（３−５）及び（３−６）中、Ｒ40は水素又は炭素数１から２０のアルキルを表し、一般式（３−７）中、Ｒ41は水素又は炭素数１から１０のアルキルを表し、一般式（３−１）及び（３−３）中、ｎは１〜６の整数を表し、一般式（３−３）中、ｍは独立して１又は２を表し、一般式（３−５）及び（３−６）中、ｐは０〜２の整数を表す。 In General Formula (3-4), X 40 represents —O— or —S—, and in General Formula (3-7), X 41 independently represents —CH 2 —, —CH 2 CH 2 —, or In the general formulas (3-5) and (3-6), R 40 represents hydrogen or alkyl having 1 to 20 carbon atoms, and in the general formula (3-7), R 41 represents hydrogen or Represents alkyl having 1 to 10 carbon atoms, and in general formulas (3-1) and (3-3), n represents an integer of 1 to 6, and in general formula (3-3), m is independently 1 Or 2 is represented and p represents the integer of 0-2 in general formula (3-5) and (3-6).
一般式（４−２）中、Ｒ42、Ｒ43、Ｒ44、およびＲ45は、それぞれ独立して水素又はメチルを表す。 In general formula (4-2), R 42 , R 43 , R 44 , and R 45 each independently represent hydrogen or methyl.
［１２］ 前記ジアミン及び前記テトラカルボン酸二無水物は、前記ジアミンとしてＡ成分である前記構造式（１−１）〜（１−６）、（１−１０）、（１−１１）の群から選択される一又は二以上のジアミン、及び前記テトラカルボン酸二無水物としてＡ成分である前記構造式（２−１）〜（２−３）の群から選択される一又は二以上のテトラカルボン酸二無水物のいずれか一方又は両方を含み、さらに前記ジアミン及び前記テトラカルボン酸二無水物は、前記ジアミンとしてＢ成分である前記一般式（３−１）、（３−３）〜（３−７）及び前記構造式（３−２）の群から選択される一又は二以上のジアミン、及び前記テトラカルボン酸二無水物としてＢ成分である前記一般式（４−２）及び前記構造式（４−１）、（４−３）の群から選択される一又は二以上のテトラカルボン酸二無水物のいずれか一方又は両方を含むことを特徴とする［１１］記載の光配向膜。 [12] The group of the structural formulas (1-1) to (1-6), (1-10), and (1-11), in which the diamine and the tetracarboxylic dianhydride are component A as the diamine. And one or more diamines selected from the group of the structural formulas (2-1) to (2-3) which are A components as the tetracarboxylic dianhydride The diamine and the tetracarboxylic dianhydride include one or both of carboxylic dianhydrides, and the diamine and the tetracarboxylic dianhydride are B components as the diamine. 3-7) and one or two or more diamines selected from the group of the structural formula (3-2), and the general formula (4-2) and the structure which are B components as the tetracarboxylic dianhydride From the group of formulas (4-1) and (4-3) One or more, characterized in that it comprises one or both of the tetracarboxylic acid dianhydride [11] photo-alignment film according the-option.
［１３］ 前記一般式（３−１）、（３−３）〜（３−７）で表されるジアミンが、前記一般式（３−１）、（３−３）〜（３−７）中、Ｘ40は−Ｏ−を表し、Ｘ41は独立して−ＣＨ2−又は−Ｏ−を表し、Ｒ40は水素又は炭素数１から２０のアルキルを表し、Ｒ41は
炭素数１から１０のアルキルを表し、ｎは１〜４の整数を表し、ｍは１を表し、ｐは０〜２の整数を表すジアミンであることを特徴とする［１１］又は［１２］に記載の光配向膜。
[13] The diamines represented by the general formulas (3-1), (3-3) to (3-7) are represented by the general formulas (3-1), (3-3) to (3-7). In the formula, X 40 represents —O—, X 41 independently represents —CH 2 — or —O—, R 40 represents hydrogen or alkyl having 1 to 20 carbons, and R 41 represents from 1 carbons. The light according to [11] or [12], wherein 10 represents alkyl, n represents an integer of 1 to 4, m represents 1, and p represents a diamine representing an integer of 0 to 2. Alignment film.
[１４] 下記式αで求められるポリイミドの主鎖の配向指数Δが０．５以上である液晶
配向膜であることを特徴とする[１]又は［１１］に記載の光配向膜。
Δ＝（｜Ａ‖−Ａ⊥｜）／｛（Ａ‖＋Ａ⊥）×ｄ｝ （α）
[14] The photoalignment film according to [1] or [11], which is a liquid crystal alignment film having an orientation index Δ of a main chain of polyimide obtained by the following formula α of 0.5 or more.
Δ = (| A‖−A⊥ |) / {(A‖ + A⊥) × d} (α)
式（α）中、Ａ‖は、直線偏光の赤外光を光配向膜の表面に対して垂直に、かつ赤外光の偏光方向がポリイミドの主鎖の平均配向方向に平行になるように照射したときの波数１，３６０ｃｍ-1付近のイミド環のＣ−Ｎ−Ｃ伸縮振動による積分吸光度を表し、Ａ⊥は、直線偏光の赤外光を光配向膜の表面に対して垂直に、かつ赤外光の偏光方向がポリイミドの主鎖の平均配向方向に垂直になるように照射したときの波数１，３６０ｃｍ-1付近のイミド環のＣ−Ｎ−Ｃ伸縮振動による積分吸光度を表し、ｄは液晶配向膜の膜厚（ｎｍ）を表す。 In Formula (α), A‖ is such that linearly polarized infrared light is perpendicular to the surface of the photo-alignment film, and the polarization direction of infrared light is parallel to the average orientation direction of the polyimide main chain. It represents the integrated absorbance due to the C—N—C stretching vibration of the imide ring near the wave number of 1,360 cm −1 when irradiated, and A⊥ represents the linearly polarized infrared light perpendicular to the surface of the photo-alignment film. And represents the integrated absorbance due to C—N—C stretching vibration of the imide ring near the wave number of 1,360 cm −1 when irradiated so that the polarization direction of infrared light is perpendicular to the average orientation direction of the main chain of the polyimide, d represents the film thickness (nm) of the liquid crystal alignment film.
［１５］ 対向配置されている一対の基板と、前記一対の基板それぞれの対向している面の一方又は両方に形成されている電極と、前記一対の基板それぞれの対向している面に形成された液晶配向膜と、前記一対の基板間に形成された液晶層とを有する液晶表示素子において、前記液晶配向膜は、［１］〜［１４］のいずれか一項に記載の光配向膜であることを特徴とする液晶表示素子。 [15] A pair of substrates disposed opposite to each other, an electrode formed on one or both of the surfaces facing each other of the pair of substrates, and a surface facing each of the pair of substrates. In the liquid crystal display element having the liquid crystal alignment film and the liquid crystal layer formed between the pair of substrates, the liquid crystal alignment film is the photo-alignment film according to any one of [1] to [14]. There is a liquid crystal display element.
［１６］ 下記一般式（１）で表されるジアミン。 [16] A diamine represented by the following general formula (1).
一般式（１）中、Ａ1及びＡ2は、それぞれ独立して炭素数６から３０の芳香環、炭素数１から１０の脂環、又は炭素数１から１０のアルキレンを表し、それぞれオキシ及びカルボニルを含んでいてもよく、Ｔは以下の（Ｄ）〜（Ｇ）の群から選ばれるいずれかを表す。ただしＴが（Ｄ）のときＡ1およびＡ2が共に１，４−または１，３−フェニレン環であることはない。 In general formula (1), A 1 and A 2 each independently represent an aromatic ring having 6 to 30 carbon atoms, an alicyclic ring having 1 to 10 carbon atoms, or alkylene having 1 to 10 carbon atoms, Carbonyl may be included, and T represents any one selected from the following groups (D) to (G). However, when T is (D), A 1 and A 2 are not 1,4- or 1,3-phenylene rings.
［１７］下記構造式（１−１０）または（１−１１）で表される[１６]に記載のジアミン。 [17] The diamine according to [16] represented by the following structural formula (1-10) or (1-11).
[１８] 下記一般式（２）で表されるテトラカルボン酸二無水物。 [18] A tetracarboxylic dianhydride represented by the following general formula (2).
一般式（２）中、一般式（２）中、Ａ3及びＡ4は、それぞれ独立して炭素数６から２０の芳香環又は炭素数１から２０の脂肪族基を表し、それぞれオキシ及びカルボニルを含んでいてもよく、Ｔは下記（Ｄ）から（Ｇ）の群から選ばれるいずれかを表す。 In general formula (2), in general formula (2), A 3 and A 4 each independently represents an aromatic ring having 6 to 20 carbon atoms or an aliphatic group having 1 to 20 carbon atoms, and represents oxy and carbonyl, respectively. And T represents any one selected from the following groups (D) to (G).
［１９］ 下記構造式（２−７）で表される［１８］記載のテトラカルボン酸二無水物。 [19] The tetracarboxylic dianhydride according to [18] represented by the following structural formula (2-7).
ポリアミック酸の原料のＡ成分である、テトラカルボン酸二無水物とジアミンとのうち、少なくともいずれか一方が前記不飽和結合含有基を有する化合物であるポリアミック酸の膜に、イミド化前に光照射を行い、続いてこれをイミド化させて光配向膜とすることにより、液晶組成物の配向安定性に優れ、電圧保持率が高く、かつイオン密度が低い光配向膜を得ることができる。このようにして作製された光配向膜を用いてディスプレイを製造
すれば、大画面又は高精細なディスプレイにおいても均一な配向を得ることができる。またラビング処理等の接触式の配向処理に伴う光配向膜の汚染に起因する電気特性の悪化を防ぐことができる。
Light irradiation before imidization is performed on the polyamic acid film, which is a compound having a unsaturated bond-containing group, at least one of tetracarboxylic dianhydride and diamine, which is the component A of the raw material of polyamic acid. And subsequently imidizing it to obtain a photoalignment film, a photoalignment film having excellent alignment stability of the liquid crystal composition, high voltage holding ratio, and low ion density can be obtained. If a display is manufactured using the photo-alignment film thus produced, a uniform orientation can be obtained even on a large screen or a high-definition display. In addition, it is possible to prevent deterioration of electrical characteristics due to contamination of the photo-alignment film accompanying contact-type alignment processing such as rubbing processing.
本発明の光配向膜は、ポリアミック酸溶液を基板に塗布し、溶媒を除去して作製した膜中のポリアミック酸を光の照射によって所定の方向に配向させてイミド化して形成された光配向膜である。前記ポリアミック酸は、二つの酸無水物基とこれらの結合基から成るテトラカルボン酸二無水物と、二つのアミノとこれらの結合基から成るジアミンとを原料とし、これらの原料を用いて得られた反応生成物である。前記ポリアミック酸の原料のＡ成分として、前記酸二無水物の結合基及び前記アミノの結合基の少なくともいずれかは、１〜４個の炭素−炭素二重結合又は三重結合を含む二価の不飽和結合含有基を含んでいる。 The photo-alignment film of the present invention is a photo-alignment film formed by applying a polyamic acid solution to a substrate and removing the solvent to align the polyamic acid in the film in a predetermined direction by light irradiation and imidize it. It is. The polyamic acid is obtained by using tetracarboxylic dianhydride consisting of two acid anhydride groups and their bonding groups, and two amino and diamine consisting of these bonding groups as raw materials. Reaction product. As the component A of the raw material of the polyamic acid, at least one of the acid dianhydride bonding group and the amino bonding group is a divalent non-valent group containing 1 to 4 carbon-carbon double bonds or triple bonds. Contains a saturated bond-containing group.
前記不飽和結合含有基中の炭素−炭素二重結合又は三重結合は、少ない光量で高い配向性を得るために、数多く共役している方が良い。しかしながら数多く共役していると熱や光に対する安定性が悪くなることがある。また可視光領域の吸収が大きくなるため、光配向膜としたとき着色が大きくなることがある。したがって二重結合の数は１から２個が、三重結合の数は１から３個が好適であり、二重結合の数は１個が、三重結合の数は２から３個がさらに好適である。 The carbon-carbon double bond or triple bond in the unsaturated bond-containing group is preferably conjugated in a large number in order to obtain high orientation with a small amount of light. However, when many are conjugated, stability against heat and light may be deteriorated. Further, since the absorption in the visible light region is increased, coloring may be increased when the photo-alignment film is formed. Accordingly, the number of double bonds is preferably 1 to 2, the number of triple bonds is preferably 1 to 3, the number of double bonds is preferably 1, and the number of triple bonds is more preferably 2 to 3. is there.
Ｔに二重結合が含まれる場合、シス又はトランスの２つの異性体が存在するが、本発明の光配向膜はこれらのどちらの異性体を用いても構わない。 When T contains a double bond, there are two isomers of cis and trans, and any of these isomers may be used in the photo-alignment film of the present invention.
前記テトラカルボン酸二無水物が前記不飽和結合含有基を含む場合は、前記ポリアミック酸の原料であるアミンのＢ成分として、前記不飽和結合含有基を含まない他のジアミンを用いることができる。 When the tetracarboxylic dianhydride includes the unsaturated bond-containing group, another diamine that does not include the unsaturated bond-containing group can be used as the B component of the amine that is a raw material of the polyamic acid.
前記炭素−炭素二重結合又は三重結合を含む不飽和結合含有ジアミンには、一般式（１）で表されるジアミンが挙げられる。前記不飽和結合含有ジアミンは、一般式（１）で表されるジアミンの一つでもよいし二つ以上でもよい。 Examples of the unsaturated bond-containing diamine containing a carbon-carbon double bond or triple bond include a diamine represented by the general formula (1). The unsaturated bond-containing diamine may be one of the diamines represented by the general formula (1) or two or more.
前記一般式（１）中、Ａ1及びＡ2は、それぞれ独立して炭素数６から２０の芳香環、炭素数１から１０の脂環、又は炭素数１から１０のアルキレンを表す。Ａ1及びＡ2は、それぞれオキシ及びカルボニルを含んでいてもよい。Ａ1及びＡ2は公知の芳香族基、脂環基、アルキルから選択できるが、製造が容易で光配向膜にした場合の特性が良く、さらに光配向膜に高いＶＨＲを付与する観点から、下記（Ｉ）〜（ＶＩＩ）で表される基が好ましく、（Ｉ）〜（Ｖ）および（ＶＩＩ）で表される基がより好ましい。なお、式（ＶＩ）または（ＶＩＩ）中、ｎは１から１０の整数を表す。 In the general formula (1), A 1 and A 2 each independently represent an aromatic ring having 6 to 20 carbon atoms, an alicyclic ring having 1 to 10 carbon atoms, or alkylene having 1 to 10 carbon atoms. A 1 and A 2 may contain oxy and carbonyl, respectively. A 1 and A 2 can be selected from known aromatic groups, alicyclic groups, and alkyls, but are easy to produce and have good characteristics when used as a photo-alignment film, and from the viewpoint of imparting a high VHR to the photo-alignment film, The groups represented by the following (I) to (VII) are preferred, and the groups represented by (I) to (V) and (VII) are more preferred. In formula (VI) or (VII), n represents an integer of 1 to 10.
Ａ1及びＡ2が前記（Ｉ）〜（ＩＩＩ）で表される芳香族基であるポリアミック酸は、良好な配向性を示すが、着色が大きくなる。またＡ1及びＡ2が（ＩＶ）〜（ＶＩＩ）で表されるポリアミック酸は、着色は小さくなるが、配向性が若干悪くなる。（ＩＶ）〜（ＶＩＩ）をＡ1又はＡ2に採用したときのポリアミック酸の配向性は、前記（Ｉ）〜（ＩＩＩ）のような芳香環からなる構成単位を含む前記他のジアミンを前記不飽和結合含有ジアミンとして併用して、前記芳香環からなる構成単位をポリアミック酸の主鎖中に導入することによって、向上させることが出来る。 The polyamic acid in which A 1 and A 2 are the aromatic groups represented by the above (I) to (III) exhibits good orientation, but the coloring becomes large. In addition, the polyamic acid in which A 1 and A 2 are represented by (IV) to (VII) is less colored but the orientation is slightly deteriorated. The orientation of the polyamic acid when (IV) to (VII) is adopted as A 1 or A 2 is the same as that of the other diamine containing a structural unit consisting of an aromatic ring as in the above (I) to (III). It can improve by introducing together the structural unit which consists of the said aromatic ring in the principal chain of polyamic acid, using together as unsaturated bond containing diamine.
また前記一般式（１）中、Ｔで表される不飽和結合含有基は、１〜３個の炭素−炭素二重結合又は１〜４個の三重結合を含む二価の不飽和結合含有基である。前記不飽和結合含有基は、良好な光配向性を有し、製造が容易な（Ａ）〜（Ｇ）で表される基が好適である。このときより高い光配向性を示すことから、（Ｃ）〜（Ｇ）で表される基がさらに好適である。 In the general formula (1), the unsaturated bond-containing group represented by T is a divalent unsaturated bond-containing group containing 1 to 3 carbon-carbon double bonds or 1 to 4 triple bonds. It is. The unsaturated bond-containing group is preferably a group represented by (A) to (G) that has good photoalignment and is easy to produce. The groups represented by (C) to (G) are more preferable because they exhibit higher photoalignment at this time.
Ｔが前記（Ｄ）〜（Ｇ）で表される一般式（１）のジアミンは、以下のスキーム１に従って合成することができる。 The diamine of the general formula (1) in which T is represented by the above (D) to (G) can be synthesized according to the following scheme 1.
式中Ｔ1は１，４−フェニレン、炭素−炭素二重結合、三重結合、又は上記（Ｄ）を表し、Ｘは塩素、臭素、又はヨウ素を表し、Ｒ20はアミノ又はニトロを１つ有する基を表す。 In the formula, T 1 represents 1,4-phenylene, a carbon-carbon double bond, a triple bond, or the above (D), X represents chlorine, bromine, or iodine, and R 20 has one amino or nitro. Represents a group.
すなわちＬａｍｂｅｒｔ Ｂｒａｎｄｓｍａ著、Ｐｒｅｐａｒａｔｉｖｅ Ａｃｅｔｙｌｅｎｉｃ Ｃｈｅｍｉｓｔｒｙ、第２版、１９８８年、ＥＬＳＥＶＩＥＲ社又はヨーロピアン・ジャーナル・オーガニック・ケミストリー、３８７９（２００１）等の文献記載の方法に従い、前記スキーム１における（１−１）で表されるジハロゲン化物と前記スキーム１における（１−２）で表されるアセチレン化合物とをパラジウム触媒および必要によって加えられる助触媒存在下、反応させることによって、前記スキーム１における（１）で表されるジアミン又は（１−３）で表されるジニトロ化合物が合成できる。このジニトロ化合物をＯｒｇａｎｉｃ Ｓｙｎｔｈｅｓｉｓ，Ｃｏｌｌｅｃｔｉｖｅ
Ｖｏｌｕｍｅ，２，１３０（１９４３）等に記載の方法と同様にして、塩化すず等を用い還元することにより、目的とする前記一般式（１）で表されるジアミンが得られる。
That is, according to the method described in the literature of Lambert Brandsma, Preparative Acetyl Chemistry, 2nd edition, 1988, ELSEVIER or European Journal Organic Chemistry, 3879 (2001), it is represented by (1-1) in Scheme 1 above. Is reacted with the acetylene compound represented by (1-2) in Scheme 1 in the presence of a palladium catalyst and a cocatalyst that is added if necessary, and is represented by (1) in Scheme 1. Dinitro compounds represented by diamine or (1-3) can be synthesized. This dinitro compound is converted to Organic Synthesis, Collective.
In the same manner as described in Volume, 2, 130 (1943), etc., the target diamine represented by the general formula (1) is obtained by reduction using tin chloride or the like.
ここにおいて前記スキーム１における（１−１）で表される化合物として、市販のシス−１，２−ジクロロエチレン、トランス−１，２−ジクロロエチレンやＪ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，９１，５６７３（１９６９）やＴｅｔｒａｈｅｄｒｏｎ，２７，３３，（１９７１）等に記載のジブロモアセチレンやジヨードアセチレン、Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔ．，４０，８５７９，（１９９９）に記載の１，４−ジヨードエチニルベンゼンが使用できる。また前記スキーム１における（１−２）で表される化合物は市販の３−エチニルアニリン、４−エチニルアニリン、Ｊ．Ｏｒｇ．Ｃｈｅｍ．Ｓｏｃ．，３７，８４１（１９７２）に記載の４−（２−プロピンオキシ）アニリン、又はＪ．Ｏｒｇ．Ｃｈｅｍ．Ｓｏｃ．，３９，７２５（１９７４）に記載の４−ニトロフェノールプロピオル酸エステル等が使用できる。 Here, as the compound represented by (1-1) in the scheme 1, commercially available cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, Am. Chem. Soc. , 91, 5673 (1969), Tetrahedron, 27, 33, (1971) and the like, dibromoacetylene and diiodoacetylene, Tetrahedron Lett. 1,4-diiodoethynylbenzene described in JP, 40, 8579, (1999). In addition, the compound represented by (1-2) in the scheme 1 is commercially available 3-ethynylaniline, 4-ethynylaniline, J.P. Org. Chem. Soc. , 37, 841 (1972), or J.I. Org. Chem. Soc. , 39, 725 (1974), 4-nitrophenol propiolate and the like can be used.
スキーム１の反応で用いられる触媒として、テトラキス(トリフェニルホスフィン)パラジウム（０）等の０価のパラジウム触媒や、ジクロロビストリフェニルフォスフィンパラジウム（２）等の二価のパラジウム触媒が好適である。また助触媒としてはヨウ化銅や塩化銅等の１価の銅塩が好適である。また溶媒としてはジエチルアミン、トリエチルアミン、ピロリジン、またはピペリジン等のアミン系やこれらとテトラヒドロフラン又はエチレングリコールジメチルエーテル等の溶媒との混合物が好適である。さらに反応温度は０℃〜これらの溶媒の沸点までの間で選ぶことが出来るが、反応率を向上させると共に副反応を抑えるため、室温から１００℃の範囲が好適である。 As the catalyst used in the reaction of Scheme 1, a zero-valent palladium catalyst such as tetrakis (triphenylphosphine) palladium (0) or a divalent palladium catalyst such as dichlorobistriphenylphosphine palladium (2) is preferable. As the promoter, monovalent copper salts such as copper iodide and copper chloride are suitable. The solvent is preferably an amine such as diethylamine, triethylamine, pyrrolidine, or piperidine, or a mixture of these with a solvent such as tetrahydrofuran or ethylene glycol dimethyl ether. Furthermore, the reaction temperature can be selected from 0 ° C. to the boiling point of these solvents, but a range from room temperature to 100 ° C. is preferable in order to improve the reaction rate and suppress side reactions.
一般式（１）で表される化合物および中間体はカラムクロマトグラフィー又は再結晶によって精製することができる。同定は1ＨＮＭＲ、13Ｃ ＮＭＲ、ＩＲ等の分光学的手法、又はマススペクトルによって行うことができる。 The compound and intermediate represented by the general formula (1) can be purified by column chromatography or recrystallization. Identification can be performed by spectroscopic techniques such as 1 HNMR, 13 C NMR, IR, or mass spectrum.
前記一般式（１）で表されるジアミンにおいて、Ａ1−Ｔ−Ａ2で表されるジアミン残基の、後述する本発明の光配向膜におけるジアミンの好適な例として以下の（２０）〜（５５）が挙げられる。 In the diamine represented by the general formula (1), the following (20) to (20) as preferable examples of the diamine in the photo-alignment film of the present invention to be described later of the diamine residue represented by A 1 -TA 2. (55).
前記不飽和結合含有基を含まない他のジアミンは、任意の成分である成分Ｂとして光配向膜の用途に応じて適宜選択することができる。前記他のジアミンは、前記不飽和結合含有ジアミン以外のジアミンの一つでもよいし、二つ以上でもよい。例えば光配向膜が液晶配向膜として使用される場合では、前記他のジアミンには、液晶配向膜用のポリアミック酸の原料として公知のジアミンを用いることができる。より具体的には、ＩＰＳ用の液晶配向膜を製造する場合、液晶組成物のプレチルト角を小さくする目的で比較的分子量の小さいジアミンを用いればよい。またＴＮ、ＶＡ、又はＯＣＢ用の液晶配向膜として大きなプレチルト角が液晶に必要な場合、大きな分子量を有するジアミンを用いればよい。 The other diamine not containing the unsaturated bond-containing group can be appropriately selected as Component B, which is an optional component, according to the use of the photo-alignment film. The other diamine may be one of diamines other than the unsaturated bond-containing diamine, or may be two or more. For example, when the photo-alignment film is used as a liquid crystal alignment film, a known diamine can be used as the other diamine as a raw material for the polyamic acid for the liquid crystal alignment film. More specifically, when producing a liquid crystal alignment film for IPS, a diamine having a relatively low molecular weight may be used for the purpose of reducing the pretilt angle of the liquid crystal composition. When a liquid crystal alignment film for TN, VA, or OCB requires a large pretilt angle, a diamine having a large molecular weight may be used.
このような公知のジアミンとして特に制限はないが、好適なものとして以下の表１〜４の化合物を挙げることが出来る。 Although there is no restriction | limiting in particular as such a well-known diamine, The compound of the following Tables 1-4 can be mentioned as a suitable thing.
また好ましい前記他のジアミンには、下記一般式（３）で表されるジアミンが挙げられる。 Moreover, the diamine represented by following General formula (3) is mentioned to said other preferable diamine.
一般式（３）中、Ｒ1は下記一般式（５）〜（８）で表される基から選ばれる二価の有機基を表す。 In general formula (3), R 1 represents a divalent organic group selected from the groups represented by the following general formulas (5) to (8).
一般式（５）中、Ｒ4はＨ又は炭素数１〜１２のアルキルを表し、環Ａはそれぞれ独立して１，４−フェニレン又は１，４−シクロへキシレンを表し、Ｚ1及びＺ2はそれぞれ独立して単結合、ＣＨ2、ＣＨ2ＣＨ2又はＯを表し、ｒは０〜３、ｓはそれぞれ独立して０〜５、ｔ１は０〜３、ｔ２は０〜３の整数を表す。また、１，４−フェニレン又は１，４−シクロへキシレンの任意のＨは炭素数１〜４のアルキルで置換されていてもよい。一般式（５）を含む前記他のジアミンとしては、前記表３における１−３５〜１−３８、１−４０及び１−４１が挙げられる。 In the general formula (5), R 4 represents H or alkyl having 1 to 12 carbon atoms, each ring A independently represents 1,4-phenylene or 1,4-cyclohexylene, and Z 1 and Z 2 Each independently represents a single bond, CH 2 , CH 2 CH 2 or O, r is 0 to 3, s is each independently 0 to 5, t1 is 0 to 3, t2 is an integer of 0 to 3. To express. Further, any H in 1,4-phenylene or 1,4-cyclohexylene may be substituted with alkyl having 1 to 4 carbon atoms. Examples of the other diamine containing the general formula (5) include 1-35 to 1-38, 1-40 and 1-41 in Table 3.
一般式（６）中、Ｘ1及びＸ2は単結合、Ｏ、ＣＯＯ、ＯＣＯ、ＮＨ、ＣＯＮＨ又は炭素数１〜１２のアルキレンを表し、Ｇ1及びＧ2は単結合、又は芳香族環及び脂環式環から選ばれる１〜３個の環を含む二価の基を表し、Ｒ5はＨ、Ｆ、ＣＮ、ＯＨ又は炭素数１〜３０のアルキル、ペルフルオロアルキル若しくはアルコキシを表す。ベンゼン環に対する置換基の結合位置及び２個の遊離基の位置は任意の位置である。但し、Ｇ2が単結合でありＸ2が単結合でもなくアルキレンでもない場合は、Ｒ5はＨ又はアルキルであり、またＧ1及びＧ2が共に単結合である場合は、Ｘ1、Ｘ2及びＲ5の合計の炭素数が３以上である。一般式（６）を含む前記他のジアミンとしては、前記表１、３及び４における１−９〜１−１２、１−４３〜１−５２が挙げられる。 In General Formula (6), X 1 and X 2 represent a single bond, O, COO, OCO, NH, CONH, or alkylene having 1 to 12 carbon atoms, G 1 and G 2 represent a single bond, an aromatic ring, and A divalent group containing 1 to 3 rings selected from an alicyclic ring is represented, and R 5 represents H, F, CN, OH, or alkyl having 1 to 30 carbon atoms, perfluoroalkyl or alkoxy. The bonding position of the substituent to the benzene ring and the positions of the two free radicals are arbitrary positions. However, when G 2 is a single bond and X 2 is neither a single bond nor alkylene, R 5 is H or alkyl, and when G 1 and G 2 are both single bonds, X 1 , X The total carbon number of 2 and R 5 is 3 or more. Examples of the other diamine containing the general formula (6) include 1-9 to 1-12 and 1 to 43 to 1-52 in Tables 1, 3 and 4.
一般式（７）中、Ｘ3及びＸ4はそれぞれ独立して単結合、ＣＨ2、ＣＨ2ＣＨ2又はＯを表し、Ｒ6及びＲ7はＨ、炭素数１〜１２のアルキル、又は炭素数１〜１２のペルフルオロアルキルを表す。ｕ１、ｕ２、ｕ３、ｕ４、及びｕ５はそれぞれ独立して０〜３の整数を表す。また、１，４−フェニレンの任意のＨは炭素数１〜４のアルキルで置換されていてもよい。一般式（７）を含む前記他のジアミンとしては、前記表1及び２における１−１５〜１−１９、１−２６、１−２８、１−３３が挙げられる。 In general formula (7), X 3 and X 4 each independently represent a single bond, CH 2 , CH 2 CH 2 or O, R 6 and R 7 are H, alkyl having 1 to 12 carbons, or carbon The perfluoroalkyl of number 1-12 is represented. u1, u2, u3, u4, and u5 each independently represent an integer of 0 to 3. Moreover, arbitrary H of 1, 4-phenylene may be substituted by the C1-C4 alkyl. Examples of the other diamine containing the general formula (7) include 1-15 to 1-19, 1-26, 1-28, and 1-33 in Tables 1 and 2.
一般式（８）中、Ｘ5又はＸ6は単結合、Ｏ、又はＳを表し、ｍ１又はｍ２は０又は１の整数を表し、ｎは０〜１０の整数を表す。また、ベンゼン環に対する置換基及び遊離基の結合位置は任意の位置である。一般式（８）を含む前記他のジアミンとしては、前記表１〜３における１−１４、１−２４、又は１−４２が挙げられる。 In General Formula (8), X 5 or X 6 represents a single bond, O, or S, m1 or m2 represents 0 or an integer of 1, and n represents an integer of 0 to 10. Moreover, the bonding position of the substituent and free radical to the benzene ring is an arbitrary position. As said other diamine containing General formula (8), 1-14 in the said Tables 1-3, 1-24, or 1-42 is mentioned.
本発明の光配向膜を含む液晶表示素子を作製する際、基板の張り合わせや液晶組成物の注入口をふさぐため、熱又は光硬化性の高分子材料を使用することができる。これらのシール剤や封止剤を使用すると、不純物が溶出し、それらが光配向膜へ付着して液晶表示素子の特性を悪化させる場合がある。これを防ぐ目的で、下記一般式（２０）で表されるシロキサン系のジアミンを前記他のジアミンとして用いることが出来る。 When a liquid crystal display element including the photo-alignment film of the present invention is produced, a heat or photo-curable polymer material can be used in order to close the substrates and the liquid crystal composition inlet. If these sealants or sealants are used, impurities may elute and adhere to the photo-alignment film, which may deteriorate the characteristics of the liquid crystal display element. In order to prevent this, a siloxane-based diamine represented by the following general formula (20) can be used as the other diamine.
一般式（２０）において、Ｒ10及びＲ11は独立して炭素数１〜３のアルキル又はフェニルを表す。Ｒ10とＲ11は同じ基であっても異なる基であってもよい。また、Ｒ12は独立してメチレン、フェニレン又はアルキル置換されたフェニレンを表す。ｍは独立して１〜６の整数を表し、ｎは１〜１０の整数を表す。一般式（２０）で表される前記他のジアミンには、下記の化合物又はポリマーが挙げられる。 In the general formula (20), R 10 and R 11 represents an alkyl or phenyl having 1 to 3 carbon atoms independently. R 10 and R 11 may be the same group or different groups. R 12 independently represents methylene, phenylene or alkyl-substituted phenylene. m independently represents an integer of 1 to 6, and n represents an integer of 1 to 10. Examples of the other diamine represented by the general formula (20) include the following compounds or polymers.
式（２０−２）においてポリマーの分子量は８５０から３，０００である。 In the formula (20-2), the molecular weight of the polymer is 850 to 3,000.
これらのシロキサン系ジアミンの添加量は、上記効果を発現しその他の特性の悪化を防ぐ目的で、ポリアミック酸の原料成分全体に対し０．５モル％から３０モル％が好適であり、１モル％から１０モル％がさらに好適である。 The addition amount of these siloxane-based diamines is preferably 0.5 mol% to 30 mol% with respect to the total raw material components of the polyamic acid for the purpose of exhibiting the above effects and preventing other characteristics from being deteriorated. To 10 mol% is more preferred.
前記テトラカルボン酸二無水物には、前記ポリアミック酸の原料である酸のＡ成分として、前記不飽和結合含有基を有する不飽和結合含有テトラカルボン酸二無水物を用いることができる。前記ジアミンが前記不飽和結合含有基を有する場合は、前記テトラカルボン酸二無水物には、前記ポリアミック酸の原料である酸のＢ成分として、前記不飽和結合含有基を有さない他のテトラカルボン酸二無水物を用いることができる。 As the tetracarboxylic dianhydride, an unsaturated bond-containing tetracarboxylic dianhydride having the unsaturated bond-containing group can be used as the component A of the acid that is the raw material of the polyamic acid. In the case where the diamine has the unsaturated bond-containing group, the tetracarboxylic dianhydride includes, as a component B of the acid that is a raw material of the polyamic acid, other tetra groups having no unsaturated bond-containing group. Carboxylic dianhydrides can be used.
前記不飽和結合含有テトラカルボン酸二無水物には、一般式（２）で表されるテトラカルボン酸二無水物が挙げられる。前記不飽和結合含有テトラカルボン酸二無水物は、一般式（２）で表されるテトラカルボン酸二無水物の一つでもよいし、二つ以上でもよい。 Examples of the unsaturated bond-containing tetracarboxylic dianhydride include tetracarboxylic dianhydrides represented by the general formula (2). The unsaturated bond-containing tetracarboxylic dianhydride may be one of tetracarboxylic dianhydrides represented by the general formula (2), or may be two or more.
一般式（２）中、Ａ3及びＡ4は、それぞれ独立して炭素数６から２０の芳香環又は炭素数１から２０の脂肪族基を表す。Ａ3及びＡ4は、それぞれオキシ及びカルボニルを含んでいてもよい。このようなＡ3及びＡ4には、前述した不飽和結合含有ジアミンにおけるＡ1及びＡ2と同じ基を具体的に例示することができる。またＴは、前述した不飽和結合含有
ジアミンと同様に、１〜３個の炭素−炭素二重結合又は１〜４個の三重結合を含む不飽和結合含有基であり、下記（Ａ）から（Ｇ）の群から選ばれる不飽和結合含有基のいずれかであることが好ましい。
In General Formula (2), A 3 and A 4 each independently represent an aromatic ring having 6 to 20 carbon atoms or an aliphatic group having 1 to 20 carbon atoms. A 3 and A 4 may contain oxy and carbonyl, respectively. Specific examples of A 3 and A 4 include the same groups as A 1 and A 2 in the aforementioned unsaturated bond-containing diamine. T is an unsaturated bond-containing group containing 1 to 3 carbon-carbon double bonds or 1 to 4 triple bonds in the same manner as the unsaturated bond-containing diamine described above. It is preferably any one of unsaturated bond-containing groups selected from the group of G).
Ａ3及びＡ4には、公知の芳香族基、脂環式基、アルキルから選択できるが、製造が容易であり、光配向膜にした場合の特性が良く、さらに光配向膜に高いＶＨＲを付与する観点から、下記（ＶＩＩＩ）〜（Ｘ）が好ましい。Ａ3及びＡ4が（ＶＩＩＩ）〜（Ｘ）で表される芳香族基であるポリアミック酸は、光に対する反応性が若干低下するため、前記（Ｃ）から（Ｇ）のような二重結合又は三重結合が共役する基をＴとして選択することが効果的である。 A 3 and A 4 can be selected from known aromatic groups, alicyclic groups, and alkyls, but are easy to produce, have good characteristics when used as a photo-alignment film, and have a high VHR for the photo-alignment film. From the viewpoint of imparting, the following (VIII) to (X) are preferable. Since the polyamic acid in which A 3 and A 4 are aromatic groups represented by (VIII) to (X) is slightly reduced in reactivity to light, a double bond such as (C) to (G) above is used. Alternatively, it is effective to select T as a group to which a triple bond is conjugated.
Ａ3及びＡ4は、光配向膜に高いＶＨＲを付与する観点から、（ＶＩＩＩ）で表される基であることがさらに好ましい。 A 3 and A 4 are more preferably a group represented by (VIII) from the viewpoint of imparting high VHR to the photo-alignment film.
Ｔが前記（Ｄ）〜（Ｇ）で表される一般式（２）のテトラカルボン酸二無水物は、以下のスキーム２に従って合成することができる。 The tetracarboxylic dianhydride of the general formula (2) in which T is represented by the above (D) to (G) can be synthesized according to the following scheme 2.
式中Ｔ2は１，４−フェニレン、炭素−炭素二重結合、炭素−炭素三重結合、又は上記（Ｄ）を表し、Ｘは塩素、臭素、又はヨウ素を表し、Ｒ21はカルボン酸又はカルボン酸エステルの残基を２つ有する基を表す。 In the formula, T 2 represents 1,4-phenylene, a carbon-carbon double bond, a carbon-carbon triple bond, or the above (D), X represents chlorine, bromine, or iodine, and R 21 represents a carboxylic acid or a carboxylic acid. It represents a group having two acid ester residues.
すなわち上記の方法と同様にＬａｍｂｅｒｔ Ｂｒａｎｄｓｍａ著、Ｐｒｅｐａｒａｔｉｖｅ Ａｃｅｔｙｌｅｎｉｃ Ｃｈｅｍｉｓｔｒｙ、第２版、１９８８年、ＥＬＳＥＶＩＥＲ社又はヨーロピアン・ジャーナル・オーガニック・ケミストリー、３８７９（２００１）等の文献記載の方法に従い、前記スキーム２における（１−４）で表されるジハロゲン化物と前記スキーム２における（１−５）で表されるアセチレン化合物とをパラジウム触媒および必要によって加えられる助触媒存在下、反応させることによって前記スキーム２における（１−６）で表されるテトラカルボン酸又はテトラカルボン酸エステルを有する化合物が合成できる。前記スキーム２における（１−６）で表されるテトラカルボン酸又はテトラカルボン酸エステルは塩酸や水酸化ナトリウム水溶液等と加熱することによって加水分解され、テトラカルボン酸に誘導できる。このテトラカルボン酸は、無水酢酸等の脱水剤で処理することによって、目的とする前記一般式（２）に誘導する事が出来る。 That is, according to the method described in the literature such as Lambert Brandsma, Preparative Acetyl Chemistry, 2nd edition, 1988, ELSEVIER or European Journal Organic Chemistry, 3879 (2001), etc. 1-4) and the acetylene compound represented by (1-5) in the above-mentioned scheme 2 in the presence of a palladium catalyst and a cocatalyst that is added if necessary. A compound having a tetracarboxylic acid or a tetracarboxylic acid ester represented by -6) can be synthesized. The tetracarboxylic acid or tetracarboxylic acid ester represented by (1-6) in Scheme 2 is hydrolyzed by heating with hydrochloric acid, an aqueous sodium hydroxide solution or the like, and can be derived into tetracarboxylic acid. This tetracarboxylic acid can be derived into the desired general formula (2) by treating with a dehydrating agent such as acetic anhydride.
ここにおいて前記スキーム２における（１−４）で表される化合物として、市販の１，４−ジブロモベンゼン、１，４−ジヨードベンゼンや上記シス−１，２−ジクロロエチレン、トランス−１，２−ジクロロエチレン、ジブロモアセチレン、ジヨードアセチレン、又は１，４−ジヨードエチニルベンゼンが使用できる。また前記スキーム２における（１−５）で表される化合物は特開平０４−０１３６５０号公報に記載の４−エチニルフタル酸 ジエチルエステルや独国特許出願公開第３４３０１７４号明細書に記載の４−プロピニルオキシフタル酸等が使用できる。 Here, as the compound represented by (1-4) in the above-mentioned scheme 2, commercially available 1,4-dibromobenzene, 1,4-diiodobenzene, the above cis-1,2-dichloroethylene, trans-1,2- Dichloroethylene, dibromoacetylene, diiodoacetylene, or 1,4-diiodoethynylbenzene can be used. Further, the compound represented by (1-5) in the above-mentioned scheme 2 is 4-ethynylphthalic acid diethyl ester described in JP-A No. 04-013650 or 4-propynyl described in German Patent Application Publication No. 3430174. Oxyphthalic acid can be used.
一般式（２）で表される化合物および中間体はカラムクロマトグラフィー又は再結晶によって精製することができる。同定は1ＨＮＭＲ、13Ｃ ＮＭＲ、ＩＲ等の分光学的手
法、又はマススペクトルによって行うことができる。
The compound represented by the general formula (2) and the intermediate can be purified by column chromatography or recrystallization. Identification can be performed by spectroscopic techniques such as 1 HNMR, 13 C NMR, IR, or mass spectrum.
これらの化合物の合成は以下の実施例で詳述する。 The synthesis of these compounds is detailed in the examples below.
またＡ3−Ｔ−Ａ4で表される酸二無水物残基の、後述する本発明の光配向膜における酸二無水物の好適な例として以下の（５６）〜（７０）が挙げられる。 The acid dianhydride residue represented by A 3 -T-A 4, include the following (56) - (70) Suitable examples of the acid dianhydride in photo-alignment film of the present invention to be described later .
前記不飽和結合含有基を有さない他のテトラカルボン酸二無水物は、任意の成分であるＢ成分として光配向膜の用途に応じて適宜選択することができる。前記他のテトラカルボン酸二無水物は、前記不飽和結合含有テトラカルボン酸二無水物以外のテトラカルボン酸二無水物の一つでもよいし、二つ以上でもよい。例えば光配向膜が液晶配向膜として使用される場合では、前記他のテトラカルボン酸二無水物には、液晶配向膜用のポリアミック酸の原料として公知のテトラカルボン酸二無水物を用いることができる。より具体的には、光配向膜の光配向性を大きくしたい場合、液晶組成物との相互作用を大きくするために芳香族系のテトラカルボン酸二無水物を用いればよい。またポリアミック酸の着色が大きい場合、脂肪族系のテトラカルボン酸二無水物を用いればこれを改善できる。またＶＨＲが低い場合、脂環構造を有するテトラカルボン酸二無水物を用いればこれを改善できる。 The other tetracarboxylic dianhydride having no unsaturated bond-containing group can be appropriately selected depending on the use of the photo-alignment film as an optional component B component. The other tetracarboxylic dianhydride may be one of tetracarboxylic dianhydrides other than the unsaturated bond-containing tetracarboxylic dianhydride, or may be two or more. For example, when the photo-alignment film is used as a liquid crystal alignment film, a known tetracarboxylic dianhydride can be used as the polyamic acid raw material for the liquid crystal alignment film as the other tetracarboxylic dianhydride. . More specifically, when it is desired to increase the photoalignment property of the photoalignment film, an aromatic tetracarboxylic dianhydride may be used in order to increase the interaction with the liquid crystal composition. If the polyamic acid is highly colored, this can be improved by using an aliphatic tetracarboxylic dianhydride. Moreover, when VHR is low, this can be improved by using a tetracarboxylic dianhydride having an alicyclic structure.
このような公知のテトラカルボン酸二無水物としては、特に限定されないが、以下の表
５〜８の化合物を挙げることが出来る。
Although it does not specifically limit as such a well-known tetracarboxylic dianhydride, The compound of the following Tables 5-8 can be mentioned.
これらの化合物の中には異性体を含むものがあるが、これらの異性体混合物であってもかまわない。また、上記表の酸二無水物を組み合わせて使用してもよい。また本発明に使用するテトラカルボン酸二無水物は上記化合物以外でもよい。 Some of these compounds include isomers, but a mixture of these isomers may be used. Moreover, you may use it combining the acid dianhydride of the said table | surface. The tetracarboxylic dianhydride used in the present invention may be other than the above compounds.
前記他のテトラカルボン酸二無水物として好ましいテトラカルボン酸二無水物には、下記一般式（４）で表されるテトラカルボン酸二無水物が挙げられる。 Tetracarboxylic dianhydrides preferable as the other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides represented by the following general formula (4).
一般式（４）において、Ｒ2は下記一般式（９）〜（１７）で表される基から選ばれる四価の基を表す。 In the general formula (4), R 2 represents a tetravalent group selected from the groups represented by the following general formulas (9) to (17).
一般式（９）中、Ｇ3は単結合、炭素数１〜１２のアルキレン、１，４−フェニレン、又は１，４−シクロヘキシレンを表し、Ｘ6はそれぞれ独立して単結合又は−ＣＨ2−を表す。一般式（９）を含む前記他のテトラカルボン酸二無水物としては、前記表７及び８における２−２６、２−２７、２−２９及び２−３３が挙げられる。 In General Formula (9), G 3 represents a single bond, alkylene having 1 to 12 carbon atoms, 1,4-phenylene, or 1,4-cyclohexylene, and X 6 each independently represents a single bond or —CH 2. -Represents. Examples of the other tetracarboxylic dianhydrides containing the general formula (9) include 2-26, 2-27, 2-29, and 2-33 in Tables 7 and 8 above.
一般式（１０）中、Ｒ32、Ｒ33、Ｒ34、及びＲ35はＨ、メチル、エチル、又はフェニルを表す。一般式（１０）を含む前記他のテトラカルボン酸二無水物としては、前記表５及び８における２−２及び２−３８が挙げられる。 In general formula (10), R 32 , R 33 , R 34 , and R 35 represent H, methyl, ethyl, or phenyl. As said other tetracarboxylic dianhydride containing General formula (10), 2-2 and 2-38 in the said Table 5 and 8 are mentioned.
一般式（１１）中、Ａ6はシクロヘキサン環又はベンゼン環を表す。一般式（１１）を含む前記他のテトラカルボン酸二無水物としては、前記表５及び６における２−１及び２−１３が挙げられる。 In general formula (11), A 6 represents a cyclohexane ring or a benzene ring. As said other tetracarboxylic dianhydride containing General formula (11), 2-1 and 2-13 in the said Table 5 and 6 are mentioned.
一般式（１２）中、Ｇ4は単結合、−ＣＨ2−、−ＣＨ2ＣＨ2−、−Ｏ−、−ＣＯ−、−Ｓ−、−Ｃ（ＣＨ3）2−、又は−Ｃ（ＣＦ3）2−を表し、Ａ6はそれぞれ独立してシクロヘキサン環又はベンゼン環を表す。一般式（１２）を含む前記他のテトラカルボン酸二無水物としては、前記表５、６及び８における２−３〜２−７、２−１１、２−１４〜２−１６、２−１８、２−１９及び２−３２が挙げられる。 In the general formula (12), G 4 represents a single bond, -CH 2 -, - CH 2 CH 2 -, - O -, - CO -, - S -, - C (CH 3) 2 -, or -C ( CF 3 ) 2 — and A 6 each independently represents a cyclohexane ring or a benzene ring. Examples of the other tetracarboxylic dianhydrides containing the general formula (12) include 2-3 to 2-7, 2-11, 2-14 to 2-16, and 2-18 in Tables 5, 6 and 8. 2-19 and 2-32.
一般式（１３）中、Ｒ36はＨ、又はメチルを表す。一般式（１３）を含む前記他のテトラカルボン酸二無水物としては、前記表６における２−２０が挙げられる。 In the general formula (13), R 36 represents H or methyl. As said other tetracarboxylic dianhydride containing General formula (13), 2-20 in the said Table 6 is mentioned.
一般式（１４）中、Ｘ6はそれぞれ独立して単結合又は−ＣＨ2−を表し、ｖは１又は２を表す。一般式（１４）を含む前記他のテトラカルボン酸二無水物としては、前記表７における２−２２〜２−２４が挙げられる。 In general formula (14), X 6 each independently represents a single bond or —CH 2 —, and v represents 1 or 2. As said other tetracarboxylic dianhydride containing General formula (14), 2-22-2-24 in the said Table 7 are mentioned.
一般式（１５）中、Ｘ6は単結合又は−ＣＨ2−を表す。一般式（１５）を含む前記他のテトラカルボン酸二無水物としては、前記表６及び７における２−１２及び２−２１が挙げられる。 In general formula (15), X 6 represents a single bond or —CH 2 —. As said other tetracarboxylic dianhydride containing General formula (15), 2-12 and 2-21 in the said Table 6 and 7 are mentioned.
一般式（１６）中、Ｒ37はＨ、メチル、エチル、又はフェニルを表し、Ａ6はシクロヘキサン環又はベンゼン環を表す。一般式（１６）を含む前記他のテトラカルボン酸二無水物としては、前記表８における２−３５及び２−３６が挙げられる。 In the general formula (16), R 37 represents H, methyl, ethyl, or phenyl, A 6 represents a cyclohexane ring or a benzene ring. As said other tetracarboxylic dianhydride containing General formula (16), 2-35 and 2-36 in the said Table 8 are mentioned.
一般式（１７）中、ｗ１及びｗ２は０又は１を表す。ただしｗ1＝１でｗ２＝０である
ことはない。一般式（１７）を含む前記他のテトラカルボン酸二無水物としては、前記表７及び８における２−３０及び２−３１が挙げられる。
In general formula (17), w1 and w2 represent 0 or 1. However, w1 = 1 and w2 = 0 are not satisfied. As said other tetracarboxylic dianhydride containing General formula (17), 2-30 and 2-31 in the said Table 7 and 8 are mentioned.
前記ポリアミック酸の原料の総量に対する、前記不飽和結合含有テトラカルボン酸二無水物及び前記不飽和結合含有ジアミン（すなわちＡ成分）のモル比は、十分な液晶配向性を発現させる観点から、０．３〜１．０であることが好ましく、０．５〜１．０であることがより好ましい。他のテトラカルボン酸二無水物及びジアミン（すなわちＢ成分）の使用量は、Ａ1〜Ａ4の構造、及び、得られるポリアミック酸の着色や光配向性、得られる光配向膜を用いる液晶表示素子の電気特性やプレチルト角等の諸物性に応じて適宜に決めることができる。 The molar ratio of the unsaturated bond-containing tetracarboxylic dianhydride and the unsaturated bond-containing diamine (that is, the component A) to the total amount of the raw material of the polyamic acid is from the viewpoint of developing sufficient liquid crystal alignment. It is preferably 3 to 1.0, more preferably 0.5 to 1.0. The amount of other tetracarboxylic dianhydrides and diamines (that is, B component) used is the structure of A 1 to A 4 , the coloration and photo-alignment of the resulting polyamic acid, and the liquid crystal display using the resulting photo-alignment film It can be appropriately determined according to various physical properties such as electrical characteristics and pretilt angle of the element.
本発明の光配向膜は、前記ポリアミック酸の原料である前記テトラカルボン酸二無水物とジアミンとを反応させてなるポリアミック酸と、これを溶解させる溶媒とを含有する、ポリアミック酸の溶液（ワニス）の膜を形成し、このポリアミック酸の膜に光を照射してポリアミック酸を配向させ、光を照射した膜中のポリアミック酸をイミド化させることによって得ることができる。 The photo-alignment film of the present invention comprises a polyamic acid solution (varnish) containing a polyamic acid obtained by reacting the tetracarboxylic dianhydride as a raw material of the polyamic acid and a diamine, and a solvent for dissolving the polyamic acid. ), The polyamic acid film is irradiated with light to orient the polyamic acid, and the polyamic acid in the film irradiated with light is imidized.
前記ポリアミック酸は、前述したテトラカルボン酸二無水物とジアミンとの反応生成物であり、ポリイミドを主成分とする光配向膜を形成することができる成分である。このようなポリアミック酸としては、テトラカルボン酸二無水物とジアミンとが等量で反応したポリアミック酸そのものの他に、例えば１）ポリアミック酸を部分的に脱水閉環反応させた部分ポリイミド、又は２）前記ポリアミック酸の原料として用いるテトラカルボン酸二無水物の一部を有機ジカルボン酸に置き換えて反応させて得られたポリアミック酸−ポリアミド共重合体を含む。このようなポリマーを本発明の光配向膜に用いる場合、イミド化に伴う液晶配向能力の増大効果が低下することがあるので、ポリイミドやポリアミドの割合はなるべく小さいほうがよい。また前記ポリアミック酸の重合度は特に限定されないが、例えば重量平均分子量が、配向膜の経時劣化を防ぐために１０，０００以上が好ましく、また取り扱い易さの点から２００，０００以下が好ましい。 The polyamic acid is a reaction product of the aforementioned tetracarboxylic dianhydride and diamine, and is a component capable of forming a photo-alignment film containing polyimide as a main component. As such a polyamic acid, in addition to the polyamic acid itself obtained by reacting an equal amount of tetracarboxylic dianhydride and diamine, for example, 1) a partial polyimide obtained by partially dehydrating and ring-closing the polyamic acid, or 2) It includes a polyamic acid-polyamide copolymer obtained by reacting a part of the tetracarboxylic dianhydride used as a raw material for the polyamic acid with an organic dicarboxylic acid. When such a polymer is used for the photo-alignment film of the present invention, the effect of increasing the liquid crystal alignment ability accompanying imidation may be reduced, so the proportion of polyimide or polyamide should be as small as possible. The degree of polymerization of the polyamic acid is not particularly limited. For example, the weight average molecular weight is preferably 10,000 or more to prevent deterioration of the alignment film with time, and is preferably 200,000 or less from the viewpoint of ease of handling.
前記溶媒には、前記ポリアミック酸及び後述する他の成分を溶解することができる公知の溶媒を用いることができる。このような溶媒には、例えばＮ−メチル−２−ピロリドン（ＮＭＰ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメチルスルホキシド（ＤＭＳＯ）、エチレングリコールモノブチルエーテル（ＢＣ）、エチレングリコールモノエチルエーテル、γ−ブチロラクトン、の一種又はこれら二種類以上の混合物等が挙げられる。 As the solvent, a known solvent that can dissolve the polyamic acid and other components described later can be used. Examples of such solvents include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), ethylene glycol monobutyl ether (BC), and ethylene glycol monoethyl ether. , Γ-butyrolactone, or a mixture of two or more of these.
光配向膜に要求される特性をさらに効果的に発現させる目的で、前記ポリアミック酸は他のポリアミック酸と混合して使用してもよい。（このような複数のポリマーをブレンドすることを「ポリマーブレンド」と呼ぶ。）このとき十分な光配向性を付与するため、本発明におけるポリアミック酸の含有量は他の固形分に対し５０重量％以上が好適であり、８０重量％以上がさらに好適である。 For the purpose of more effectively expressing the properties required for the photo-alignment film, the polyamic acid may be used by mixing with other polyamic acid. (Blending such a plurality of polymers is called a “polymer blend”.) At this time, in order to impart sufficient photo-orientation, the content of polyamic acid in the present invention is 50% by weight relative to other solids. The above is preferable, and 80% by weight or more is more preferable.
上記ポリマーブレンドにおいて薄膜化したときの表面エネルギーの値が異なる複数のポリマーでこれを行った場合、表面張力の低い成分は自発的に膜表面に偏析しやすい。このようなポリマーブレンドを行うことによって、光配向膜の表面に良好な液晶配向性を示す層を、バルク（膜中）に良好な電気的特性を発現する層を形成し、これら両方の特性に優れた配向膜を得る方法が、特開平８−４３８３１号公報に開示されている。 When this is performed with a plurality of polymers having different surface energy values when thinned in the polymer blend, components with low surface tension tend to segregate spontaneously on the film surface. By performing such a polymer blend, a layer exhibiting good liquid crystal orientation is formed on the surface of the photo-alignment film, and a layer that expresses good electrical characteristics in the bulk (in the film) is formed. A method for obtaining an excellent alignment film is disclosed in JP-A-8-43831.
本発明においてもこのようなポリマーブレンドを行うことが出来る。このときプレチル
ト角を発現するポリアミック酸を表面張力の低い成分とし、より大きな表面張力を発現するポリマーとして、本発明におけるポリアミック酸を選択するのが、高い配向性や電圧保持率を光配向膜に付与する上で好ましい。このときプレチルト角を発現するポリアミック酸として本発明におけるポリアミック酸を使用してもよい。ブレンドされるポリマーの表面張力はポリアミック酸の構造（側鎖又は／及びフッ素やケイ素の有無）や分子量等によって調整することができる。
Such a polymer blend can also be performed in the present invention. At this time, the polyamic acid that exhibits a pretilt angle is used as a component having a low surface tension, and the polyamic acid in the present invention is selected as a polymer that exhibits a larger surface tension. It is preferable in giving. At this time, the polyamic acid in the present invention may be used as a polyamic acid that exhibits a pretilt angle. The surface tension of the polymer to be blended can be adjusted by the structure of polyamic acid (side chain or / and presence or absence of fluorine or silicon), molecular weight, and the like.
光配向膜としてのより良い特性を発現させるため、本発明におけるポリアミック酸は、他のさらに公知の全てのポリマーから選ばれる一種類以上と混合されてもよい。このとき全ポリマー中に占める本発明におけるポリアミック酸の割合は、本発明の効果を発現させるため、５０重量％以上が好ましく、８０重量％以上がより好ましい。 In order to develop better properties as a photo-alignment film, the polyamic acid in the present invention may be mixed with one or more selected from all other known polymers. At this time, the proportion of the polyamic acid in the present invention in the total polymer is preferably 50% by weight or more, and more preferably 80% by weight or more in order to express the effect of the present invention.
本発明におけるポリアミック酸及び他の固形分の上記の溶媒中の濃度は特に限定されるものではなく、下記の種々の塗布法に合わせ、最適な値を選べばよい。通常、塗布時のムラやピンホール等を抑えるため、ワニス重量に対し、好ましくは０．１〜３０重量％、より好ましくは１〜１０重量％である。 The concentration of the polyamic acid and other solid contents in the above-mentioned solvent in the present invention is not particularly limited, and an optimum value may be selected according to the following various coating methods. Usually, in order to suppress unevenness and pinholes at the time of application, the content is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the varnish weight.
本発明におけるワニスに有機シリコン化合物を添加することは、光配向膜のガラス基板への密着性や硬さを調節する観点から好ましい。本発明におけるワニスに添加する有機シリコン化合物は特に限定されるものではないが、例えば、アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン、ビニ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、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、ビニルトリエトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のシランカップリング剤、ジメチルポリシロキサン、ポリジメチルシロキサン、ポリジフェニルシロキサン等のシリコーンオイルが挙げられる。 Addition of an organic silicon compound to the varnish in the present invention is preferable from the viewpoint of adjusting the adhesion and hardness of the photo-alignment film to the glass substrate. The organosilicon compound to be added to the varnish in the present invention is not particularly limited. For example, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, N- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycyl Silane coupling agents such as sidoxypropylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and silicone oils such as dimethylpolysiloxane, polydimethylsiloxane, and polydiphenylsiloxane. That.
該有機シリコン化合物のワニスへの添加割合は、上記の光配向膜に要求される特性を損なうことなく、光配向膜を用いた液晶表示素子における表示不良を改善することが出来る範囲であれば特に制限はない。しかしながら、これらを多く添加すると、光配向膜としたとき液晶の配向不良が生ずることがある。したがって、これらの濃度はワニスに含有されるポリマーの重量に対し、０．０１〜５重量％の範囲であることが好ましく、特に好ましくは０．１〜３重量％の範囲である。 The addition ratio of the organosilicon compound to the varnish is particularly within the range that can improve the display defect in the liquid crystal display element using the photo-alignment film without impairing the characteristics required for the photo-alignment film. There is no limit. However, if a large amount of these are added, liquid crystal alignment defects may occur when the photo-alignment film is formed. Therefore, these concentrations are preferably in the range of 0.01 to 5% by weight, particularly preferably in the range of 0.1 to 3% by weight, based on the weight of the polymer contained in the varnish.
ポリアミック酸のカルボン酸残基と反応してポリアミック酸同士を繋ぐ、いわゆる架橋剤を本発明の液晶配向剤に添加することも、特性の経時劣化や環境による劣化を防ぐために重要である。このような架橋剤としては、特許第３０４９６９９号公報、特開２００５−２７５３６０号公報、特開平１０−２１２４８４号公報等に記載されているような多官能エポキシ、イソシアネート材料等が挙げられる。また架橋剤自身が反応して網目構造のポリマーとなり、ポリアミック酸もしくはポリイミドを用いて作製した液晶配向剤を用いる液晶配向膜の強度を向上するような材料も上記と同様な目的に使用することが出来る。このような架橋剤としては、特開平１０−３１０６０８号公報、特開２００４−３４１０３０号公報等に記載されているような多官能ビニルエーテル、マレイミド、またはビスアリルナジイミド誘導体等が挙げられる。なお本発明に用いられる架橋剤はこれら以外でもよい。 It is also important to add a so-called cross-linking agent that reacts with the carboxylic acid residue of the polyamic acid to link the polyamic acids to the liquid crystal aligning agent of the present invention in order to prevent deterioration of characteristics over time and environmental degradation. Examples of such a crosslinking agent include polyfunctional epoxies and isocyanate materials as described in Japanese Patent No. 3049699, Japanese Patent Application Laid-Open No. 2005-275360, Japanese Patent Application Laid-Open No. 10-212484, and the like. In addition, a material that improves the strength of a liquid crystal alignment film using a liquid crystal aligning agent prepared by using a polyamic acid or polyimide may be used for the same purpose as described above. I can do it. Examples of such a crosslinking agent include polyfunctional vinyl ethers, maleimides, and bisallyl nadiimide derivatives as described in JP-A-10-310608, JP-A-2004-341030, and the like. The crosslinking agent used in the present invention may be other than these.
本発明の液晶配向剤の作製に用いられるポリマー（ポリアミック酸もしくはポリイミド）に対するこれらの架橋剤の割合は、本発明の効果を発現させるため、５〜２００重量％の範囲が好ましく、１０〜１００重量％の範囲がより好ましい。 The ratio of these crosslinking agents with respect to the polymer (polyamic acid or polyimide) used for the preparation of the liquid crystal aligning agent of the present invention is preferably in the range of 5 to 200% by weight, and 10 to 100% by weight in order to express the effects of the present invention. % Range is more preferred.
液晶組成物に対し十分な配向性を発現する観点から、本発明の光配向膜は、以下の手順で製造されることが好ましい。
（１）前記ワニスを刷毛塗り法、浸漬法、スピンナー法、スプレー法、印刷法等により基板上に塗布する。
（２）基板上に形成されたワニスの膜から、５０〜１２０℃、好ましくは８０〜１００℃で溶媒を蒸発させる。
（３）直線偏光を前記膜に照射して前記膜中のポリアミック酸を配向させる。
（４）ポリアミック酸を配向させた前記膜を１５０〜４００℃、好ましくは１８０〜２８０℃で加熱しイミド化する。
From the viewpoint of expressing sufficient alignment with the liquid crystal composition, the photo-alignment film of the present invention is preferably produced by the following procedure.
(1) The varnish is applied onto a substrate by a brush coating method, a dipping method, a spinner method, a spray method, a printing method, or the like.
(2) The solvent is evaporated from the varnish film formed on the substrate at 50 to 120 ° C., preferably 80 to 100 ° C.
(3) Irradiate the linearly polarized light on the film to orient the polyamic acid in the film.
(4) The film in which the polyamic acid is oriented is heated at 150 to 400 ° C., preferably 180 to 280 ° C., and imidized.
なお、本発明の光配向膜を液晶配向膜として用いた液晶表示素子において所定のプレチルト角を発現させたい場合、光を照射する際に基板に対し任意の角度から直線偏光を照射する方法や、基板に対し垂直方向からの直線偏光照射と任意の角度からの非偏光照射とを組み合わせる方法で行うことができる。 In the liquid crystal display element using the photo-alignment film of the present invention as a liquid crystal alignment film, when a predetermined pretilt angle is to be expressed, a method of irradiating the substrate with linearly polarized light from an arbitrary angle when irradiating light, It can be performed by combining linearly polarized light irradiation from a direction perpendicular to the substrate and non-polarized light irradiation from an arbitrary angle.
さらに、ワニスの塗布前に基板表面上をシランカップリング剤で処理し、その上に成膜すれば、膜と基板との接着性が改善される。 Furthermore, if the surface of the substrate is treated with a silane coupling agent before coating the varnish and a film is formed thereon, the adhesion between the film and the substrate is improved.
本発明の光配向膜の製造において、前記ポリアミック酸の配向には直線偏光が用いられる。ポリアミック酸主鎖は、直線偏光の照射によって、直線偏光の偏光方向に対して垂直な方向又は平行な方向に配向する。前記直線偏光は、前記膜中のポリアミック酸を配向させることができる光であれば特に限定されない。前記ポリアミック酸の光配向処理における直線偏光の照射量は１Ｊ／ｃｍ2以上であることが好ましい。また直線偏光の波長は３００〜４００ｎｍであることが好ましい。直線偏光の膜表面に対する照射角度は特に限定されないが、液晶に対する強い配向規制力を発現させたい場合、膜表面に対してなるべく垂直であることが配向処理の時間を短縮する観点から好ましい。 In the production of the photo-alignment film of the present invention, linearly polarized light is used for the alignment of the polyamic acid. The polyamic acid main chain is oriented in a direction perpendicular to or parallel to the polarization direction of the linearly polarized light by irradiation with the linearly polarized light. The linearly polarized light is not particularly limited as long as it is light capable of orienting the polyamic acid in the film. The irradiation amount of linearly polarized light in the photo-alignment treatment of the polyamic acid is preferably 1 J / cm 2 or more. The wavelength of linearly polarized light is preferably 300 to 400 nm. Although the irradiation angle with respect to the film surface of linearly polarized light is not particularly limited, it is preferable from the viewpoint of shortening the time for the alignment treatment that it is as perpendicular as possible to the film surface when it is desired to develop a strong alignment regulating force for the liquid crystal.
また本発明の光配向膜の製造において、プレチルト角を発現させたい場合に前記膜に照射される光は、偏光であっても非偏光であってもよい。プレチルト角を発現させたい場合に前記膜に照射される光の照射量は１Ｊ／ｃｍ2以上であることが好ましく、その波長は３００〜４００ｎｍであることが好ましい。プレチルト角を発現させたい場合に前記膜に照射される光の前記膜表面に対する照射角度は特に限定されないが、３０〜６０°であることが配向処理の時間を短縮する観点から好ましい。 In the production of the photo-alignment film of the present invention, the light irradiated to the film when it is desired to express the pretilt angle may be polarized light or non-polarized light. When it is desired to develop a pretilt angle, the amount of light applied to the film is preferably 1 J / cm 2 or more, and the wavelength is preferably 300 to 400 nm. When it is desired to develop a pretilt angle, the irradiation angle of the light applied to the film with respect to the film surface is not particularly limited, but is preferably 30 to 60 ° from the viewpoint of shortening the alignment treatment time.
本発明の光配向膜は、液晶配向膜として用いられる場合に液晶に対する配向規制力を十分に発現させ、配向不良の惹起を抑制する観点から、下記式αで求められる光配向膜におけるポリイミドの主鎖の配向指数Δが０．５以上であることが好ましい。配向指数Δは大きければ大きいほど良いが、光配向膜の製造時の生産性を上げ、また光配向膜の光分解による性能低下を抑制する観点から、３０以下であることが好ましく、０．９〜１０であることがより好ましい。
Δ＝（｜Ａ‖−Ａ⊥｜）／｛（Ａ‖＋Ａ⊥）×ｄ｝ （α）
The photo-alignment film of the present invention, when used as a liquid crystal alignment film, exhibits a sufficient alignment regulating force for liquid crystals and suppresses the occurrence of alignment failure. The chain orientation index Δ is preferably 0.5 or more. The larger the orientation index Δ, the better, but it is preferably 30 or less from the viewpoint of increasing the productivity during the production of the photo-alignment film and suppressing the performance degradation due to the photodecomposition of the photo-alignment film. 10 to 10 is more preferable.
Δ = (| A‖−A⊥ |) / {(A‖ + A⊥) × d} (α)
式（α）中、Ａ‖は、直線偏光の赤外光を光配向膜の表面に対して垂直に、かつ赤外光の偏光方向がポリイミドの主鎖の平均配向方向に平行になるように照射したときの波数１，３６０ｃｍ-1付近のイミド環のＣ−Ｎ−Ｃ伸縮振動による吸収バンドのピーク値又は積分吸光度を表し、Ａ⊥は、直線偏光の赤外光を光配向膜の表面に対して垂直に、かつ赤外光の偏光方向がポリイミドの主鎖の平均配向方向に垂直になるように照射したときの波数１，３６０ｃｍ-1付近のイミド環のＣ−Ｎ−Ｃ伸縮振動による吸収バンドのピーク値又は積分吸光度を表す。ｄは光配向膜の膜厚（ｎｍ）である。 In Formula (α), A‖ is such that linearly polarized infrared light is perpendicular to the surface of the photo-alignment film, and the polarization direction of infrared light is parallel to the average orientation direction of the polyimide main chain. Represents the peak value or integrated absorbance of the absorption band due to C—N—C stretching vibration of the imide ring near the wave number of 1,360 cm −1 when irradiated, and A⊥ represents the linearly polarized infrared light on the surface of the photo-alignment film. C—N—C stretching vibration of imide ring near wave number 1,360 cm −1 when irradiated so that the polarization direction of infrared light is perpendicular to the average orientation direction of the main chain of polyimide. Represents the peak value of the absorption band or the integrated absorbance. d is the film thickness (nm) of the photo-alignment film.
Ａ‖及びＡ⊥は、赤外線分光光度計（好ましくはＦＴ−ＩＲ）の光源と、基板とその表面に形成された光配向膜とを有する試料を保持する試料ホルダーとの間に偏光子を配置し、ポリイミドの主鎖の配向方向が偏光子の偏光方向と平行になるようにして試料ホルダーに前記試料を固定し、赤外吸光度を測定し、試料を試料ホルダーに固定した状態で偏光子を９０度回転させて偏光子を通過した赤外光の偏光方向がポリイミドの主鎖の配向方向と垂直になるようにして赤外吸光度を測定することによって求めることができる。なお、この方法では、シリコンやフッ化カルシウム（ホタル石：ＣａＦ2）等赤外光が透過する基板上に作製された試料が用いられる。 A‖ and A⊥ arrange a polarizer between a light source of an infrared spectrophotometer (preferably FT-IR) and a sample holder holding a sample having a substrate and a photo-alignment film formed on the surface thereof. Then, fix the sample to the sample holder so that the orientation direction of the main chain of the polyimide is parallel to the polarization direction of the polarizer, measure the infrared absorbance, and fix the polarizer with the sample fixed to the sample holder. It can be determined by measuring the infrared absorbance so that the polarization direction of the infrared light rotated 90 degrees and passed through the polarizer is perpendicular to the orientation direction of the main chain of the polyimide. In this method, a sample made on a substrate that transmits infrared light, such as silicon or calcium fluoride (fluorite: CaF 2 ), is used.
ｄは段差計又はエリプソメータ等の公知の膜厚測定装置によって測定することができる。またｄは、前記ワニスの粘度や基板へのワニスの塗布条件によって調整することができる。前記ワニスの粘度は、ポリアミック酸等の固形分の濃度や、ワニスの養生（攪拌時間）によって調整することができる。 d can be measured by a known film thickness measuring device such as a step meter or an ellipsometer. Moreover, d can be adjusted with the viscosity of the said varnish and the application | coating conditions of the varnish to a board | substrate. The viscosity of the varnish can be adjusted by the concentration of solids such as polyamic acid and the curing (stirring time) of the varnish.
また光配向膜におけるポリイミドの主鎖の平均配向方向は、光配向膜の表面に対して垂直な方向から光配向膜を見たときにポリイミドの主鎖が平均して配向している方向を言い、直線偏光の赤外光を光配向膜の表面に対して垂直に照射しながら、光配向膜の表面に対する垂線を回転軸として光配向膜を回転させたときのＡ‖−Ａ⊥の正負及びその値によって判断することができる。つまりＡ‖−Ａ⊥が正でありかつ最大値であるとき、ポリイミド主鎖の平均配向方向は直線偏光の偏光方向と平行であり、負でありかつ最小値であるとき、ポリイミドの主鎖の平均配向方向は直線偏光の偏光方向に対して垂直である。 The average orientation direction of the main chain of polyimide in the photo-alignment film refers to the direction in which the main chain of polyimide is oriented on average when the photo-alignment film is viewed from a direction perpendicular to the surface of the photo-alignment film. When the photo-alignment film is rotated about the perpendicular to the surface of the photo-alignment film while irradiating linearly polarized infrared light perpendicularly to the surface of the photo-alignment film, It can be judged by the value. That is, when A‖-A⊥ is positive and maximum, the average orientation direction of the polyimide main chain is parallel to the polarization direction of linearly polarized light, and when negative and minimum, the polyimide main chain The average orientation direction is perpendicular to the polarization direction of linearly polarized light.
本発明の光配向膜は、液晶ディスプレイ用の液晶組成物の配向用途以外に、光学補償材やその他すべての液晶材料の配向制御に用いることが出来る。 The photo-alignment film of the present invention can be used for alignment control of an optical compensation material and all other liquid crystal materials in addition to the alignment use of a liquid crystal composition for a liquid crystal display.
本発明は、対向配置されている一対の基板と、前記一対の基板それぞれの対向している面の一方又は両方に形成されている電極と、前記一対の基板それぞれの対向している面に形成された液晶配向膜と、前記一対の基板間に形成された液晶層とを有する液晶表示素子において、前記液晶配向膜が本発明の光配向膜である液晶表示素子を提供する。 The present invention is formed on a pair of substrates disposed opposite to each other, an electrode formed on one or both of the surfaces facing each of the pair of substrates, and a surface facing each of the pair of substrates. A liquid crystal display element having a liquid crystal alignment film formed and a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the photo-alignment film of the present invention.
前記基板は、その用途に応じて適当な基板が用いられる。前記基板は、表示の観点によれば、ガラス等の透明の基板が好ましく、光配向膜におけるポリイミド主鎖の配向指数Δを確認する観点によれば、シリコンやフッ化カルシウム等の赤外光を透過する基板が好ましい。 As the substrate, an appropriate substrate is used according to the application. From the viewpoint of display, the substrate is preferably a transparent substrate such as glass. From the viewpoint of confirming the orientation index Δ of the polyimide main chain in the photo-alignment film, infrared light such as silicon or calcium fluoride is used. A transparent substrate is preferred.
前記電極は、基板の一面に形成される電極であれば特に限定されない。このような電極には、例えばＩＴＯや金属の蒸着膜等が挙げられる。また電極は、基板の一方の面の全面に形成されていてもよいし、例えばパターン化されている所望の形状に形成されていてもよい。電極の前記所望の形状には、例えば櫛型又はジグザグ構造等が挙げられる。電極は、一対の基板のうちの一方の基板に形成されていてもよいし、両方の基板に形成されていてもよい。電極の形成の形態は液晶表示素子の種類に応じて異なり、例えばＩＰＳ型液晶表示素子の場合は前記一対の基板の一方に電極が配置され、その他の液晶表示素子の場合は前記一対の基板の双方に電極が配置される。前記基板又は電極の上に前記液晶配向膜が形成される。 The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such electrodes include ITO and metal vapor deposition films. Further, the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape that is patterned, for example. Examples of the desired shape of the electrode include a comb shape or a zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both substrates. The form of electrode formation varies depending on the type of liquid crystal display element. For example, in the case of an IPS liquid crystal display element, an electrode is disposed on one of the pair of substrates, and in the case of other liquid crystal display elements, the electrodes of the pair of substrates are arranged. Electrodes are arranged on both sides. The liquid crystal alignment film is formed on the substrate or electrode.
前記液晶層は、液晶配向膜が形成された面が対向している前記一対の基板によって液晶組成物が挟持される形で形成される。液晶層の形成では、微粒子や樹脂シート等の、前記一対の基板の間に介在して適当な間隔を形成するスペーサを必要に応じて用いることができる。 The liquid crystal layer is formed in such a manner that the liquid crystal composition is sandwiched between the pair of substrates facing each other on which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a spacer such as fine particles or a resin sheet that is interposed between the pair of substrates to form an appropriate interval can be used as necessary.
前記液晶組成物には、特に限定されず公知の液晶組成物を用いることができる。 The liquid crystal composition is not particularly limited, and a known liquid crystal composition can be used.
本発明の光配向膜は、液晶配向膜として液晶表示素子を形成したときに、公知の全ての液晶組成物に対してその特性を改善できるが、前述した方法によって製造された本発明の光配向膜は、特に、ラビング処理の行いにくい大画面ディスプレイの配向欠陥改善に効果が大きい。このような大画面ディスプレイはＴＦＴにより駆動制御されている。またこのようなＴＦＴ型液晶表示素子に使用される液晶組成物は、特許第３０８６２２８号公報、特許２６３５４３５号公報、特表平５−５０１７３５号公報、及び特開平９−２５５９５６号公報に記載されている。したがって本発明の光配向膜は、これらに記載された液晶組成物と組み合わせて用いるのが好ましい。 When the liquid crystal display element is formed as a liquid crystal alignment film, the photo alignment film of the present invention can improve the characteristics of all known liquid crystal compositions, but the photo alignment film of the present invention manufactured by the method described above. The film is particularly effective for improving alignment defects of large screen displays that are difficult to rub. Such a large screen display is driven and controlled by TFTs. Liquid crystal compositions used in such TFT type liquid crystal display elements are described in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Publication No. 5-501735, and Japanese Patent Application Laid-Open No. 9-255556. Yes. Therefore, the photo-alignment film of the present invention is preferably used in combination with the liquid crystal composition described therein.
ＶＡ方式の液晶表示素子においては、視野角を改善するため、電場をかけたときに倒れる液晶組成物の方向を放射状に制御することが行われている。その方法の１つとして、光配向膜の上にマスクを置き、複数の配向処理を行うことが検討されている。本発明の光配向膜はこのような配向分割を行う上でも好適である。 In a VA liquid crystal display element, in order to improve a viewing angle, the direction of a liquid crystal composition that falls when an electric field is applied is controlled radially. As one of the methods, it has been studied to place a mask on the photo-alignment film and perform a plurality of alignment treatments. The photo-alignment film of the present invention is also suitable for performing such alignment division.
本発明の液晶表示素子におけるプレチルト角は、例えば中央精機製液晶特性評価装置ＯＭＳ−ＣＡ３型を用いて、Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ， Ｖｏｌ．４８， Ｎｏ．５， ｐ．１７８３−１７９２ （１９７７）に記載されているクリスタルローテーション法によって測定することができる。 The pretilt angle in the liquid crystal display element of the present invention can be determined using, for example, a liquid crystal characteristic evaluation apparatus OMS-CA3 manufactured by Chuo Seiki, Journal of Applied Physics, Vol. 48, no. 5, p. 1783-1792 (1977), and can be measured by the crystal rotation method.
本発明の液晶表示素子は、液晶表示素子の信頼性に係る電気特性において優れている。このような電気特性としては、電圧保持率及びイオン密度が挙げられる。 The liquid crystal display element of the present invention is excellent in electrical characteristics relating to the reliability of the liquid crystal display element. Such electrical characteristics include voltage holding ratio and ion density.
電圧保持率（ＶＨＲ）は、フレーム周期間に液晶表示素子に印加された電圧が液晶表示素子に保持される割合であり、液晶表示素子の表示特性を示す。本発明の液晶表示素子は、４．５Ｖ及び周波数３０Ｈｚの矩形波を用い、６０℃の温度の条件で測定される電圧保持率が９０．０％以上であり、４．５Ｖおよび周波数０．３Ｈｚの矩形波を用い、６０℃の温度の条件で測定される電圧保持率が８５．０％以上であることが、表示不良を防ぐ観点から好ましい。 The voltage holding ratio (VHR) is a ratio at which the voltage applied to the liquid crystal display element during the frame period is held in the liquid crystal display element, and indicates display characteristics of the liquid crystal display element. The liquid crystal display element of the present invention uses a rectangular wave of 4.5 V and a frequency of 30 Hz, has a voltage holding ratio measured at a temperature of 60 ° C. of 90.0% or more, 4.5 V and a frequency of 0.3 Hz. From the viewpoint of preventing display defects, it is preferable that the voltage holding ratio measured at 60 ° C. is 85.0% or more.
イオン密度は、液晶表示素子内の不純物イオンの挙動を示す指標であることが知られている。本発明の液晶表示素子は、イオン密度が５００ｐＣ以下であることが、液晶表示素子の焼き付きを防ぐ観点から好ましい。 It is known that the ion density is an index indicating the behavior of impurity ions in the liquid crystal display element. The liquid crystal display element of the present invention preferably has an ion density of 500 pC or less from the viewpoint of preventing image sticking of the liquid crystal display element.
以下実施例により、本発明の光配向膜における実際の製法及び効果を具体的に示す。実施例中、ＮＭＲはジメチルスルホキシド中で測定した。分子量の測定はＧＰＣを用い、ポリスチレンを標準溶液とし、溶出液はＤＭＦを用いた。粘度は、回転粘度計（東機産業株式会社製、ＴＶ−２０）を用い測定した。光照射は井内盛栄堂製２５０Ｗ高圧水銀灯を用い、波長３１０〜３８０ｎｍ付近の紫外線を照射した。照射は室温、空気中で行った。なお本発明はこれらの実施例に限定されるものではない。 The actual production method and effects of the photo-alignment film of the present invention will be specifically described below with reference to examples. In the examples, NMR was measured in dimethyl sulfoxide. For the measurement of molecular weight, GPC was used, polystyrene was used as a standard solution, and DMF was used as an eluent. The viscosity was measured using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., TV-20). For the light irradiation, a 250 W high-pressure mercury lamp manufactured by Seiei Inai was used, and ultraviolet rays having a wavelength of about 310 to 380 nm were irradiated. Irradiation was performed in air at room temperature. The present invention is not limited to these examples.
液晶表示素子の評価法
以下に実施例で用いた液晶表示素子の評価法を記載する。
１．配向性
偏光顕微鏡観察による目視により行った。
２．プレチルト角
クリスタルローテーション法により行った。
３．電圧保持率
「水嶋他、第１４回液晶討論会予稿集 ｐ７８」に記載の方法により、二通りの測定方法で行った。第一の測定条件は、ゲート幅６９μｓ、周波数３０Ｈｚ、波高±４．５Ｖであり、温度６０℃で行った。第二の測定条件は、ゲート幅６９μｓ、周波数０．３Ｈｚ、波高±４．５Ｖであり、温度６０℃で行った。
４．液晶中のイオン量測定（イオン密度）
応用物理、第６５巻、第１０号、１０６５（１９９６）に記載の方法に従い、東陽テクニカ社製、液晶物性測定システム６２５４型を用いて測定した。周波数０．０１Ｈｚの三角波を用い、±１０Ｖの電圧範囲、温度６０℃で測定した。
５．偏光ＩＲ
ＦＴ−ＩＲ装置（分光器：Ｍａｔｔｓｏｎ Ｇａｌａｘｙ ３０２０、検出器：ｍｅｒｃｕｒｙ ｃａｄｍｉｕｍ ｔｅｌｌｕｒｉｄｅ）を用い、測定温度３２℃、積算４００回の条件で測定した。
６．膜厚測定
エリプソメータ（溝尻光学工業所 ＤＶＡ−ＦＬ３Ｇ）を用い、６３２．８ｎｍのレーザー光を照射して測定した。
Evaluation Method of Liquid Crystal Display Element The evaluation method of the liquid crystal display element used in the examples is described below.
1. Orientation It was performed by visual observation with a polarizing microscope.
2. Pretilt angle It was performed by the crystal rotation method.
3. Voltage holding ratio The measurement was carried out by two methods according to the method described in “Mizushima et al., Proceedings of the 14th Liquid Crystal Symposium p78”. The first measurement conditions were a gate width of 69 μs, a frequency of 30 Hz, a wave height of ± 4.5 V, and a temperature of 60 ° C. The second measurement conditions were a gate width of 69 μs, a frequency of 0.3 Hz, a wave height of ± 4.5 V, and a temperature of 60 ° C.
4). Measurement of ion content in liquid crystal (ion density)
According to the method described in Applied Physics, Vol. 65, No. 10, 1065 (1996), measurement was performed using a liquid crystal property measuring system 6254 type manufactured by Toyo Technica. Using a triangular wave with a frequency of 0.01 Hz, measurement was performed at a voltage range of ± 10 V and a temperature of 60 ° C.
5). Polarization IR
Using an FT-IR apparatus (spectrometer: Mattson Galaxy 3020, detector: mercury cadmium telluride), measurement was performed under conditions of a measurement temperature of 32 ° C. and a total of 400 times.
6). Measurement of film thickness Using an ellipsometer (Dove-Optical Industries DVA-FL3G), the film thickness was measured by irradiating 632.8 nm laser light.
実施例１
下記組成からなるワニスＡの調製
Example 1
Preparation of varnish A having the following composition
４，４’−ジアミノトラン（１．２５３４ｇ、６．０１８ｍｍｏｌ）をＮＭＰ（Ｎ−メチル−２−ピロリドン、２２．５ｇ）に溶解し、ＰＭＤＡ（０．５９０１ｇ、３．００９ｍｍｏｌ）及びＣＢＴＡ（０．６５６４ｇ、３．００９ｍｍｏｌ）を室温以下に保ちながら加えた。２時間攪拌後、ＢＣ（エチレングリコールモノブチルエーテル、２２．５ｇ）を加えた。このものの粘度は３５０ｍＰａ・ｓであった。この溶液を６０℃で約４時間攪拌したところ、粘度３３ｍＰａ・ｓのワニスを得た（重量平均分子量；４５，０００）。 4,4′-Diaminotolane (1.2534 g, 6.018 mmol) was dissolved in NMP (N-methyl-2-pyrrolidone, 22.5 g), PMDA (0.5901 g, 3.009 mmol) and CBTA (0. 6564 g, 3.009 mmol) was added while keeping the temperature below room temperature. After stirring for 2 hours, BC (ethylene glycol monobutyl ether, 22.5 g) was added. The viscosity of this product was 350 mPa · s. When this solution was stirred at 60 ° C. for about 4 hours, a varnish with a viscosity of 33 mPa · s was obtained (weight average molecular weight; 45,000).
実施例２
下記組成からなるワニスＢの調製
Example 2
Preparation of varnish B having the following composition
４，４’−ジアミノジフェニル−１，４−ブタジイン（１．３２１６ｇ、５．６９０ｍｍｏｌ）をＮＭＰ（２２．５ｇ）に溶解し、ＰＭＤＡ（０．６２０５ｇ、２．８４５ｍｍｏｌ）及びＣＢＴＡ（０．５５７９ｇ、２．８４５ｍｍｏｌ）を室温以下に保ちながら加えた。２時間攪拌後、ＢＣ（２２．５ｇ）を加えた。このものの粘度は１７０ｍＰａ・ｓであった。この溶液を６０℃で約２時間攪拌したところ、粘度２８ｍＰａ・ｓのワニスを得た（重量平均分子量；３７，０００）。 4,4′-Diaminodiphenyl-1,4-butadiyne (1.3216 g, 5.690 mmol) was dissolved in NMP (22.5 g), PMDA (0.6205 g, 2.845 mmol) and CBTA (0.5579 g, 2.845 mmol) was added while keeping the temperature below room temperature. After stirring for 2 hours, BC (22.5 g) was added. The viscosity of this product was 170 mPa · s. When this solution was stirred at 60 ° C. for about 2 hours, a varnish having a viscosity of 28 mPa · s was obtained (weight average molecular weight; 37,000).
実施例３
下記組成からなるワニスＣの調製
Example 3
Preparation of varnish C having the following composition
４，４’−ジアミノスチルベン（１．２５９０ｇ、５．５９２ｍｍｏｌ）をＮＭＰ（２２．５ｇ）に溶解し、ＰＭＤＡ（０．６５３５ｇ、２.９９６ｍｍｏｌ）及びＣＢＴＡ（０．５８７５ｇ、２．９９６ｍｍｏｌ）を室温以下に保ちながら加えた。２時間攪拌後、ＢＣ（２２．５ｇ）を加えた。このものの粘度は１４０ｍＰａ・ｓであった。この溶液を６０℃で約２時間攪拌したところ、粘度３２ｍＰａ・ｓのワニスを得た（重量平均分子量；４６，０００）。 4,4′-Diaminostilbene (1.2590 g, 5.592 mmol) was dissolved in NMP (22.5 g) and PMDA (0.6535 g, 2.996 mmol) and CBTA (0.5875 g, 2.996 mmol) were added at room temperature. Added while keeping below. After stirring for 2 hours, BC (22.5 g) was added. The viscosity of this product was 140 mPa · s. When this solution was stirred at 60 ° C. for about 2 hours, a varnish having a viscosity of 32 mPa · s was obtained (weight average molecular weight; 46,000).
実施例４
化合物（１−９）の合成及びこれを用いた下記ワニスＤの合成
Example 4
Synthesis of compound (1-9) and synthesis of varnish D below using the same
（ワニスの合成）
ＵＳ６５１４９９５又はＪ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１２３，９６７５（２００１）に従って合成した化合物（１−９）（０．９８２９ｇ、７．３２５ｍｍｏｌ）をＮＭＰ（２２．５ｇ）に溶解し、ＰＭＤＡ（０．７１８３ｇ、３．６６３ｍｍｏｌ）及びＣＢＴＡ（０．７９８９ｇ、３．６６３ｍｍｏｌ）を室温以下に保ちながら加えた。６０℃で２時間攪拌後、ＢＣ（２２．５ｇ）を加えた。このものの粘度は２１０ｍＰａ・ｓであった。この溶液を６０℃で約４時間攪拌したところ、粘度３１ｍＰａ・ｓのワニスを得た（重量平均分子量；３８，０００）。
(Synthesis of varnish)
US6514995 or J.H. Am. Chem. Soc. , 123, 9675 (2001), compound (1-9) (0.9829 g, 7.325 mmol) was dissolved in NMP (22.5 g), PMDA (0.7183 g, 3.663 mmol) and CBTA (0 .7989 g, 3.663 mmol) was added while keeping the temperature below room temperature. After stirring at 60 ° C. for 2 hours, BC (22.5 g) was added. The viscosity of this product was 210 mPa · s. When this solution was stirred at 60 ° C. for about 4 hours, a varnish having a viscosity of 31 mPa · s was obtained (weight average molecular weight; 38,000).
実施例５
下記組成からなるワニスＥの調製
Example 5
Preparation of varnish E having the following composition
ＤＤＭ（１．８３４０ｇ、９．２５０ｍｍｏｌ）をＮＭＰ（２２．５ｇ）に溶解し、ジフェニル−１，４−ブタジイン−３，３’，４，４’−テトラカルボン酸二無水物（３．１６６０ｇ、９．２５０ｍｍｏｌ）を室温以下に保ちながら加えた。２時間攪拌後、ＢＣ（２２．５ｇ）を加えた。このものの粘度は５８ｍＰａ・ｓであった。この溶液を５０℃で約１時間攪拌したところ、粘度３０ｍＰａ・ｓのワニスを得た（重量平均分子量；４９，０００）。 DDM (1.8340 g, 9.250 mmol) was dissolved in NMP (22.5 g), and diphenyl-1,4-butadiyne-3,3 ′, 4,4′-tetracarboxylic dianhydride (3.1660 g, 9.250 mmol) was added while keeping the temperature below room temperature. After stirring for 2 hours, BC (22.5 g) was added. The viscosity of this product was 58 mPa · s. When this solution was stirred at 50 ° C. for about 1 hour, a varnish with a viscosity of 30 mPa · s was obtained (weight average molecular weight; 49,000).
実施例６
化合物（２−７）の合成及びこれを用いた下記ワニスＦの合成
Example 6
Synthesis of compound (2-7) and synthesis of the following varnish F using the same
（化合物（２−７）の合成）
４−エチニルフタル酸 ジエチルエステル（１０．０ｇ、４１ｍｍｏｌ）、シス−１，２−ジクロロエチレン（２．０ｇ、２１ｍｍｏｌ）、Ｐｄ（ＰＰｈ3）4（１．１５ｇ、１．０ｍｍｏｌ）、ＣｕＩ（０．３８ｇ、２．０ｍｍｏｌ）の混合物をジブチルアミン（５０ｍＬ）中、窒素雰囲気下、室温で２４時間反応させた。溶媒を減圧留去後、残さをカラムクロマトグラフィー（シリカゲル／トルエン：酢酸エチル＝５：１（ｖ／ｖ））で精製し、目的とする化合物を得た。１７．３ｇ、収率８２％。
(Synthesis of Compound (2-7))
4-Ethynylphthalic acid diethyl ester (10.0 g, 41 mmol), cis-1,2-dichloroethylene (2.0 g, 21 mmol), Pd (PPh 3 ) 4 (1.15 g, 1.0 mmol), CuI (0. 38 g, 2.0 mmol) was reacted in dibutylamine (50 mL) at room temperature under a nitrogen atmosphere for 24 hours. After evaporating the solvent under reduced pressure, the residue was purified by column chromatography (silica gel / toluene: ethyl acetate = 5: 1 (v / v)) to obtain the target compound. 17.3 g, 82% yield.
得られた化合物（１７．０ｇ、３２．９ｍｍｏｌ）をエタノール（８０ｍＬ）中に溶解し、１０％水酸化ナトリウム水溶液（６０ｍＬ）を加え、１時間還流した。冷却後、溶媒を留去し、残さに６Ｍ塩酸１００ｍＬを加えた。析出した沈殿をろ過し、１００℃で１０時間真空乾燥することによって、目的物を得た。１１．７ｇ、収率９１％。 The obtained compound (17.0 g, 32.9 mmol) was dissolved in ethanol (80 mL), 10% aqueous sodium hydroxide solution (60 mL) was added, and the mixture was refluxed for 1 hr. After cooling, the solvent was distilled off, and 100 mL of 6M hydrochloric acid was added to the residue. The deposited precipitate was filtered and vacuum dried at 100 ° C. for 10 hours to obtain the desired product. 11.7 g, 91% yield.
得られた化合物（１１．０ｇ、２７．２ｍｍｏｌ）及び無水酢酸（５０ｍｌ）の混合物を３時間還流した。冷却後、析出した沈殿をろ過し、８０℃で５時間真空乾燥することによって、目的の化合物（２−７）を得た。７．４ｇ、収率７４％。得られた化合物（２−７）の1Ｈ ＮＭＲスペクトルのピークを以下に示す。
1Ｈ ＮＭＲ（ｐｐｍ）；８．００（ｄ，２Ｈ，Ｊ＝１．５０Ｈｚ），７．９６（ｄｄ，２Ｈ，Ｊ＝８．００，１．５０Ｈｚ），７．７８（ｄｄ，２Ｈ，Ｊ＝８．００，１．５０Ｈｚ），６．５２（ｓ，２Ｈ）。
A mixture of the obtained compound (11.0 g, 27.2 mmol) and acetic anhydride (50 ml) was refluxed for 3 hours. After cooling, the deposited precipitate was filtered and vacuum dried at 80 ° C. for 5 hours to obtain the target compound (2-7). 7.4 g, 74% yield. The peak of 1 H NMR spectrum of the obtained compound (2-7) is shown below.
1 H NMR (ppm); 8.00 (d, 2H, J = 1.50 Hz), 7.96 (dd, 2H, J = 8.00, 1.50 Hz), 7.78 (dd, 2H, J = 8.00, 1.50 Hz), 6.52 (s, 2H).
（ワニスの合成）
化合物（２−７）（１．６２５１ｇ、４．４１３ｍｍｏｌ）をＮＭＰ（２２．５ｇ）に溶解し、ＤＤＭ（０．８７４８ｇ、４．４１３ｍｍｏｌ）を室温以下に保ちながら加えた。６０℃で２時間攪拌後、ＢＣ（２２．５ｇ）を加えた。このものの粘度は１２７ｍＰａ・ｓであった。この溶液を６０℃で約４時間攪拌したところ、粘度３７ｍＰａ・ｓのワニスを得た（重量平均分子量；４９，０００）。
(Synthesis of varnish)
Compound (2-7) (1.6251 g, 4.413 mmol) was dissolved in NMP (22.5 g), and DDM (0.8748 g, 4.413 mmol) was added while keeping the temperature at room temperature or lower. After stirring at 60 ° C. for 2 hours, BC (22.5 g) was added. The viscosity of this product was 127 mPa · s. When this solution was stirred at 60 ° C. for about 4 hours, a varnish having a viscosity of 37 mPa · s was obtained (weight average molecular weight; 49,000).
実施例７
下記組成からなるワニスＧの調製
Example 7
Preparation of varnish G having the following composition
４，４’−ジアミノジフェニル−１，４−ブタジイン（０．９２５６ｇ、３．９８５ｍｍｏｌ）、及び化合物（１−４０）（０．５４２７ｇ、０．９９６２ｍｍｏｌ）をＮＭＰ（２２．５ｇ）に溶解し、ＰＭＤＡ（０．５４３２ｇ、２．４９１ｍｍｏｌ）及びＣＢＴＡ（０．４８８４ｇ、２．４９１ｍｍｏｌ）を室温以下に保ちながら加えた。２時間攪拌後、ＢＣ（２２．５ｇ）を加えた。このものの粘度は９８ｍＰａ・ｓであった。この溶液を６０℃で約２時間攪拌したところ、粘度２７ｍＰａ・ｓのワニスを得た（重量平均分子量；４６，０００）。 4,4′-diaminodiphenyl-1,4-butadiyne (0.9256 g, 3.985 mmol) and compound (1-40) (0.5427 g, 0.9962 mmol) were dissolved in NMP (22.5 g), PMDA (0.5432 g, 2.491 mmol) and CBTA (0.4884 g, 2.491 mmol) were added while keeping the temperature below room temperature. After stirring for 2 hours, BC (22.5 g) was added. The viscosity of this product was 98 mPa · s. When this solution was stirred at 60 ° C. for about 2 hours, a varnish having a viscosity of 27 mPa · s was obtained (weight average molecular weight; 46,000).
実施例８
下記組成からなるワニスＨの調製
Example 8
Preparation of varnish H having the following composition
Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，６８，２６００（１９４６）に従って合成した４−アミノ−４’−ブロモジフェニルメタン（７４ｇ、２８０ｍｍｏｌ）、トリメチルシリルアセチレン（３０ｇ、３１０ｍｍｏｌ）、ＰｄＣｌ2（ＰＰｈ3）2（４．９ｇ、７．０ｍｍｏｌ）、およびヨウ化銅（２．６ｇ、１４．０ｍｍｏｌ）の混合物をトリエチルアミン（１５０ｍｌ）中５０℃で３０分攪拌し、その後３時間還流させた。冷却後溶媒を減圧留去した。残さにトルエン（３００ｍＬ）を加え、純水（３００ｍＬ）で３回洗浄した。有機層を無水ＭｇＳＯ4で乾燥し、ろ過後溶媒を減圧流去した。得られた４−アミノ−４’−トリメチルシリルエチニルジフェニルメタンの粗生成物は精製せずに次の反応に用いた。 J. et al. Am. Chem. Soc. , 68, 2600 (1946), 4-amino-4′-bromodiphenylmethane (74 g, 280 mmol), trimethylsilylacetylene (30 g, 310 mmol), PdCl 2 (PPh 3 ) 2 (4.9 g, 7.0 mmol), And a mixture of copper iodide (2.6 g, 14.0 mmol) was stirred in triethylamine (150 ml) at 50 ° C. for 30 minutes and then refluxed for 3 hours. After cooling, the solvent was distilled off under reduced pressure. Toluene (300 mL) was added to the residue and washed three times with pure water (300 mL). The organic layer was dried over anhydrous MgSO 4 and filtered, and the solvent was removed under reduced pressure. The obtained crude product of 4-amino-4′-trimethylsilylethynyldiphenylmethane was used in the next reaction without purification.
上記生成物（８２ｇ、２９０ｍｍｏｌ）にテトラブチルアンモニウムフロリドＴＨＦ溶液（１Ｍ、２９３ｍＬ）を室温以下で加えた。室温で一晩攪拌した後、溶媒を減圧留去した。上記と同様にトルエン−純水系で抽出操作を行った後、乾燥および溶媒を減圧留去した
。得られた粗生成物をカラムクロマトグラフィー（シリカゲル／トルエン）で精製し、４−アミノ−４’−エチニルジフェニルメタンを得た。収量４８ｇ、収率８２％。
To the above product (82 g, 290 mmol) was added tetrabutylammonium fluoride THF solution (1M, 293 mL) at room temperature or lower. After stirring overnight at room temperature, the solvent was distilled off under reduced pressure. After performing extraction operation in a toluene-pure water system in the same manner as described above, drying and the solvent were distilled off under reduced pressure. The obtained crude product was purified by column chromatography (silica gel / toluene) to obtain 4-amino-4′-ethynyldiphenylmethane. Yield 48 g, 82% yield.
上記化合物（５．０ｇ、２４ｍｍｏｌ）、１，４−ジヨードベンゼン（３．６ｇ、１１ｍｍｏｌ）、ＰｄＣｌ2（ＰＰｈ3）2（８４０ｍｇ、１．２ｍｍｏｌ）、およびヨウ化銅（４６０ｍｇ、２．４ｍｍｏｌ）の混合物をトリエチルアミン（３０ｍｌ）中５０℃で３０分攪拌し、その後３時間還流させた。冷却後溶媒を減圧留去した。残さをカラムクロマトグラフィー（シリカゲル／塩化メチレン→塩化メチレン：メタノール＝５０：１（ｖ／ｖ））で精製し、目的とする化合物（１−１０）を得た。収量１．５ｇ、収率２６％。得られた化合物（１−１０）の1Ｈ ＮＭＲスペクトルのピークを以下に示す。
1Ｈ ＮＭＲ；７．４８（ｓ，４Ｈ）、７．４３（ｄ，４Ｈ，Ｊ＝８．１５Ｈｚ）、７．１６（ｄ，４Ｈ，Ｊ＝８．１５Ｈｚ）、６．９７（ｄ，４Ｈ、Ｊ＝８．２０Ｈｚ）、６．６４（ｄ，４Ｈ、Ｊ＝８．４０Ｈｚ）３．８９（ｓ，４Ｈ）、３．５９（ｂｒｓ、４Ｈ）．
The above compound (5.0 g, 24 mmol), 1,4-diiodobenzene (3.6 g, 11 mmol), PdCl 2 (PPh 3 ) 2 (840 mg, 1.2 mmol), and copper iodide (460 mg, 2.4 mmol) ) Was stirred in triethylamine (30 ml) at 50 ° C. for 30 minutes and then refluxed for 3 hours. After cooling, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel / methylene chloride → methylene chloride: methanol = 50: 1 (v / v)) to obtain the desired compound (1-10). Yield 1.5 g, yield 26%. The peak of 1 H NMR spectrum of the obtained compound (1-10) is shown below.
1 H NMR; 7.48 (s, 4H), 7.43 (d, 4H, J = 8.15 Hz), 7.16 (d, 4H, J = 8.15 Hz), 6.97 (d, 4H) , J = 8.20 Hz), 6.64 (d, 4H, J = 8.40 Hz) 3.89 (s, 4H), 3.59 (brs, 4H).
化合物（１−１０）（０．８６４２ｇ、１．７６９ｍｍｏｌ）をＮＭＰ（１１．２ｇ）に溶解し、ＰＭＤＡ（０．３８５８ｇ、１．７６９ｍｍｏｌ）を室温以下に保ちながら加えた。６０℃で２時間攪拌後、ＢＣ（１１．２ｇ）を加えた。その後７０℃で約３時間攪拌することによって、粘度４０ｍＰａ・ｓのワニスＨを得た（重量平均分子量；９６，０００）。 Compound (1-10) (0.8642 g, 1.769 mmol) was dissolved in NMP (11.2 g), and PMDA (0.3858 g, 1.769 mmol) was added while keeping the temperature at room temperature or lower. After stirring at 60 ° C. for 2 hours, BC (11.2 g) was added. Thereafter, varnish H having a viscosity of 40 mPa · s was obtained by stirring at 70 ° C. for about 3 hours (weight average molecular weight: 96,000).
実施例９
下記組成からなるワニスＩの調製
Example 9
Preparation of varnish I having the following composition
上記４−アミノ−４’−エチニルジフェニルメタン（５．０ｇ、２４ｍｍｏｌ）、Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔ．，４０，８５７９，（１９９９）に従って合成した１，４−ジヨードエチニルベンゼン（４．５ｇ、１２ｍｍｏｌ）、ＰｄＣｌ2（ＰＰｈ3）2（８４０ｍｇ、１．２ｍｍｏｌ）、およびヨウ化銅（４６０ｍｇ、２．４ｍｍｏｌ）の混合物をトリエチルアミン（３０ｍＬ）中５０℃で３０分攪拌し、その後３時間還流させた。冷却後溶媒を減圧留去した。残さをカラムクロマトグラフィー（シリカゲル／塩化メチレン→塩化メチレン：メタノール＝５０：１（ｖ／ｖ））で精製し、目的とする化合物（１−１１）を得た。収量２．２ｇ、収率１７％。得られた化合物（１−１１）の1Ｈ ＮＭＲスペクトルのピークを以下に示す。
1Ｈ ＮＭＲ；７．４０（ｓ，４Ｈ）、７．３６（ｄ，４Ｈ，Ｊ＝８．２０Ｈｚ）、７．１８（ｄ，４Ｈ，Ｊ＝８．２０Ｈｚ）、６．９７（ｄ，４Ｈ、Ｊ＝８．４０Ｈｚ）、６．６４（ｄ，４Ｈ、Ｊ＝８．４０Ｈｚ）３．８９（ｓ，４Ｈ）、３．６０（ｂｒｓ、４Ｈ）．
4-amino-4′-ethynyldiphenylmethane (5.0 g, 24 mmol), Tetrahedron Lett. , 40, 8579, (1999), 1,4-diiodoethynylbenzene (4.5 g, 12 mmol), PdCl 2 (PPh 3 ) 2 (840 mg, 1.2 mmol), and copper iodide (460 mg, 2 .4 mmol) was stirred in triethylamine (30 mL) at 50 ° C. for 30 minutes and then refluxed for 3 hours. After cooling, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel / methylene chloride → methylene chloride: methanol = 50: 1 (v / v)) to obtain the desired compound (1-11). Yield 2.2 g, 17% yield. The peak of 1 H NMR spectrum of the obtained compound (1-11) is shown below.
1 H NMR; 7.40 (s, 4H), 7.36 (d, 4H, J = 8.20 Hz), 7.18 (d, 4H, J = 8.20 Hz), 6.97 (d, 4H) , J = 8.40 Hz), 6.64 (d, 4H, J = 8.40 Hz) 3.89 (s, 4H), 3.60 (brs, 4H).
化合物（１−１１）（０．８８８８ｇ、１．６５６ｍｍｏｌ）をＮＭＰ（１１．２ｇ）に
溶解し、ＰＭＤＡ（０．３６１２ｇ、１．６５６ｍｍｏｌ）を室温以下に保ちながら加えた。６０℃で２時間攪拌後、ＢＣ（１１．２ｇ）を加えた。その後７０℃で約２時間攪拌することによって、粘度３８ｍＰａ・ｓのワニスＩを得た（重量平均分子量；８３，０００）。
Compound (1-11) (0.8888 g, 1.656 mmol) was dissolved in NMP (11.2 g), and PMDA (0.3612 g, 1.656 mmol) was added while keeping the temperature below room temperature. After stirring at 60 ° C. for 2 hours, BC (11.2 g) was added. Thereafter, the mixture was stirred at 70 ° C. for about 2 hours to obtain Varnish I having a viscosity of 38 mPa · s (weight average molecular weight; 83,000).
実施例１０
サンプル瓶にワニスＡを３ｇ計り取り、ＢＣを加え５ｇとした。片面にＩＴＯ電極を設けた透明ガラス基板上に、この約３重量％のポリアミック酸溶液を滴下し、スピンナー法により塗布した（２，３００ｒｐｍ、１５秒）。塗布後、基板を８０℃で５分間加熱し、溶媒を蒸発させた後、偏光板を介して直線偏光を照射した（３６５ｎｍでエネルギー約５Ｊ／ｃｍ2）。光照射後の基板をオーブン中で２３０℃３０分間加熱処理し、膜厚約６０ｎｍの光配向膜を得た。
Example 10
3 g of varnish A was weighed into a sample bottle and BC was added to make 5 g. About 3% by weight of this polyamic acid solution was dropped on a transparent glass substrate provided with an ITO electrode on one side and applied by a spinner method (2,300 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C. for 5 minutes to evaporate the solvent, and then irradiated with linearly polarized light through the polarizing plate (energy of about 5 J / cm 2 at 365 nm). The substrate after the light irradiation was heat-treated in an oven at 230 ° C. for 30 minutes to obtain a photo-alignment film having a thickness of about 60 nm.
ＩＴＯ電極上に上記の光配向膜が形成された基板２枚を、それぞれの光配向膜について照射された直線偏光の偏光方向が平行になるように、かつ光配向膜が形成されている面を対向させ、さらに対向する光配向膜の間に液晶組成物を注入させるための空隙を形成して合わせ、セル厚７μｍの液晶セルＡ（液晶表示素子）を組み立てた。このセルに下記に示す液晶組成物Ａを注入した。 The two substrates on which the above-mentioned photo-alignment film is formed on the ITO electrode are arranged so that the polarization directions of the linearly polarized light irradiated to the respective photo-alignment films are parallel to each other and the surface on which the photo-alignment film is formed A liquid crystal cell A (liquid crystal display element) having a cell thickness of 7 μm was assembled by forming a gap for injecting the liquid crystal composition between the opposed photo-alignment films. Liquid crystal composition A shown below was injected into this cell.
この液晶セルＡを目視により観察したところ、液晶が流動した方向に沿って液晶が並ぶいわゆる流動配向が若干観察された。この液晶セルＡを１１０℃で３０分間アイソトロピック処理を行い、室温まで冷却した。この液晶セルＡを顕微鏡で観察したところ、液晶の配向欠陥は観察されなかった。偏光顕微鏡をクロスニコル状態にし、液晶セルＡを回転させたときの明瞭な明及び暗状態となった（微小な白点はギャップ剤による光ぬけ）。液晶
セルＡの暗状態の写真を図１に示す。
When this liquid crystal cell A was observed with the naked eye, so-called flow alignment in which the liquid crystals were aligned along the direction in which the liquid crystals flowed was slightly observed. This liquid crystal cell A was subjected to an isotropic treatment at 110 ° C. for 30 minutes and cooled to room temperature. When this liquid crystal cell A was observed with a microscope, liquid crystal alignment defects were not observed. When the polarizing microscope was set in a crossed Nicol state and the liquid crystal cell A was rotated, clear light and dark states were obtained (the minute white dots were light-exposed by the gap agent). A photograph of the dark state of the liquid crystal cell A is shown in FIG.
この液晶セルＡのプレチルト角、ＶＨＲ（電圧保持率）及びイオン密度を以下の表９に示す。 Table 9 below shows the pretilt angle, VHR (voltage holding ratio), and ion density of the liquid crystal cell A.
実施例１１
ワニスＡをワニスＢに変えた以外は、上記実施例１０と同様な方法で液晶セルＢを作製した。この液晶セルＢではアイソトロピック処理前に流動配向は観察されなかった。アイソトロピック処理後、偏光顕微鏡で液晶セルＢを写真観察したところ、液晶には配向欠陥はなく、液晶組成物はきれいに配向していることがわかった。また液晶セルＢを回転させたとき明瞭な明及び暗状態が観察された。液晶セルＢの暗状態の写真を図２に示す（微小な白点はギャップ剤による光ぬけ）。またこの液晶セルＢのプレチルト角、ＶＨＲ及びイオン密度を以下の表１０に示す。
Example 11
A liquid crystal cell B was produced in the same manner as in Example 10 except that the varnish A was changed to the varnish B. In this liquid crystal cell B, no flow alignment was observed before the isotropic treatment. When the liquid crystal cell B was photographically observed with a polarizing microscope after the isotropic treatment, it was found that there was no alignment defect in the liquid crystal and the liquid crystal composition was neatly aligned. When the liquid crystal cell B was rotated, clear bright and dark states were observed. A dark state photograph of the liquid crystal cell B is shown in FIG. 2 (the minute white dots are light-exposed by the gap agent). The pretilt angle, VHR, and ion density of the liquid crystal cell B are shown in Table 10 below.
実施例１２
ワニスＡをワニスＣに変えた以外は、上記実施例１０と同様な方法で液晶セルＣを作製した。この液晶セルＣではアイソトロピック処理前に流動配向が若干観察された。アイソトロピック処理後、偏光顕微鏡で液晶セルＣを写真観察したところ、液晶には配向欠陥はなく、液晶組成物はきれいに配向していることがわかった。液晶セルＣを回転させたときの明及び暗状態も実施例１０とほぼ同様な結果であった。またこの液晶セルＣのプレチルト角、ＶＨＲ及びイオン密度を以下の表１１に示す。
Example 12
A liquid crystal cell C was produced in the same manner as in Example 10 except that the varnish A was changed to the varnish C. In this liquid crystal cell C, some flow alignment was observed before isotropic treatment. When the liquid crystal cell C was photographically observed with a polarizing microscope after the isotropic treatment, it was found that there was no alignment defect in the liquid crystal and the liquid crystal composition was neatly aligned. The bright and dark states when the liquid crystal cell C was rotated were almost the same as in Example 10. Table 11 below shows the pretilt angle, VHR, and ion density of the liquid crystal cell C.
実施例１３
ワニスＡをワニスＥに変えた以外は、上記実施例１０と同様な方法で液晶セルＥを作製した。この液晶セルＥではアイソトロピック処理前に流動配向は観察されなかった。アイソトロピック処理後、偏光顕微鏡で液晶セルＥを写真観察したところ、液晶には配向欠陥はなく、液晶組成物はきれいに配向していることがわかった。液晶セルＥを回転させたときの明及び暗状態も実施例１１とほぼ同様な結果であった。またこの液晶セルＥのプレチルト角、ＶＨＲ及びイオン密度を以下の表１２に示す。
Example 13
A liquid crystal cell E was produced in the same manner as in Example 10 except that the varnish A was changed to the varnish E. In this liquid crystal cell E, no flow alignment was observed before the isotropic treatment. When the liquid crystal cell E was photographically observed with a polarizing microscope after the isotropic treatment, it was found that the liquid crystal had no alignment defect and the liquid crystal composition was aligned finely. The bright and dark states when the liquid crystal cell E was rotated were almost the same as in Example 11. The pretilt angle, VHR, and ion density of the liquid crystal cell E are shown in Table 12 below.
実施例１４
ワニスＡをワニスＧに変え、直線偏光を基板に対し７０度の角度から照射した以外は、上記実施例１０と同様な方法で液晶セルＧを作製した。この液晶セルＧではアイソトロピック処理前に流動配向は観察されなかった。アイソトロピック処理後、偏光顕微鏡で液晶セルＧを写真観察したところ、液晶には配向欠陥はなく、液晶組成物はきれいに配向していることがわかった。液晶セルＧを回転させたときの明及び暗状態も実施例１１とほぼ同様な結果であった。またこの液晶セルＧのプレチルト角、ＶＨＲ及びイオン密度を以下の表１３に示す。
Example 14
A liquid crystal cell G was produced in the same manner as in Example 10 except that the varnish A was changed to the varnish G, and linearly polarized light was applied to the substrate from an angle of 70 degrees. In this liquid crystal cell G, no flow alignment was observed before the isotropic treatment. When the liquid crystal cell G was photographically observed with a polarizing microscope after the isotropic treatment, it was found that there was no alignment defect in the liquid crystal and the liquid crystal composition was neatly aligned. The bright and dark states when the liquid crystal cell G was rotated were almost the same as in Example 11. The pretilt angle, VHR, and ion density of the liquid crystal cell G are shown in Table 13 below.
実施例１５
ワニスＡをワニスＨに変えた以外は、上記実施例１０と同様な方法で液晶セルＨを作製した。この液晶セルＨではアイソトロピック処理前に流動配向が若干観察された。アイソトロピック処理後、偏光顕微鏡で液晶セルＨを写真観察したところ、液晶には配向欠陥はなく、液晶組成物はきれいに配向していることがわかった。液晶セルＨを回転させたときの明及び暗状態も実施例１０とほぼ同様な結果であった。またこの液晶セルＨのプレチルト角、ＶＨＲ及びイオン密度を以下の表１４に示す。
Example 15
A liquid crystal cell H was produced in the same manner as in Example 10 except that the varnish A was changed to the varnish H. In this liquid crystal cell H, some flow alignment was observed before the isotropic treatment. When the liquid crystal cell H was photographically observed with a polarizing microscope after the isotropic treatment, it was found that there was no alignment defect in the liquid crystal and the liquid crystal composition was finely aligned. The bright and dark states when the liquid crystal cell H was rotated were almost the same as in Example 10. The pretilt angle, VHR, and ion density of the liquid crystal cell H are shown in Table 14 below.
実施例１６
ワニスＡをワニスＩに変えた以外は、上記実施例１０と同様な方法で液晶セルＩを作製した。この液晶セルＩではアイソトロピック処理前に流動配向は察されなかった。アイソトロピック処理後、偏光顕微鏡で液晶セルＩを写真観察したところ、液晶には配向欠陥はなく、液晶組成物はきれいに配向していることがわかった。液晶セルＩを回転させたときの明及び暗状態も実施例１１とほぼ同様な結果であった。またこの液晶セルＩのプレチルト角、ＶＨＲ及びイオン密度を以下の表１５に示す。
Example 16
A liquid crystal cell I was produced in the same manner as in Example 10 except that the varnish A was changed to the varnish I. In this liquid crystal cell I, no flow alignment was observed before the isotropic treatment. When the liquid crystal cell I was photographically observed with a polarizing microscope after the isotropic treatment, it was found that the liquid crystal had no alignment defects and the liquid crystal composition was aligned finely. The bright and dark states when the liquid crystal cell I was rotated were almost the same as in Example 11. The pretilt angle, VHR, and ion density of the liquid crystal cell I are shown in Table 15 below.
比較例１
特開平１１−１５００１号公報に記載されている４，４’−ジアミノカルコンを用い、以下の組成で実施例１と同様にワニスＪを調製した（粘度；１４ｍＰａ・ｓ、重量平均分子量；２４，０００）。
Comparative Example 1
Using 4,4′-diaminochalcone described in JP-A-11-15001, varnish J was prepared in the same manner as in Example 1 with the following composition (viscosity: 14 mPa · s, weight average molecular weight; 24, 000).
ワニスＡの代わりにワニスＪを用いた以外は、実施例１０と同様な方法で液晶セルＪを製作した。偏光顕微鏡で液晶セルＪを観察したところ、アイソトロピック処理前において著しい流動配向が観察された。アイソトロピック処理後に偏光顕微鏡で観察したところ、
液晶には著しい配向欠陥が観察された。液晶セルＪの暗状態を表した偏光顕微鏡写真を図３に示す。またこの液晶セルＨのプレチルト角、ＶＨＲ及びイオン密度を以下の表１６に示す。
A liquid crystal cell J was produced in the same manner as in Example 10 except that varnish J was used instead of varnish A. When the liquid crystal cell J was observed with a polarizing microscope, remarkable fluid alignment was observed before the isotropic treatment. When observed with a polarizing microscope after isotropic treatment,
Remarkable alignment defects were observed in the liquid crystal. A polarizing microscope photograph showing the dark state of the liquid crystal cell J is shown in FIG. The pretilt angle, VHR, and ion density of the liquid crystal cell H are shown in Table 16 below.
比較例２
Ｍｏｌ．Ｃｒｙｓｔ．Ｌｉｑ．Ｃｒｙｓｔ．Ｖｏｌ．４１２， ２９３（２００４）に記載されている４，４’−ジアミノアゾベンゼンを用い、以下の組成で実施例１と同様にワニスＫを調製した（粘度；３７ｍＰａ・ｓ、重量平均分子量；５８，０００）。
Comparative Example 2
Mol. Cryst. Liq. Cryst. Vol. 412, 293 (2004) was used, and varnish K was prepared in the same manner as in Example 1 with the following composition (viscosity: 37 mPa · s, weight average molecular weight: 58,000). ).
ワニスＡの代わりにワニスＫを用いた以外は、実施例１０と同様な方法で液晶セルＫを製作した。偏光顕微鏡で液晶セルＫを観察したところ、この液晶セルＫではアイソトロピック処理前に流動配向は観察されなかった。アイソトロピック処理後、配向欠陥は観察されずきれいな配向が観察された。液晶セルＫを回転させたときの明及び暗状態も実施例１１とほぼ同様な結果であった。またこの液晶セルＫのプレチルト角、ＶＨＲ及びイオン密度を以下の表１７に示す。この系の場合配向性は良好であるが、電気特性が悪いことが分かる。 A liquid crystal cell K was produced in the same manner as in Example 10 except that varnish K was used instead of varnish A. When the liquid crystal cell K was observed with a polarizing microscope, no flow alignment was observed in the liquid crystal cell K before the isotropic treatment. After the isotropic treatment, no alignment defects were observed, and clean alignment was observed. The bright and dark states when the liquid crystal cell K was rotated were almost the same as in Example 11. Table 17 below shows the pretilt angle, VHR, and ion density of the liquid crystal cell K. In this system, the orientation is good, but the electrical characteristics are poor.
比較例３
２３０℃３０分間のポリアミック酸膜の加熱処理後に直線偏光を照射した以外は実施例１１と同様な方法で液晶セルＬを作製した。偏光顕微鏡で液晶セルＬを観察したところ、アイソトロピック処理前において流動配向が観察された。アイソトロピック処理後に偏光顕微鏡で観察したところ配向欠陥が観察された。液晶セルＬの暗状態を表した偏光顕微鏡写真を図４に示す。またこの液晶セルＬのプレチルト角、ＶＨＲ及びイオン密度を以下の表１８に示す。
Comparative Example 3
A liquid crystal cell L was produced in the same manner as in Example 11 except that linearly polarized light was irradiated after the heat treatment of the polyamic acid film at 230 ° C. for 30 minutes. When the liquid crystal cell L was observed with a polarizing microscope, fluid alignment was observed before the isotropic treatment. When observed with a polarizing microscope after the isotropic treatment, alignment defects were observed. FIG. 4 shows a polarizing microscope photograph showing the dark state of the liquid crystal cell L. Table 18 below shows the pretilt angle, VHR, and ion density of the liquid crystal cell L.
上記実施例と比較例との比較で明らかなように、本発明の光配向膜を有する液晶表示素子は、その液晶において欠陥のない良好な配向性を示し、またＶＨＲが高く、イオン密度も小さい。 As is clear from the comparison between the above examples and comparative examples, the liquid crystal display element having the photo-alignment film of the present invention exhibits good alignment without defects in the liquid crystal, has a high VHR, and a low ion density. .
実施例１７〜２１
基板をシリコン基板に変えた以外は実施例１０、１１、１２、１５、及び１６と同様な方法に従って光配向膜を作製した。この光配向膜の配向指数Δを偏光ＩＲによって測定した結果を以下の表１９に示す。
Examples 17-21
A photo-alignment film was produced in the same manner as in Examples 10, 11, 12, 15, and 16 except that the substrate was changed to a silicon substrate. The results of measuring the orientation index Δ of this photo-alignment film by polarized IR are shown in Table 19 below.
比較例４及び５
基板をシリコン基板に変えた以外は比較例１及び３と同様な方法に従って光配向膜を作製した。この光配向膜の配向指数Δを偏光ＩＲによって測定した結果を以下の表２０に示す。
Comparative Examples 4 and 5
A photo-alignment film was produced according to the same method as in Comparative Examples 1 and 3 except that the substrate was changed to a silicon substrate. The results of measuring the orientation index Δ of this photo-alignment film by polarized IR are shown in Table 20 below.
表１９及び表２０から明らかなように、実施例１７〜２１の光配向膜は、０．５以上、より詳しくは０．８５以上の配向指数Δを示しており、特に実施例１７〜１９及び２１の光配向膜は、０．５以上、より詳しくは０．９以上の配向指数Δを示しており、高い液晶配向能を有することがわかる。一方、比較例４及び５の光配向膜は全く液晶配向能を持たないことが想像できる。 As is clear from Table 19 and Table 20, the photo-alignment films of Examples 17 to 21 show an orientation index Δ of 0.5 or more, more specifically 0.85 or more. In particular, Examples 17 to 19 and The photo-alignment film 21 has an orientation index Δ of 0.5 or more, more specifically 0.9 or more, and it can be seen that it has a high liquid crystal alignment ability. On the other hand, it can be imagined that the photo-alignment films of Comparative Examples 4 and 5 have no liquid crystal alignment ability.
なお、前記第一の測定条件による電圧保持率は、高いほど良く、好ましくは９０．０％以上、より好ましくは９８．０％以上、さらに好ましくは９８．５％以上であり、また前記第二の測定条件による電圧保持率は、好ましくは８３．０％以上、より好ましくは８５．０％以上、さらに好ましくは８７．０％以上であれば、液晶表示素子が、電圧が印加された後次に印加されるまでの電圧低下がなく、これに伴う表示の劣化がない点で優れていることを示している。 The voltage holding ratio under the first measurement condition is better as it is higher, preferably 90.0% or more, more preferably 98.0% or more, and further preferably 98.5% or more. The voltage holding ratio under the measurement conditions is preferably 83.0% or more, more preferably 85.0% or more, and further preferably 87.0% or more. It is excellent in that there is no voltage drop until it is applied to, and there is no display deterioration associated therewith.
また、前記イオン密度は、小さいほど液晶表示素子として優れていることを示し、６００ｐＣ以下であることが好ましく、５００ｐＣ以下であることがより好ましく、４００ｐＣ以下であることがさらに好ましく、３００ｐＣ以下であることがより一層好ましい。 Further, the smaller the ion density, the better the liquid crystal display element, and it is preferably 600 pC or less, more preferably 500 pC or less, further preferably 400 pC or less, and more preferably 300 pC or less. It is even more preferable.
Claims (19)
前記ジアミンがＡ成分である下記一般式（１）で表される不飽和結合含有ジアミンの一又は二以上を含むか、
又は前記テトラカルボン酸二無水物がＡ成分である下記一般式（２）で表される不飽和結合含有テトラカルボン酸二無水物の一又は二以上を含むか、
又は前記ジアミンがＡ成分である前記不飽和結合含有ジアミンの一又は二以上を含みかつ前記テトラカルボン酸二無水物がＡ成分である前記不飽和結合含有テトラカルボン酸二無水物の一又は二以上を含むことを特徴とする光配向膜。
３個の炭素−炭素二重結合又は１〜４個の三重結合を含む二価の不飽和結合含有基を表す。）
３個の炭素−炭素二重結合又は１〜４個の三重結合を含む二価の不飽和結合含有基を表す。） In a photo-alignment film formed by aligning a polyamic acid produced using at least diamine and tetracarboxylic dianhydride as raw materials in a predetermined direction by light irradiation and then imidizing,
The diamine contains one or more unsaturated bond-containing diamines represented by the following general formula (1), which is an A component,
Or the tetracarboxylic dianhydride contains one or more unsaturated bond-containing tetracarboxylic dianhydrides represented by the following general formula (2), which is the A component,
Or, the diamine contains one or more of the unsaturated bond-containing diamine which is the component A, and the tetracarboxylic dianhydride is one or more of the unsaturated bond-containing tetracarboxylic dianhydride, which is the component A. A photo-alignment film comprising:
This represents a divalent unsaturated bond-containing group containing 3 carbon-carbon double bonds or 1 to 4 triple bonds. )
This represents a divalent unsaturated bond-containing group containing 3 carbon-carbon double bonds or 1 to 4 triple bonds. )
有機基を表す。）
立して１，４−フェニレン又は１，４−シクロへキシレンを表し、Ｚ1及びＺ2はそれぞれ独立して単結合、ＣＨ2、ＣＨ2ＣＨ2又はＯを表し、ｒは０〜３、ｓはそれぞれ独立して０〜５、ｔ１は０〜３、ｔ２は０〜３の整数を表す。また、１，４−フェニレン又は１，４−シクロへキシレンの任意のＨは炭素数１〜４のアルキルで置換されていてもよい。）
炭素数１〜１２のアルキレンを表し、Ｇ1及びＧ2は単結合、又は芳香族環及び脂環式環から選ばれる１〜３個の環を含む二価の基を表し、Ｒ5はＨ、Ｆ、ＣＮ、ＯＨ又は炭素数１〜３０のアルキル、ペルフルオロアルキル若しくはアルコキシを表す。ベンゼン環に対する置換基の結合位置及び２個の遊離基の位置は任意の位置である。但し、Ｇ2が単結合でありＸ2が単結合でもなくアルキレンでもない場合は、Ｒ5はＨ又はアルキルであり、またＧ1及びＧ2が共に単結合である場合は、Ｘ1、Ｘ2及びＲ5の合計の炭素数が３以上である。）
はＯを表し、Ｒ6及びＲ7はそれぞれ独立してＨ、炭素数１〜１２のアルキル、又は炭素数
１〜１２のペルフルオロアルキルを表す。ｕ１、ｕ２、ｕ３、ｕ４、及びｕ５はそれぞれ独立して０〜３の整数を表す。また、１，４−フェニレンの任意のＨは炭素数１〜４のアルキルで置換されていてもよい。）
る四価の基を表す。）
、又は１，４−シクロヘキシレンを表し、Ｘ6はそれぞれ独立して単結合又はＣＨ2を表す。）
チル、エチル、又はフェニルを表す。）
3）2、又はＣ（ＣＦ3）2を表し、環Ａ6はそれぞれ独立してシクロヘキサン環又はベンゼン環を表す。）
を表す。）
クロヘキサン環又はベンゼン環を表す。）
3 ) 2 or C (CF 3 ) 2 and each ring A 6 independently represents a cyclohexane ring or a benzene ring. )
Represents. )
前記ジアミン及び前記テトラカルボン酸二無水物は、前記ジアミンとしてＡ成分である下記構造式（１−１）〜（１−１１）の群から選択される一又は二以上のジアミン、及び前記テトラカルボン酸二無水物としてＡ成分である下記構造式（２−１）〜（２−７）の群から選択される一又は二以上のテトラカルボン酸二無水物のいずれか一方又は両方を含み、
さらに前記ジアミン及び前記テトラカルボン酸二無水物は、前記ジアミンとしてＢ成分である下記一般式（３−１）、（３−３）〜（３−７）及び下記構造式（３−２）の群から選択される一又は二以上のジアミン、及び前記テトラカルボン酸二無水物としてＢ成分である下記一般式（４−２）及び下記構造式（４−１）、（４−３）〜（４−７）の群から選択される一又は二以上のテトラカルボン酸二無水物のいずれか一方又は両方を含むことを特徴とする光配向膜。
The diamine and the tetracarboxylic dianhydride are one or more diamines selected from the group of the following structural formulas (1-1) to (1-11) which are A components as the diamine, and the tetracarboxylic acid Including one or both of one or two or more tetracarboxylic dianhydrides selected from the group of the following structural formulas (2-1) to (2-7) which are A components as the acid dianhydride,
Further, the diamine and the tetracarboxylic dianhydride are represented by the following general formulas (3-1), (3-3) to (3-7) and the following structural formula (3-2), which are B components as the diamine. One or two or more diamines selected from the group and the following general formula (4-2) and the following structural formulas (4-1) and (4-3) to (4-3) which are B components as the tetracarboxylic dianhydride 4-7) The photo-alignment film | membrane characterized by including any one or both of the 1 or 2 or more tetracarboxylic dianhydride selected from the group of 4-7).
さらに前記ジアミン及び前記テトラカルボン酸二無水物は、前記ジアミンとしてＢ成分である前記一般式（３−１）、（３−３）〜（３−７）及び前記構造式（３−２）の群から選択される一又は二以上のジアミン、及び前記テトラカルボン酸二無水物としてＢ成分である前記一般式（４−２）及び前記構造式（４−１）、（４−３）の群から選択される一又は二以上のテトラカルボン酸二無水物のいずれか一方又は両方を含むことを特徴とする請求項１１記載の光配向膜。 The diamine and the tetracarboxylic dianhydride are selected from the group of the structural formulas (1-1) to (1-6), (1-10), and (1-11) which are the A component as the diamine. One or two or more diamines and one or two or more tetracarboxylic acids selected from the group of the structural formulas (2-1) to (2-3) which are component A as the tetracarboxylic dianhydride Including one or both of the anhydrides,
Furthermore, the said diamine and the said tetracarboxylic dianhydride of the said General formula (3-1), (3-3)-(3-7), and the said Structural formula (3-2) which are B components as said diamine. One or two or more diamines selected from the group, and the group of the general formula (4-2) and the structural formulas (4-1) and (4-3) which are B components as the tetracarboxylic dianhydride The photo-alignment film according to claim 11, comprising one or both of one or two or more tetracarboxylic dianhydrides selected from:
から１０のアルキルを表し、ｎは１〜４の整数を表し、ｍは１を表し、ｐは０〜２の整数を表すジアミンであることを特徴とする請求項１１又は１２に記載の光配向膜。 In the general formulas (3-1) and (3-3) to (3-7), the diamines represented by the general formulas (3-1) and (3-3) to (3-7) are represented by X 40 represents —O—, X 41 independently represents —CH 2 — or —O—, R 40 represents hydrogen or alkyl having 1 to 20 carbons, and R 41 represents 1 carbon.
The photo-alignment according to claim 11, wherein n represents an alkyl of 1 to 10, n represents an integer of 1 to 4, m represents 1, and p represents an integer of 0 to 2. film.
Δ＝（｜Ａ‖−Ａ⊥｜）／｛（Ａ‖＋Ａ⊥）×ｄ｝ （α）
（式（α）中、Ａ‖は、直線偏光の赤外光を、光配向膜の表面に対して垂直に、かつ赤外光の偏光方向がポリイミドの主鎖の平均配向方向に平行になるように照射したときの波数１，３６０ｃｍ-1付近のイミド環のＣ−Ｎ−Ｃ伸縮振動による積分吸光度を表し、Ａ⊥は、直線偏光の赤外光を、光配向膜の表面に対して垂直に、かつ赤外光の偏光方向がポリイミドの主鎖の平均配向方向に垂直になるように照射したときの波数１，３６０ｃｍ-1付近のイミド環のＣ−Ｎ−Ｃ伸縮振動による積分吸光度を表し、ｄは液晶配向膜の膜厚（ｎｍ）を表す。） The photo-alignment film according to claim 1 or 11, which is a liquid crystal alignment film having an orientation index Δ of a main chain of polyimide obtained by the following formula α of 0.5 or more.
Δ = (| A‖−A⊥ |) / {(A‖ + A⊥) × d} (α)
(In formula (α), A‖ represents linearly polarized infrared light perpendicular to the surface of the photo-alignment film, and the polarization direction of the infrared light is parallel to the average orientation direction of the main chain of the polyimide. Represents the integrated absorbance due to the C—N—C stretching vibration of the imide ring in the vicinity of wave number 1,360 cm −1 when irradiated as above, and A⊥ represents the linearly polarized infrared light with respect to the surface of the photo-alignment film. Integral absorbance due to C—N—C stretching vibration of imide ring near wave number 1,360 cm −1 when irradiated so that the polarization direction of infrared light is perpendicular to the average orientation direction of polyimide main chain D represents the film thickness (nm) of the liquid crystal alignment film.)
前記液晶配向膜は、請求項１〜１４のいずれか一項に記載の光配向膜であることを特徴とする液晶表示素子。 A pair of substrates arranged opposite to each other, electrodes formed on one or both of the opposed surfaces of each of the pair of substrates, and liquid crystal alignment formed on the opposed surfaces of each of the pair of substrates In a liquid crystal display element having a film and a liquid crystal layer formed between the pair of substrates,
The liquid crystal display element according to claim 1, wherein the liquid crystal alignment film is a photo-alignment film according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007029477A JP5481771B2 (en) | 2006-03-16 | 2007-02-08 | Photo-alignment film and liquid crystal display element |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006072566 | 2006-03-16 | ||
| JP2006072566 | 2006-03-16 | ||
| JP2007029477A JP5481771B2 (en) | 2006-03-16 | 2007-02-08 | Photo-alignment film and liquid crystal display element |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013174510A Division JP2014024846A (en) | 2006-03-16 | 2013-08-26 | Optical alignment film, and liquid crystal display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007279691A true JP2007279691A (en) | 2007-10-25 |
| JP5481771B2 JP5481771B2 (en) | 2014-04-23 |
Family
ID=38681148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007029477A Active JP5481771B2 (en) | 2006-03-16 | 2007-02-08 | Photo-alignment film and liquid crystal display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5481771B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009173792A (en) * | 2008-01-25 | 2009-08-06 | Chisso Corp | Alignment film, liquid crystal display element having the same, and composition for alignment layer |
| JP2009230133A (en) * | 2008-03-24 | 2009-10-08 | Samsung Electronics Co Ltd | Photo alignment material, display substrate having alignment layer manufactured by using the same, and method for manufacturing display substrate |
| JP2010049230A (en) * | 2008-03-21 | 2010-03-04 | Chisso Corp | Photo-alignment material, alignment layer and liquid crystal display comprising this |
| JP2010101999A (en) * | 2008-10-22 | 2010-05-06 | Chisso Corp | Liquid crystal alignment layer, liquid crystal aligning agent, and liquid crystal display element |
| JP2010197999A (en) * | 2009-01-29 | 2010-09-09 | Chisso Corp | Aligning agent and liquid crystal polyimide used for the same |
| JP2011076009A (en) * | 2009-10-01 | 2011-04-14 | Hitachi Displays Ltd | Liquid crystal display device |
| JP2011133825A (en) * | 2009-12-25 | 2011-07-07 | Jsr Corp | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
| JP2013173820A (en) * | 2012-02-23 | 2013-09-05 | Pi R & D Co Ltd | Novel polyimide and printing composition including the same |
| KR20150081279A (en) * | 2012-10-31 | 2015-07-13 | 제이엔씨 주식회사 | Liquid crystal display element and method for manufacturing same |
| WO2015146330A1 (en) * | 2014-03-28 | 2015-10-01 | Jnc株式会社 | Liquid crystal display element |
| JP2016050235A (en) * | 2014-08-29 | 2016-04-11 | 国立大学法人北陸先端科学技術大学院大学 | Composite material |
| JP2017043770A (en) * | 2015-08-28 | 2017-03-02 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Monomer, polymer, compensation film, optical film, and display device |
| CN107304362A (en) * | 2016-04-21 | 2017-10-31 | 三星显示有限公司 | It is orientated layer composition and includes the liquid crystal display of the orientation layer composition |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996037807A1 (en) * | 1995-05-26 | 1996-11-28 | Hitachi Chemical Company, Ltd. | Liquid-crystal alignment film |
| JPH0980440A (en) * | 1995-09-13 | 1997-03-28 | Japan Synthetic Rubber Co Ltd | Production of liquid crystal oriented film and liquid crystal display device |
| JPH11218765A (en) * | 1998-01-30 | 1999-08-10 | Hitachi Ltd | Method for orienting high molecular thin film and liquid crystal display device |
| JP2001056469A (en) * | 1999-08-19 | 2001-02-27 | Fuji Photo Film Co Ltd | Liquid crystal oriented film, method for orienting liquid crystalline molecule, optical compensation sheet and stn liquid crystal display device |
| JP2001517317A (en) * | 1996-03-29 | 2001-10-02 | エルシコン・インコーポレーテッド | Method and material for inducing pretilt in liquid crystal and liquid crystal display |
| JP2002003454A (en) * | 2000-04-07 | 2002-01-09 | Chisso Corp | New diamino compound, polymer synthesized by using the diamino compound, and varnish, oriented film and liquid crystal display element, obtained by using the polymer |
| JP2004119080A (en) * | 2002-09-24 | 2004-04-15 | Sumitomo Bakelite Co Ltd | Material and coating varnish for insulating film, and insulating film and semiconductor device using them |
| JP2005049835A (en) * | 2003-07-14 | 2005-02-24 | Chisso Corp | Polyimide-based varnish capable of forming alignment layer for liquid crystal display element of horizontal electric field system, alignment layer, and liquid crystal display element of horizontal electric field system having the alignment layer |
| JP2005255981A (en) * | 2004-02-12 | 2005-09-22 | Chisso Corp | Diamine, polymer, liquid crystal aligned film, and liquid crystal display element |
| WO2007064160A1 (en) * | 2005-12-01 | 2007-06-07 | Lg Chem. Ltd. | Method of producing liquid crystal aligning layer, liquid crystal aligning layer produced using the same, and liquid crystal display including liquid crystal aligning layer |
-
2007
- 2007-02-08 JP JP2007029477A patent/JP5481771B2/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996037807A1 (en) * | 1995-05-26 | 1996-11-28 | Hitachi Chemical Company, Ltd. | Liquid-crystal alignment film |
| JPH0980440A (en) * | 1995-09-13 | 1997-03-28 | Japan Synthetic Rubber Co Ltd | Production of liquid crystal oriented film and liquid crystal display device |
| JP2001517317A (en) * | 1996-03-29 | 2001-10-02 | エルシコン・インコーポレーテッド | Method and material for inducing pretilt in liquid crystal and liquid crystal display |
| JPH11218765A (en) * | 1998-01-30 | 1999-08-10 | Hitachi Ltd | Method for orienting high molecular thin film and liquid crystal display device |
| JP2001056469A (en) * | 1999-08-19 | 2001-02-27 | Fuji Photo Film Co Ltd | Liquid crystal oriented film, method for orienting liquid crystalline molecule, optical compensation sheet and stn liquid crystal display device |
| JP2002003454A (en) * | 2000-04-07 | 2002-01-09 | Chisso Corp | New diamino compound, polymer synthesized by using the diamino compound, and varnish, oriented film and liquid crystal display element, obtained by using the polymer |
| JP2004119080A (en) * | 2002-09-24 | 2004-04-15 | Sumitomo Bakelite Co Ltd | Material and coating varnish for insulating film, and insulating film and semiconductor device using them |
| JP2005049835A (en) * | 2003-07-14 | 2005-02-24 | Chisso Corp | Polyimide-based varnish capable of forming alignment layer for liquid crystal display element of horizontal electric field system, alignment layer, and liquid crystal display element of horizontal electric field system having the alignment layer |
| JP2005255981A (en) * | 2004-02-12 | 2005-09-22 | Chisso Corp | Diamine, polymer, liquid crystal aligned film, and liquid crystal display element |
| WO2007064160A1 (en) * | 2005-12-01 | 2007-06-07 | Lg Chem. Ltd. | Method of producing liquid crystal aligning layer, liquid crystal aligning layer produced using the same, and liquid crystal display including liquid crystal aligning layer |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009173792A (en) * | 2008-01-25 | 2009-08-06 | Chisso Corp | Alignment film, liquid crystal display element having the same, and composition for alignment layer |
| JP2010049230A (en) * | 2008-03-21 | 2010-03-04 | Chisso Corp | Photo-alignment material, alignment layer and liquid crystal display comprising this |
| US8771809B2 (en) | 2008-03-24 | 2014-07-08 | Samsung Display Co., Ltd. | Photoalignment material, display substrate having an alignment layer formed using the same, and method of manufacturing the display substrate |
| JP2009230133A (en) * | 2008-03-24 | 2009-10-08 | Samsung Electronics Co Ltd | Photo alignment material, display substrate having alignment layer manufactured by using the same, and method for manufacturing display substrate |
| JP2010101999A (en) * | 2008-10-22 | 2010-05-06 | Chisso Corp | Liquid crystal alignment layer, liquid crystal aligning agent, and liquid crystal display element |
| JP2010197999A (en) * | 2009-01-29 | 2010-09-09 | Chisso Corp | Aligning agent and liquid crystal polyimide used for the same |
| JP2011076009A (en) * | 2009-10-01 | 2011-04-14 | Hitachi Displays Ltd | Liquid crystal display device |
| JP2011133825A (en) * | 2009-12-25 | 2011-07-07 | Jsr Corp | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
| JP2013173820A (en) * | 2012-02-23 | 2013-09-05 | Pi R & D Co Ltd | Novel polyimide and printing composition including the same |
| KR20150081279A (en) * | 2012-10-31 | 2015-07-13 | 제이엔씨 주식회사 | Liquid crystal display element and method for manufacturing same |
| KR102085682B1 (en) | 2012-10-31 | 2020-03-06 | 제이엔씨 주식회사 | Liquid crystal display device and method for manufacturing same |
| US10041000B2 (en) | 2014-03-28 | 2018-08-07 | Jnc Corporation | Liquid crystal display device |
| JPWO2015146330A1 (en) * | 2014-03-28 | 2017-04-13 | Jnc株式会社 | Liquid crystal display element |
| WO2015146330A1 (en) * | 2014-03-28 | 2015-10-01 | Jnc株式会社 | Liquid crystal display element |
| JP2016050235A (en) * | 2014-08-29 | 2016-04-11 | 国立大学法人北陸先端科学技術大学院大学 | Composite material |
| JP2017043770A (en) * | 2015-08-28 | 2017-03-02 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Monomer, polymer, compensation film, optical film, and display device |
| US10877198B2 (en) | 2015-08-28 | 2020-12-29 | Samsung Electronics Co., Ltd. | Monomer, polymer, compensation film, optical film, and display device |
| CN107304362A (en) * | 2016-04-21 | 2017-10-31 | 三星显示有限公司 | It is orientated layer composition and includes the liquid crystal display of the orientation layer composition |
| CN107304362B (en) * | 2016-04-21 | 2022-07-19 | 三星显示有限公司 | Alignment layer composition and liquid crystal display including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5481771B2 (en) | 2014-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5481771B2 (en) | Photo-alignment film and liquid crystal display element | |
| KR101445245B1 (en) | Light aligning film and liquid crystal display device | |
| JP5407394B2 (en) | Photo-alignment agent, alignment film, and liquid crystal display device using the same | |
| JP5671797B2 (en) | Alignment agent and liquid crystalline polyimide used therefor | |
| JP6287577B2 (en) | Liquid crystal aligning agent, liquid crystal aligning film, manufacturing method thereof, and liquid crystal display element | |
| JP6315182B2 (en) | Liquid crystal aligning agent and liquid crystal display element | |
| KR101742838B1 (en) | Liquid crystal aligning agent and liquid crystal display element using same | |
| TWI657115B (en) | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, polymer and compound | |
| JP6375789B2 (en) | Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, retardation film and method for producing the same | |
| JP2017138575A (en) | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer and diamine | |
| JP5672762B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| JP6252752B2 (en) | Liquid crystal alignment agent | |
| JP6424609B2 (en) | Liquid crystal alignment agent, method of manufacturing liquid crystal display element, liquid crystal alignment film and liquid crystal display element | |
| JP6870289B2 (en) | Liquid crystal alignment agent, manufacturing method of liquid crystal element, liquid crystal alignment film, liquid crystal element | |
| JP6682965B2 (en) | Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal element, and method for producing liquid crystal aligning film | |
| TWI698489B (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| JP2013174860A (en) | Liquid crystal aligning agent for optical alignment, formation method of liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element | |
| JP6057075B2 (en) | Liquid crystal alignment agent | |
| TWI830451B (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| TWI791817B (en) | Liquid crystal alignment agent and manufacturing method thereof, liquid crystal alignment film and manufacturing method thereof, and liquid crystal element | |
| WO2020218331A1 (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using same | |
| JP5673869B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| TW202101093A (en) | Liquid crystal alignment agent for optical alignment, liquid crystal alignment film and liquid crystal display element having high adhesion to a sealant and capable of improving the residual image characteristics and VHR reliability of a liquid crystal display element | |
| TW202409152A (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| CN116731727A (en) | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, polymer and compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20091029 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20110331 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110426 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110928 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111115 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20120110 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20120113 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120605 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120712 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121211 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130131 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130625 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130826 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140121 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140203 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5481771 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |