JP2014191352A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element thereof - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element thereof Download PDFInfo
- Publication number
- JP2014191352A JP2014191352A JP2014061641A JP2014061641A JP2014191352A JP 2014191352 A JP2014191352 A JP 2014191352A JP 2014061641 A JP2014061641 A JP 2014061641A JP 2014061641 A JP2014061641 A JP 2014061641A JP 2014191352 A JP2014191352 A JP 2014191352A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- formula
- aligning agent
- polyamic acid
- crystal aligning
- 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 105
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229920005575 poly(amic acid) Polymers 0.000 claims description 52
- 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 29
- 125000000962 organic group Chemical group 0.000 claims description 27
- 150000004985 diamines Chemical class 0.000 claims description 25
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000005755 formation reaction Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000007888 film coating Substances 0.000 abstract description 4
- 238000009501 film coating Methods 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000003960 organic solvent Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 but not limited to Chemical compound 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、液晶配向剤、それにより製造された液晶配向膜及び液晶表示素子に関する。 The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film produced thereby, and a liquid crystal display element.
液晶表示素子の映像品質を向上させるために、液晶配向膜は、下記の性質を有するべきである。（１）良好な電気特性：残影を生じないことや、電圧保持率が高いこと等である。（２）安定したプレチルト角：均一な配向効果を達するために、液晶分子を傾斜させて液晶配向膜表面との間で一つの角度を形成することにより、液晶分子が電場により駆動された後一定の方向へ回転する必要があり、前記傾斜した角度は、即ちプレチルト角（Ｐｒｅｔｉｌｔ Ａｎｇｌｅ）であり、プレチルト角の安定性は、液晶表示素子の反応時間及び配向均一性に影響を与え、更に結像品質に影響を与える。（３）優れたフィルム塗布性：液晶配向膜を基板に塗布する時に摩擦による刷毛目及び切削屑を生じない。 In order to improve the image quality of the liquid crystal display element, the liquid crystal alignment film should have the following properties. (1) Good electrical characteristics: no shadows are produced, and the voltage holding ratio is high. (2) Stable pretilt angle: In order to achieve a uniform alignment effect, the liquid crystal molecules are tilted to form a single angle with the surface of the liquid crystal alignment film, so that the liquid crystal molecules are constant after being driven by an electric field. The tilt angle is a pretilt angle, and the stability of the pretilt angle affects the reaction time and alignment uniformity of the liquid crystal display element, and further image formation is performed. Affects quality. (3) Excellent film coatability: When applying the liquid crystal alignment film to the substrate, no brush eye or cutting waste is generated due to friction.
液晶表示素子の普及につれて、消費者の液晶表示素子の結像品質に対する要求はますます高くなり、如何に液晶表示素子の結像品質を更に改善するのかは、関連業者の努力目標である。 With the spread of liquid crystal display elements, consumers' demand for image quality of liquid crystal display elements becomes higher, and how to further improve the image quality of liquid crystal display elements is an endeavor goal of related companies.
従って、本発明の一つの目的は、液晶配向剤を提供することにある。この液晶配向剤により製造された液晶配向膜によって、安定したプレチルト角を提供することができ、液晶表示素子の反応時間を短くし、配向均一性を向上させ、更に結像品質を改善することに寄与する。 Accordingly, one object of the present invention is to provide a liquid crystal aligning agent. The liquid crystal alignment film manufactured with this liquid crystal alignment agent can provide a stable pretilt angle, shorten the reaction time of the liquid crystal display element, improve the alignment uniformity, and further improve the imaging quality. Contribute.
本発明の別の目的は、優れたフィルム塗布性を有する液晶配向剤を提供することにある。 Another object of the present invention is to provide a liquid crystal aligning agent having excellent film coatability.
本発明の一態様による液晶配向剤は、式（Ｉ）に示す構造を有するポリアミド酸誘導体（Ａ）を含む。式（Ｉ）において、Ａ１及びＡ２は、それぞれ独立した４価の有機基であり、Ａ３及びＡ４は、それぞれ独立した２価の有機基であり、Ｒは、１価の有機基であり、ｋ＋ｐ＝１、且つ、０．０１≦ｋである。
本発明の液晶配向剤は、ポリイミド、ポリアミド酸又はイミド‐アミド酸共重合体を更に含んでもよい。 The liquid crystal aligning agent of the present invention may further contain polyimide, polyamic acid, or imide-amide acid copolymer.
本発明の液晶配向剤において、Ｒは、式（ＩＩＩ）、式（ＩＶ）又は式（Ｖ）に示す有機基であってもよい。
式（ＩＩＩ）〜式（Ｖ）において、Ｒ１は、炭素数１〜２０のアルキル基、炭素数４〜２２の脂環族、式（ＶＩ）に示す有機基又は式（ＶＩＩ）に示す有機基であってもよい。
式（ＶＩ）及び式（ＶＩＩ）において、Ｒ２は、ベンゼン、シクロへキサン、炭素数１〜２０のアルキル基又は炭素数４〜２２の脂環族であってもよく、Ｒ３は、水素、炭素数１〜２０のアルキル基又は炭素数４〜２２の脂環族である。 In Formula (VI) and Formula (VII), R2 may be benzene, cyclohexane, an alkyl group having 1 to 20 carbon atoms, or an alicyclic group having 4 to 22 carbon atoms, and R3 may be hydrogen, carbon It is a C1-C20 alkyl group or C4-C22 alicyclic.
本発明の液晶配向剤において、ポリアミド酸誘導体（Ａ）の生成反応における反応物は、テトラカルボン酸二無水物（ａ‐１）、ジアミン（ａ‐２）及びモノアミン（ａ‐３）を含んでもよい。 In the liquid crystal aligning agent of the present invention, the reactant in the formation reaction of the polyamic acid derivative (A) may include tetracarboxylic dianhydride (a-1), diamine (a-2) and monoamine (a-3). Good.
本発明の別態様による液晶配向剤は、式（ＩＩ）に示す構造を有するポリアミド酸誘導体（Ｂ）を含む。式（ＩＩ）において、Ａ１及びＡ２は、それぞれ独立した４価の有機基であり、Ａ３及びＡ４は、それぞれ独立した２価の有機基であり、Ｒは、１価の有機基であり、ｋ＋ｍ１＋ｍ２＝１、０≦ｍ１、０＜ｍ２、且つ、０．０１≦ｋである。
本発明の一態様による液晶配向膜は、前述の液晶配向剤を用いて形成される。 The liquid crystal alignment film according to one embodiment of the present invention is formed using the liquid crystal aligning agent described above.
本発明の一態様による液晶表示素子は、前述の液晶配向膜を含む。 A liquid crystal display element according to one embodiment of the present invention includes the liquid crystal alignment film described above.
この液晶配向剤により形成された液晶配向膜は、安定したプレチルト角及び優れたフィルム塗布性を与えるため、この液晶配向膜によって製造された液晶表示素子は、市場の需要を満たすことができる。 Since the liquid crystal alignment film formed with this liquid crystal aligning agent provides a stable pretilt angle and excellent film coatability, the liquid crystal display device manufactured with this liquid crystal alignment film can meet the market demand.
本発明の一実施形態による液晶配向剤、液晶配向膜及びその液晶表示素子を以下の通り説明する。
（ポリアミド酸誘導体（Ａ））
ポリアミド酸誘導体（Ａ）は、式（Ｉ）に示す構造を有する。
(Polyamide acid derivative (A))
The polyamic acid derivative (A) has a structure represented by the formula (I).
ただし、Ｒは、式（ＩＩＩ）、式（ＩＶ）又は式（Ｖ）に示す有機基であってもよい。
式（ＩＩＩ）〜式（Ｖ）において、Ｒ１は、炭素数１〜２０のアルキル基、炭素数４〜２２の脂環族、式（ＶＩ）に示す有機基又は式（ＶＩＩ）に示す有機基であってもよい。
式（ＶＩ）及び式（ＶＩＩ）において、Ｒ２は、ベンゼン、シクロへキサン、炭素数１〜２０のアルキル基又は炭素数４〜２２の脂環族であってもよく、Ｒ３は、水素、炭素数１〜２０のアルキル基又は炭素数４〜２２の脂環族である。 In Formula (VI) and Formula (VII), R2 may be benzene, cyclohexane, an alkyl group having 1 to 20 carbon atoms, or an alicyclic group having 4 to 22 carbon atoms, and R3 may be hydrogen, carbon It is a C1-C20 alkyl group or C4-C22 alicyclic.
ポリアミド酸誘導体（Ａ）の生成反応は、テトラカルボン酸二無水物（ａ‐１）、ジアミン（ａ‐２）及びモノアミン（ａ‐３）を反応物として、有機溶剤において重合反応を行って得ることができる。 The formation reaction of the polyamic acid derivative (A) is obtained by conducting a polymerization reaction in an organic solvent using tetracarboxylic dianhydride (a-1), diamine (a-2) and monoamine (a-3) as reactants. be able to.
（ポリアミド酸誘導体（Ｂ））
ポリアミド酸誘導体（Ｂ）は、式（ＩＩ）に示す構造を有する。式（ＩＩ）において、Ａ１及びＡ２は、それぞれ独立した４価の有機基であり、Ａ３及びＡ４は、それぞれ独立した２価の有機基であり、Ｒは、１価の有機基であり、ｋ＋ｍ１＋ｍ２＝１、０≦ｍ１、０＜ｍ２、且つ、０．０１≦ｋである。０．０５≦ｋ≦０．７であることが好ましく、０．０５≦ｋ≦０．４であることがより好ましい。
The polyamic acid derivative (B) has a structure represented by the formula (II). In the formula (II), A1 and A2 are independent tetravalent organic groups, A3 and A4 are independent divalent organic groups, R is a monovalent organic group, k + m1 + m2 = 1, 0 ≦ m1, 0 <m2, and 0.01 ≦ k. 0.05 ≦ k ≦ 0.7 is preferable, and 0.05 ≦ k ≦ 0.4 is more preferable.
ポリアミド酸誘導体（Ａ）を脱水閉環反応させることによって、ポリアミド酸誘導体（Ｂ）を得ることができる。ｍ１＞０である場合は、ポリアミド酸誘導体（Ａ）を部分的に脱水閉環反応させることを表し、ｍ１＝０である場合は、ポリアミド酸誘導体（Ａ）を完全に脱水閉環反応させることを表す。 A polyamic acid derivative (B) can be obtained by subjecting the polyamic acid derivative (A) to a dehydration ring-closing reaction. When m1> 0, the polyamic acid derivative (A) is partially dehydrated and cyclized, and when m1 = 0, the polyamic acid derivative (A) is completely dehydrated and cyclized. .
（テトラカルボン酸二無水物（ａ‐１））
テトラカルボン酸二無水物（ａ‐１）は、式（ａ‐１‐１）、式（ａ‐１‐２）又は式（ａ‐１‐３）に示す構造であってもよいが、これらに限定されない。
The tetracarboxylic dianhydride (a-1) may have a structure represented by the formula (a-1-1), the formula (a-1-2), or the formula (a-1-3). It is not limited to.
（ジアミン（ａ‐２））
ジアミン（ａ‐２）は、式（ａ‐２‐１）又は式（ａ‐２‐２）に示す構造であってもよいが、これらに限定されない。
The diamine (a-2) may have a structure represented by the formula (a-2-1) or the formula (a-2-2), but is not limited thereto.
（モノアミン（ａ‐３））
モノアミン（ａ‐３）は、式（ａ‐３‐１）又は式（ａ‐３‐２）に示す構造であってもよいが、これらに限定されない。
The monoamine (a-3) may have a structure represented by the formula (a-3-1) or the formula (a-3-2), but is not limited thereto.
（ポリアミド酸誘導体（Ａ）の合成方法）
テトラカルボン酸二無水物（ａ‐１）、ジアミン（ａ‐２）及びモノアミン（ａ‐３）を反応物として、有機溶剤（ａ‐４）において重合反応を行うことで、ポリアミド酸誘導体（Ａ）を含む溶液を得る。
(Synthesis method of polyamic acid derivative (A))
A polyamic acid derivative (A) is obtained by performing a polymerization reaction in an organic solvent (a-4) using tetracarboxylic dianhydride (a-1), diamine (a-2) and monoamine (a-3) as reactants. Is obtained.
具体的には、まず、テトラカルボン酸二無水物（ａ‐１）及びモノアミン（ａ‐３）で、有機溶剤（ａ‐４）において、室温〜１００℃の温度、１〜５時間で第１段階反応を行う。この段階反応において、モノアミン（ａ‐３）のアミノ基とテトラカルボン酸二無水物（ａ‐１）の酸無水物基の当量比は、１：１〜３：１であってもよく、好ましくは、１：１であってもよい。 Specifically, first, tetracarboxylic dianhydride (a-1) and monoamine (a-3) are used in an organic solvent (a-4) at a temperature of room temperature to 100 ° C. for 1 to 5 hours. Perform a step reaction. In this step reaction, the equivalent ratio of the amino group of monoamine (a-3) to the acid anhydride group of tetracarboxylic dianhydride (a-1) may be 1: 1 to 3: 1, preferably May be 1: 1.
その後、第１段階反応による生成物に例えば塩化チオニルのような塩素化剤を添加し、室温、１〜５時間で第２段階反応（即ち、塩化反応）を行う。この段階反応において、塩素化剤とテトラカルボン酸二無水物（ａ‐１）の酸無水物基の当量比は、１：１〜３：１であってもよく、好ましくは、１：１であってもよい。 Thereafter, a chlorinating agent such as thionyl chloride is added to the product of the first stage reaction, and the second stage reaction (ie, chlorination reaction) is performed at room temperature for 1 to 5 hours. In this stage reaction, the equivalent ratio of the chlorinating agent to the acid anhydride group of tetracarboxylic dianhydride (a-1) may be 1: 1 to 3: 1, preferably 1: 1. There may be.
次に、第２段階反応による生成物にジアミン（ａ‐２）及びテトラカルボン酸二無水物（ａ‐１）を添加し、室温〜６０℃の温度、１〜１０時間で第３段階反応を行うことで、ポリアミド酸誘導体（Ａ）を含む溶液を得る。この段階反応において、ジアミン（ａ‐２）のアミノ基とテトラカルボン酸二無水物（ａ‐１）の酸無水物基の当量比は、０．５：１〜２：１であってもよく、好ましくは、０．７：１〜１．５：１であってもよい。 Next, diamine (a-2) and tetracarboxylic dianhydride (a-1) are added to the product of the second stage reaction, and the third stage reaction is performed at a temperature of room temperature to 60 ° C. for 1 to 10 hours. By performing, the solution containing a polyamic acid derivative (A) is obtained. In this stage reaction, the equivalent ratio of the amino group of diamine (a-2) and the acid anhydride group of tetracarboxylic dianhydride (a-1) may be 0.5: 1 to 2: 1. Preferably, it may be 0.7: 1 to 1.5: 1.
最後に、前記ポリアミド酸誘導体（Ａ）を含む溶液を、溶解度の悪い大量の溶剤に注入して析出させ、沈殿物が得られ、この沈殿物を洗浄した後、更に減圧条件で乾燥させることで、ポリアミド酸誘導体（Ａ）を得ることができる。得られたポリアミド酸誘導体（Ａ）は、一回又は複数回の精製を行うことができる。精製工程は、ポリアミド酸誘導体（Ａ）を有機溶剤（ａ‐４）に溶解させ、溶解度の悪い溶剤で析出させ、沈殿物が得られ、そして、沈殿物を洗浄した後、減圧条件で乾燥させる。 Finally, the solution containing the polyamic acid derivative (A) is poured into a large amount of solvent having poor solubility to precipitate, and a precipitate is obtained. After washing the precipitate, it is further dried under reduced pressure conditions. A polyamic acid derivative (A) can be obtained. The obtained polyamic acid derivative (A) can be purified once or a plurality of times. In the purification step, the polyamic acid derivative (A) is dissolved in the organic solvent (a-4), precipitated with a solvent having poor solubility, a precipitate is obtained, and the precipitate is washed and then dried under reduced pressure conditions. .
前記有機溶剤（ａ‐４）は、ポリアミド酸誘導体（Ａ）に対する溶解度の良い有機溶剤（ａ‐４‐１）、及び溶解度の悪い有機溶剤（ａ‐４‐２）を含む。溶解度の良い有機溶剤（ａ‐４‐１）は、Ｎ‐メチル‐２‐ピロリドン（ａ‐４‐１‐１）、Ｎ，Ｎ‐ジメチルホルムアミド、Ｎ，Ｎ‐ジメチルアセトアミド、Ｎ‐メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ヘキサメチルホスホルアミド、γ‐ブチロラクトン、ピリジンを含むが、これらに限定されない。上記の溶解度の良い有機溶剤（ａ‐４‐１）は、単独で使用しても、２種以上を混合して同時に使用してもよい。 The organic solvent (a-4) includes an organic solvent (a-4-1) having good solubility in the polyamic acid derivative (A) and an organic solvent (a-4-2) having poor solubility. Organic solvents (a-4-1) having good solubility are N-methyl-2-pyrrolidone (a-4-1-1), N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, Including but not limited to dimethyl sulfoxide, tetramethylurea, hexamethylphosphoramide, γ-butyrolactone, pyridine. The organic solvent (a-4-1) having good solubility may be used alone or in combination of two or more.
溶解度の悪い有機溶剤（ａ‐４‐２）は、前記溶解度の良い有機溶剤（ａ‐４‐１）と混合して使用することができるが、ポリアミド酸誘導体（Ａ）が析出されるまでには至らないことを前提とする。溶解度の悪い有機溶剤（ａ‐４‐２）は、メタノール、エタノール、イソプロパノール、ｎ‐ブタノール、シクロへキサノール、エチレングリコール、エチレングリコールメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチルエーテル、アセトン、メチルエチルケトン、シクロヘキサノン、酢酸メチル、酢酸エチル、テトラヒドロフラン、ジクロロメタン、クロロホルム、１，２‐ジクロロエタン、ベンゼン、トルエン、キシレン、ｎ‐へキサン、ｎ‐ヘプタン、ｎ‐オクタンを含むが、これらに限定されない。 The organic solvent having poor solubility (a-4-2) can be used by mixing with the organic solvent having good solubility (a-4-1), but before the polyamic acid derivative (A) is precipitated. It is assumed that this is not possible. Organic solvents with poor solubility (a-4-2) are methanol, ethanol, isopropanol, n-butanol, cyclohexanol, ethylene glycol, ethylene glycol methyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether , Ethylene glycol diethyl ether, diethyl ether, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, tetrahydrofuran, dichloromethane, chloroform, 1,2-dichloroethane, benzene, toluene, xylene, n-hexane, n-heptane, n- Including but not limited to octane.
（ポリアミド酸誘導体（Ｂ）の合成方法）
前記ポリアミド酸誘導体（Ａ）の合成方法において、第３段階反応で得られた、ポリアミド酸誘導体（Ａ）を含む溶液を脱水閉環反応させることで、ポリアミド酸誘導体（Ｂ）を含む溶液を得ることができる。反応条件及び抽出方法は、従来のポリアミド酸を脱水閉環してポリイミドが得られるのと同じであり、ここで詳しく述べない。
(Synthesis method of polyamic acid derivative (B))
In the method for synthesizing the polyamic acid derivative (A), a solution containing the polyamic acid derivative (B) is obtained by subjecting the solution containing the polyamic acid derivative (A) obtained in the third stage reaction to a dehydration ring-closing reaction. Can do. The reaction conditions and extraction method are the same as those obtained by dehydrating and cyclizing a conventional polyamic acid, and will not be described in detail here.
（液晶配向剤）
本実施形態の液晶配向剤は、ポリアミド酸誘導体（Ａ）又はポリアミド酸誘導体（Ｂ）、有機溶剤（Ｃ）を含み、また、添加剤（Ｄ）を選択的に含むことができる。
(Liquid crystal aligning agent)
The liquid crystal aligning agent of this embodiment contains a polyamic acid derivative (A) or a polyamic acid derivative (B), an organic solvent (C), and can optionally contain an additive (D).
本実施形態の液晶配向剤は、液晶配向剤の性質を改善するために、ポリイミド（Ｅ）、ポリアミド酸（Ｆ）又はイミド‐アミド酸共重合体（Ｇ）を更に含むことができる。 In order to improve the properties of the liquid crystal aligning agent, the liquid crystal aligning agent of the present embodiment can further include polyimide (E), polyamic acid (F), or imide-amide acid copolymer (G).
ポリアミド酸誘導体（Ａ）又はポリアミド酸誘導体（Ｂ）を有機溶剤（Ｃ）に溶解すると、液晶配向剤を形成することができる。液晶配向剤を調製する温度は、０℃〜１５０℃であることが好ましく、２０℃〜５０℃であることがより好ましい。 When the polyamic acid derivative (A) or the polyamic acid derivative (B) is dissolved in the organic solvent (C), a liquid crystal aligning agent can be formed. The temperature for preparing the liquid crystal aligning agent is preferably 0 ° C. to 150 ° C., and more preferably 20 ° C. to 50 ° C.
液晶配向剤は、粘度及び揮発性に応じて、含まれる固形分の含有量を調整することができ、固形分の含有量１ｗｔ％〜１０ｗｔ％で含むことが好ましい。固形分の含有量が１ｗｔ％より低い場合、塗布後の液晶配向膜の厚さが薄すぎ、その配向性を低下させてしまい、固形分の含有量が１０ｗｔ％より高い場合、塗布品質に影響を与えてしまう。 The liquid crystal aligning agent can adjust content of the solid content contained according to a viscosity and volatility, and it is preferable to contain by solid content 1wt%-10wt%. If the solid content is lower than 1 wt%, the thickness of the liquid crystal alignment film after coating is too thin and the orientation is lowered. If the solid content is higher than 10 wt%, the coating quality is affected. Will be given.
前記有機溶剤（Ｃ）は、Ｎ‐メチル‐２‐ピロリドン、Ｎ，Ｎ‐ジメチルホルムアミド、Ｎ，Ｎ‐ジメチルアセトアミド、Ｎ‐メチルカプロラクタム、ジメチルスルホキシド、γ‐ブチロラクトン、γ‐ブチロラクタム、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ‐ｎ‐プロピルエーテル、エチレングリコールモノブチルエーテル等を含むが、これらに限定されず、上記の有機溶剤（Ｃ）は、二種以上を混合して使用してもよい。上記で挙げられた有機溶剤（Ｃ）以外、ポリアミド酸誘導体（Ａ）又はポリアミド酸誘導体（Ｂ）を溶解できれば、何れも有機溶剤（Ｃ）とすることができる。 The organic solvent (C) is N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, dimethyl sulfoxide, γ-butyrolactone, γ-butyrolactam, ethylene glycol monomethyl ether Including, but not limited to, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monobutyl ether, etc., the above organic solvent (C) is used by mixing two or more kinds Also good. Any organic solvent (C) can be used as long as it can dissolve the polyamic acid derivative (A) or the polyamic acid derivative (B) other than the organic solvent (C) mentioned above.
前記添加剤（Ｄ）は、有機シラン（シロキサン）化合物（Ｄ‐１）又はエポキシ化合物（Ｄ‐２）であってもよい。 The additive (D) may be an organosilane (siloxane) compound (D-1) or an epoxy compound (D-2).
（液晶配向膜）
液晶配向膜を形成する方法は、下記の工程を含む。
(Liquid crystal alignment film)
The method for forming the liquid crystal alignment film includes the following steps.
まず、本実施形態の液晶配向剤を、パターン化された透明導電膜を有するガラス基板に塗布して被覆層を形成する。塗布方法は、ロールコーティング法、スピンコーティング法及び印刷法を含むが、これらに限定されず、慣用な方法であり、ここで詳しく述べない。 First, the liquid crystal aligning agent of this embodiment is apply | coated to the glass substrate which has the patterned transparent conductive film, and a coating layer is formed. Application methods include, but are not limited to, roll coating, spin coating, and printing, and are conventional methods and will not be described in detail here.
次に、被覆層を加熱してベーキングし、被覆層を液晶配向膜に形成させる。加熱してベーキングする目的は、液晶配向剤内の有機溶剤（Ｃ）を取り除くと同時に、ポリアミド酸誘導体（Ａ）又はポリアミド酸誘導体（Ｂ）の脱水閉環反応を促進することである。加熱してベーキングする温度は、８０℃〜３００℃であってもよく、より好ましくは、１００℃〜２４０℃である。形成された液晶配向膜の厚さは、０．００５〜０．５μｍであることが好ましい。 Next, the coating layer is heated and baked to form the coating layer on the liquid crystal alignment film. The purpose of heating and baking is to remove the organic solvent (C) in the liquid crystal aligning agent and at the same time promote the dehydration ring-closing reaction of the polyamic acid derivative (A) or the polyamic acid derivative (B). The heating and baking temperature may be 80 ° C to 300 ° C, more preferably 100 ° C to 240 ° C. The thickness of the formed liquid crystal alignment film is preferably 0.005 to 0.5 μm.
最後に、ナイロン又は綿繊維布が巻き取られたロールで液晶配向膜に対して配向摩擦を行うことで、液晶配向膜が液晶分子に対して配向性を有するようにする。 Finally, alignment friction is performed on the liquid crystal alignment film with a roll wound with nylon or cotton fiber cloth so that the liquid crystal alignment film has alignment properties with respect to the liquid crystal molecules.
（液晶表示素子）
液晶表示素子を形成する方法は、下記の工程を含む。
(Liquid crystal display element)
A method for forming a liquid crystal display element includes the following steps.
まず、前記液晶配向膜を有する一方のガラス基板にフレーム用接着剤を塗布し、前記液晶配向膜を有するもう一方のガラス基板にスペーサーを吹きかける。 First, a frame adhesive is applied to one glass substrate having the liquid crystal alignment film, and a spacer is sprayed onto the other glass substrate having the liquid crystal alignment film.
次に、前記液晶配向膜を有する２枚のガラス基板を、それぞれのフィルム塗布方向が互いに直交するか、又は、互いに平行するように組み合わせる。 Next, the two glass substrates having the liquid crystal alignment film are combined so that their film application directions are orthogonal to each other or parallel to each other.
最後に、２枚のガラス基板の隙間に液晶を注入し、注入口を密封することにより、液晶表示素子を形成することができる。 Finally, a liquid crystal display element can be formed by injecting liquid crystal into a gap between two glass substrates and sealing the injection port.
（液晶表示素子の評価法）
（一）プレチルト角の安定性：液晶（ＺＬＩ‐４７９２）が注入された液晶表示素子を、回転結晶法によってプレチルト角を測定し、測定結果に基づいてプレチルト角の変動率を計算する。具体的には、まず、回転結晶法で液晶表示素子内の９点のプレチルト角測定値を取り、更に９個のプレチルト角測定値のうち最大値と最小値との差をプレチルト角の変動率とする。プレチルト角の変動率が小さいほど、プレチルト角の安定性が高くなることを表す。プレチルト角の変動率が０．１より小さい場合、プレチルト角の安定性を優良と判定し、プレチルト角の変動率が０．１〜０．２である場合、プレチルト角の安定性を中等と判定し、プレチルト角の変動率が０．２より大きい場合、プレチルト角の安定性を劣と判定する。前記回転結晶法は、プレチルト角を測定する従来の慣用方法であり、ここで詳しく述べない。
(Evaluation method for liquid crystal display elements)
(1) Pretilt angle stability: The liquid crystal display element into which the liquid crystal (ZLI-4792) is injected is measured for the pretilt angle by the rotating crystal method, and the variation rate of the pretilt angle is calculated based on the measurement result. Specifically, first, nine pretilt angle measurement values in the liquid crystal display element are obtained by the rotating crystal method, and the difference between the maximum value and the minimum value among the nine pretilt angle measurement values is determined as the rate of change of the pretilt angle. And The smaller the fluctuation rate of the pretilt angle, the higher the stability of the pretilt angle. When the fluctuation rate of the pretilt angle is smaller than 0.1, the stability of the pretilt angle is determined to be excellent, and when the fluctuation rate of the pretilt angle is 0.1 to 0.2, the stability of the pretilt angle is determined to be moderate. If the variation rate of the pretilt angle is greater than 0.2, the stability of the pretilt angle is determined to be inferior. The rotating crystal method is a conventional method for measuring a pretilt angle and will not be described in detail here.
（二）高温でのプレチルト角の変動：液晶配向剤を基板に塗布し、それぞれ２１０℃、２２０℃及び２３０℃で加熱してベーキングし、最後に、液晶表示素子として組み合わせる。回転結晶法で３つの温度でのプレチルト角を測定し、複数の液晶表示素子のそれぞれについて１０点を測定して平均し、最大値と最小値との差を評価の標準として、数値が小さいほど、性質が優れていることを表す。 (2) Fluctuation of pretilt angle at high temperature: A liquid crystal aligning agent is applied to a substrate, heated at 210 ° C., 220 ° C. and 230 ° C. for baking, and finally combined as a liquid crystal display element. The pretilt angles at three temperatures are measured by the rotating crystal method, 10 points are measured and averaged for each of the plurality of liquid crystal display elements, and the difference between the maximum value and the minimum value is used as a standard for evaluation. , Indicating that the properties are excellent.
（三）フィルム塗布性：液晶配向剤をスピンコーティング法でインジウムスズ酸化物（ＩＴＯ）基板に塗布し、オーブンでベーキングを行い、続いて、回転速度１０００回／分、プラットフォーム移動速度６０ｍｍ／ｓ、圧入量０．４μｍで配向フィルム塗布を３回行い、偏光顕微鏡でフィルム塗布された後の液晶配向膜の表面を肉眼観察し、刷毛目及び切削屑が観察されない場合は優良と判定し、刷毛目及び切削屑が観察された場合は劣と判定する。 (3) Film coating property: A liquid crystal aligning agent is applied to an indium tin oxide (ITO) substrate by a spin coating method and baked in an oven, followed by a rotation speed of 1000 times / minute, a platform moving speed of 60 mm / s, The alignment film was applied three times with a press-in amount of 0.4 μm, and the surface of the liquid crystal alignment film after film application with a polarizing microscope was observed with the naked eye. And when cutting waste is observed, it determines with it being inferior.
（四）1Ｈ‐ＮＭＲ：サンプルを取ってＮＭＲ試験管に入れ、トリチウム化クロロホルムでサンプルを溶解させ、ブルカー社（Ｂｒｕｃｋｅｒ Ｃｏｒｐｏｒａｔｉｏｎ）製のＮＭＲアナライザーを用いて測定を行う（型番：Ｗａｔｅｒｓ ２４８７）。 (4) 1 H-NMR: Take a sample, put it in an NMR test tube, dissolve the sample with tritiated chloroform, and perform measurement using an NMR analyzer manufactured by Bruker Corporation (model number: Waters 2487).
（五）重合体分子量の測定：ウォーターズ社（Ｗａｔｅｒｓ Ｃｏｒｐｏｒａｔｉｏｎ）製のゲル浸透クロマトグラフィー（ＧＰＣ）装置を用いて測定し（型番：Ｂｒｕｋｅｒ ＡＶＡＮＣＥ ４００ＭＨｚ）、カラム温度３５℃で、臭化リチウムとリン酸を含有するジメチルホルムアミド（ＤＭＦ）を洗浄液とし、換算することでポリスチレンの時間によって重量平均分子量と数平均分子量が得られる。 (5) Measurement of polymer molecular weight: Measured using a gel permeation chromatography (GPC) apparatus manufactured by Waters Corporation (model number: Bruker AVANCE 400 MHz) at a column temperature of 35 ° C. and lithium bromide and phosphoric acid By using dimethylformamide (DMF) containing as a washing liquid and converting, the weight average molecular weight and the number average molecular weight can be obtained depending on the time of polystyrene.
（実施例）
（一）モノアミン（ａ‐３‐１）、ポリアミド酸誘導体（Ａ‐１）〜（Ａ‐６）及びイミド‐アミド酸共重合体（Ｇ‐１）の合成
(Example)
(1) Synthesis of monoamine (a-3-1), polyamic acid derivatives (A-1) to (A-6) and imido-amide acid copolymer (G-1)
（合成例１：モノアミン（ａ‐３‐１）の合成）
モノアミン（ａ‐３‐１）を合成する反応式は、下記の通りであり、まず、中間生成物（ｗ）を合成し、更に中間生成物（ｗ）によってモノアミン（ａ‐３‐１）を合成した。
The reaction formula for synthesizing the monoamine (a-3-1) is as follows. First, the intermediate product (w) is synthesized, and then the monoamine (a-3-1) is synthesized by the intermediate product (w). Synthesized.
まず、２Ｌの反応フラスコに、１０２ｇ（５５０ｍｍｏｌ）の塩化４‐ニトロベンゾイル、１２００ｇのトルエン及び７５．９ｇ（５５０ｍｍｏｌ）の炭酸カリウムを加え、室温で５分間攪拌した。別に、１２６ｇ（５００ｍｍｏｌ）の４‐（４’‐ｎ‐ペンチル）‐ジシクロへキサノールを２００ｇのトルエンに溶解させ、前記反応フラスコに緩やかに滴下し、全部滴下した後、室温で更に４時間攪拌し、純水を加えて３回抽出し、硫酸マグネシウムで有機層を乾燥させ、ろ過し、濾液をろ過収集し、減圧濃縮で乾燥させて、１８８．５ｇ（４７０ｍｍｏｌ）の中間生成物（ｗ）が得られ、収率は９４％である。中間生成物（ｗ）のスペクトルデータは、1Ｈ ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３） δ８．３０〜８．２３（２Ｈ）、８．１５〜８．２０（２Ｈ）、５．２４〜５．３６（０．６Ｈ）、４．８５〜４．９５（０．４Ｈ）、０．８〜２．１（３０Ｈ）ｐｐｍであった。 First, 102 g (550 mmol) of 4-nitrobenzoyl chloride, 1200 g of toluene and 75.9 g (550 mmol) of potassium carbonate were added to a 2 L reaction flask and stirred at room temperature for 5 minutes. Separately, 126 g (500 mmol) of 4- (4′-n-pentyl) -dicyclohexanol was dissolved in 200 g of toluene, dripped slowly into the reaction flask, and all were dripped, followed by stirring at room temperature for another 4 hours. The organic layer was dried three times with magnesium sulfate, filtered, and the filtrate was collected by filtration and dried under reduced pressure to obtain 188.5 g (470 mmol) of intermediate product (w). The yield is 94%. The spectral data of the intermediate product (w) are as follows: 1 H NMR (400 MHz, CDCl 3) δ 8.30-8.23 (2H), 8.15-8.20 (2H), 5.24-5.36 (0 .6H), 4.85 to 4.95 (0.4H), and 0.8 to 2.1 (30H) ppm.
その後、別の２Ｌの反応フラスコに、１８８．５ｇ（４７０ｍｍｏｌ）の中間生成物（ｗ）、１０００ｇのトルエン、１０ｇの１０％パラジウム炭素触媒（１０％ Ｐａｌｌａｄｉｕｍ‐ｏｎ‐ｃａｒｂｏｎ）を加え、１０分間攪拌した。更に前記反応フラスコに５０ｍＬの８０％ヒドラジン水和物（８０％ Ｈｙｄｒａｚｉｎｅ ｈｙｄｒａｔｅ）を緩やかに滴下し、全部滴下した後、更に４時間攪拌した。反応温度が室温に戻った後、空気を吸引してろ過し、濾液を収集し、減圧濃縮で溶剤を除去して、１７４ｇ（４７０ｍｍｏｌ）のモノアミン（ａ‐３‐１）が得られ、収率は１００％である。モノアミン（ａ‐３‐１）のスペクトルデータは、1Ｈ ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３） δ７．８０〜７．８６（２Ｈ）、６．５８〜６．６５（２Ｈ）、５．１５〜５．２０（０．６Ｈ）、４．７５〜４．８５（０．４Ｈ）、３．９６〜４．０６（２Ｈ）、０．８〜２．１（３０Ｈ）ｐｐｍであった。 Then, 188.5 g (470 mmol) of intermediate product (w), 1000 g of toluene, 10 g of 10% palladium on carbon catalyst (10% Palladium-on-carbon) were added to another 2 L reaction flask and stirred for 10 minutes. did. Furthermore, 50 mL of 80% hydrazine hydrate (80% hydrazine hydrate) was gently added dropwise to the reaction flask, and after all was added dropwise, the mixture was further stirred for 4 hours. After the reaction temperature returned to room temperature, air was sucked and filtered, and the filtrate was collected, and the solvent was removed by concentration under reduced pressure to obtain 174 g (470 mmol) of monoamine (a-3-1). Is 100%. Spectral data of monoamine (a-3-1) is 1 H NMR (400 MHz, CDCl3) δ 7.80-7.86 (2H), 6.58-6.65 (2H), 5.15-5.20. (0.6H), 4.75 to 4.85 (0.4H), 3.96 to 4.06 (2H), and 0.8 to 2.1 (30H) ppm.
（合成例２：ポリアミド酸誘導体（Ａ‐１）の合成）
反応フラスコに、１．４９ｇ（４ｍｍｏｌ）のモノアミン（ａ‐３‐１）及び０．３９ｇ（２ｍｍｏｌ）のテトラカルボン酸二無水物（ａ‐１‐１）を３０ｇのＮ‐メチル‐２‐ピロリドン（ａ‐４‐１‐１）に添加し、室温で２時間攪拌し、次に、反応フラスコにおける生成物を２時間塩化反応させ、続いて７．３７ｇ（２０ｍｍｏｌ）のジアミン（ａ‐２‐１）を加え、２時間攪拌し、最後、３．５３ｇ（１８ｍｍｏｌ）のテトラカルボン酸二無水物（ａ‐１‐１）を添加し、室温で更に３時間攪拌した。反応液を脱イオン水に注入してポリアミド酸誘導体（Ａ‐１）を析出させた後、それを収集し、メタノールを用いて複数回洗浄した後、６０〜７０℃の真空条件で乾燥させた。生成されたポリアミド酸誘導体（Ａ‐１）は数平均分子量（Ｍｎ）が１２０００であり、重量平均分子量が３１０００（Ｍｗ）であった。
(Synthesis Example 2: Synthesis of polyamic acid derivative (A-1))
To the reaction flask, 1.49 g (4 mmol) of monoamine (a-3-1) and 0.39 g (2 mmol) of tetracarboxylic dianhydride (a-1-1) were added to 30 g of N-methyl-2-pyrrolidone. (A-4-1-1) and stirred at room temperature for 2 hours, then the product in the reaction flask was chlorinated for 2 hours, followed by 7.37 g (20 mmol) of diamine (a-2- 1) was added, and the mixture was stirred for 2 hours. Finally, 3.53 g (18 mmol) of tetracarboxylic dianhydride (a-1-1) was added, and the mixture was further stirred at room temperature for 3 hours. The reaction solution was poured into deionized water to precipitate the polyamic acid derivative (A-1), then collected, washed several times with methanol, and then dried under vacuum conditions at 60 to 70 ° C. . The produced polyamic acid derivative (A-1) had a number average molecular weight (Mn) of 12000 and a weight average molecular weight of 31000 (Mw).
（合成例３〜７：ポリアミド酸誘導体（Ａ‐２）〜（Ａ‐６）の合成）
ポリアミド酸誘導体（Ａ‐２）〜（Ａ‐６）の合成原料が各段階において合成例２と異なったものに置換された場合、下記の表１に示し、それ以外、合成工程と条件は、合成例２と同じである。
(Synthesis Examples 3 to 7: Synthesis of polyamic acid derivatives (A-2) to (A-6))
When the synthesis raw materials of the polyamic acid derivatives (A-2) to (A-6) are replaced with those different from those of Synthesis Example 2 at each stage, they are shown in Table 1 below. Otherwise, the synthesis steps and conditions are as follows. The same as Synthesis Example 2.
（合成例８：イミド‐アミド酸共重合体（Ｇ‐１）の合成）
反応フラスコに、４．９０ｇ（２５ｍｍｏｌ）のテトラカルボン酸二無水物（ａ‐１‐１）、１３．５１ｇ（４５ｍｍｏｌ）のテトラカルボン酸二無水物（ａ‐１‐２）、５．４５ｇ（２５ｍｍｏｌ）のテトラカルボン酸二無水物（ａ‐１‐３）及び３６．８４ｇ（１００ｍｍｏｌ）のジアミン（ａ‐２‐１）を２４３ｇのＮ‐メチル‐２‐ピロリドン（ａ‐４‐１‐１）に順次添加し、固形分の含有量２０ｗｔ％の溶液を調製し、４０℃〜５０℃の温度で４時間〜５時間反応して、ポリアミド酸を含む溶液が得られる。１４ｇのピリジン及び８ｇの無水酢酸を前記のポリアミド酸溶液に添加し、１００℃〜１１０℃で３〜４時間脱水閉環反応させた。得られた溶液をメタノールに注入して析出させ、イミド‐アミド酸共重合体（Ｇ‐１）が得られ、最後に、イミド‐アミド酸共重合体（Ｇ‐１）をメタノールで洗浄した後、減圧条件で乾燥させた。生成されたイミド‐アミド酸共重合体（Ｇ‐１）は数平均分子量が２２０００であり、重量平均分子量が６２０００であった。
(Synthesis Example 8: Synthesis of Imido-Amic Acid Copolymer (G-1))
4.90 g (25 mmol) of tetracarboxylic dianhydride (a-1-1), 13.51 g (45 mmol) of tetracarboxylic dianhydride (a-1-2), 5.45 g ( 25 mmol) of tetracarboxylic dianhydride (a-1-3) and 36.84 g (100 mmol) of diamine (a-2-1) were added to 243 g of N-methyl-2-pyrrolidone (a-4-1-1) ), A solution having a solid content of 20 wt% is prepared, and reacted at a temperature of 40 ° C. to 50 ° C. for 4 hours to 5 hours to obtain a solution containing polyamic acid. 14 g of pyridine and 8 g of acetic anhydride were added to the polyamic acid solution, followed by a dehydration ring closure reaction at 100 to 110 ° C. for 3 to 4 hours. The obtained solution was poured into methanol and precipitated to obtain an imide-amide acid copolymer (G-1), and finally, the imide-amide acid copolymer (G-1) was washed with methanol. And dried under reduced pressure conditions. The resulting imide-amide acid copolymer (G-1) had a number average molecular weight of 22,000 and a weight average molecular weight of 62,000.
（二）実施例１〜実施例１２の液晶配向剤の調製及び実験方法： (2) Preparation and experimental methods of liquid crystal aligning agents of Examples 1 to 12:
ポリアミド酸誘導体（Ａ‐１）〜（Ａ‐６）及びイミド‐アミド酸共重合体（Ｇ‐１）等の重合体を、表２に示す割合でγ‐ブチロラクトンとＮ‐メチル‐２‐ピロリドンの混合溶剤に溶解させ、固形分の含有量６ｗｔ％の溶液に調製し、直径０．４５μｍのフィルタでろ過して、収集した濾液を本実施形態の液晶配向剤の実施例１〜実施例１２とする。 Polymers such as the polyamic acid derivatives (A-1) to (A-6) and the imide-amide acid copolymer (G-1) are converted into γ-butyrolactone and N-methyl-2-pyrrolidone in the proportions shown in Table 2. In a mixed solvent, and a solution having a solid content of 6 wt% is prepared, filtered through a filter having a diameter of 0.45 μm, and the collected filtrate is used in Examples 1 to 12 of the liquid crystal aligning agent of the present embodiment. And
前記各実施例の液晶配向剤をロール印刷機によってガラス基板に塗布し、２００℃の加熱板で２０分間乾燥させ、厚さ０．０８μｍのフィルムを形成した。このフィルムは、ロール回転速度１０００回／分、プラットフォーム移動速度６０ｍｍ／ｓ、圧入量０．４μｍで配向摩擦を行った。 The liquid crystal aligning agent of each said Example was apply | coated to the glass substrate with the roll printer, and it dried for 20 minutes with the 200 degreeC heating plate, and formed the film with a thickness of 0.08 micrometer. This film was subjected to orientation friction at a roll rotation speed of 1000 times / minute, a platform moving speed of 60 mm / s, and a press-fit amount of 0.4 μm.
続いて、前記液晶配向膜を有するガラス基板にフレーム用接着剤を塗布し、前記液晶配向膜を有する別のガラス基板にスペーサーを吹きかけ、続いて、液晶配向膜を有する２枚のガラス基板を、それぞれのフィルム塗布方向が互いに直交するように組み合わせ、さらに、２つのガラス基板の隙間に液晶（ＺＬＩ‐４７９２）を注入し、注入口を密封して、液晶表示素子を形成した。 Subsequently, a frame adhesive is applied to the glass substrate having the liquid crystal alignment film, a spacer is sprayed on another glass substrate having the liquid crystal alignment film, and then two glass substrates having the liquid crystal alignment film are obtained. The film coating directions were combined so that the directions were perpendicular to each other, and liquid crystal (ZLI-4792) was injected into the gap between the two glass substrates, and the injection port was sealed to form a liquid crystal display element.
得られた液晶表示素子に対して、プレチルト角、プレチルト角の安定度及びフィルム塗布性の評価を行った。評価結果は、表２に示す通りである。 The obtained liquid crystal display element was evaluated for pretilt angle, stability of pretilt angle, and film coatability. The evaluation results are as shown in Table 2.
表２から分かるように、実施例１〜実施例１２は、何れもプレチルト角の安定度が中等以上であり、高温でのプレチルト角の変動が最大で０．２４までであり、何れもフィルム塗布性が優良である。このことから、本実施形態では、液晶配向剤にポリアミド酸誘導体（Ａ）を添加することによって、製造された液晶配向膜が安定したプレチルト角及び優れたフィルム塗布性を有するようにすることができることが分かる。 As can be seen from Table 2, in all of Examples 1 to 12, the stability of the pretilt angle is moderate or higher, and the fluctuation of the pretilt angle at a high temperature is up to 0.24. Sex is excellent. Therefore, in this embodiment, by adding the polyamic acid derivative (A) to the liquid crystal aligning agent, the manufactured liquid crystal aligning film can have a stable pretilt angle and excellent film coatability. I understand.
表２において、実施例６及び実施例１０はプレチルト角の安定度が中等である以外、他の実施例は何れもプレチルト角の安定度が優良である。詳しく見ると、実施例１〜５、実施例７〜９、実施例１１〜１２のポリアミド酸誘導体（Ａ）の含有量は何れも、実施例６及び実施例１０の含有量より高く、即ち、ポリアミド酸誘導体（Ａ）は、液晶配向膜のプレチルト角の安定度を改善できることを意味する。 In Table 2, the stability of the pretilt angle is excellent in Examples 6 and 10, except that the stability of the pretilt angle is moderate. In detail, the contents of the polyamic acid derivatives (A) in Examples 1 to 5, Examples 7 to 9, and Examples 11 to 12 are all higher than those in Examples 6 and 10, that is, The polyamic acid derivative (A) means that the stability of the pretilt angle of the liquid crystal alignment film can be improved.
上記実施形態から分かるように、本発明は、液晶配向剤にポリアミド酸誘導体（Ａ）又はポリアミド酸誘導体（Ｂ）を添加することによって、液晶配向剤により製造された液晶配向膜が安定したプレチルト角及び優れたフィルム塗布性を有するようにし、液晶表示素子の結像品質を改善して、市場の需要を満たすことができる。 As can be seen from the above-described embodiment, the present invention provides a stable pretilt angle of the liquid crystal alignment film produced with the liquid crystal aligning agent by adding the polyamic acid derivative (A) or the polyamic acid derivative (B) to the liquid crystal aligning agent. In addition, it is possible to satisfy the market demand by improving the imaging quality of the liquid crystal display element by having excellent film coatability.
本発明は前述の通りに実施形態により開示されたが、これは本発明を限定するものではなく、当業者であれば、本発明の精神と範囲から逸脱しない限り、多様の変更や修飾を加えることができる。従って、本発明の保護範囲は、特許請求の範囲で指定したものを基準とするべきである。 Although the present invention has been disclosed by the embodiments as described above, this does not limit the present invention, and various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present invention. be able to. Therefore, the protection scope of the present invention should be based on what is specified in the claims.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW102110675 | 2013-03-26 | ||
| TW102110675A TWI480314B (en) | 2013-03-26 | 2013-03-26 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device having thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014191352A true JP2014191352A (en) | 2014-10-06 |
| JP5833698B2 JP5833698B2 (en) | 2015-12-16 |
Family
ID=51594877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014061641A Active JP5833698B2 (en) | 2013-03-26 | 2014-03-25 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5833698B2 (en) |
| CN (1) | CN104073261B (en) |
| TW (1) | TWI480314B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017009655A (en) * | 2015-06-17 | 2017-01-12 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, and polymer |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108885375B (en) | 2016-11-28 | 2021-05-18 | 株式会社Lg化学 | Liquid crystal alignment film, method for preparing the same, and liquid crystal display device using the same |
| KR102065718B1 (en) | 2017-10-17 | 2020-02-11 | 주식회사 엘지화학 | Liquid crystal alignment film and liquid crystal display using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62297819A (en) * | 1986-06-18 | 1987-12-25 | Nissan Chem Ind Ltd | Orientating agent for liquid crystal cell |
| JPH01180518A (en) * | 1988-01-12 | 1989-07-18 | Nissan Chem Ind Ltd | Orientation treating agent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4013052B2 (en) * | 2002-09-25 | 2007-11-28 | 日産化学工業株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| CN100437301C (en) * | 2004-02-26 | 2008-11-26 | 日产化学工业株式会社 | Liquid crystal aligning agent for photoalignment and liquid crystal display device utilizing the same |
| TWI395769B (en) * | 2006-03-22 | 2013-05-11 | Jsr Corp | Liquid crystal alignment agent and method for forming liquid crystal alignment film |
| KR100913605B1 (en) * | 2007-12-07 | 2009-08-26 | 제일모직주식회사 | Photoalignment agent of liquid crystal, photoalignment film of liquid crystal including the same, and liquid crystal display including the same |
| TWI591097B (en) * | 2011-10-25 | 2017-07-11 | 達興材料股份有限公司 | Liquid crystal alignment agent |
-
2013
- 2013-03-26 TW TW102110675A patent/TWI480314B/en active
-
2014
- 2014-03-24 CN CN201410110716.7A patent/CN104073261B/en active Active
- 2014-03-25 JP JP2014061641A patent/JP5833698B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62297819A (en) * | 1986-06-18 | 1987-12-25 | Nissan Chem Ind Ltd | Orientating agent for liquid crystal cell |
| JPH01180518A (en) * | 1988-01-12 | 1989-07-18 | Nissan Chem Ind Ltd | Orientation treating agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017009655A (en) * | 2015-06-17 | 2017-01-12 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, and polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5833698B2 (en) | 2015-12-16 |
| CN104073261B (en) | 2016-02-24 |
| TWI480314B (en) | 2015-04-11 |
| TW201437261A (en) | 2014-10-01 |
| CN104073261A (en) | 2014-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5120580B1 (en) | Liquid crystal alignment agent | |
| JP5365563B2 (en) | Liquid crystal alignment solution | |
| KR101905897B1 (en) | Diamines, liquid crystal aligning agents, liquid crystal alignment layers and liquid crystal display devices | |
| TW200900389A (en) | 3, 4-Dicarboxy-1, 2, 3, 4-tetrahydro-6-t-butyl-1-naphthalene-succinic dianhydride and liquid crystal aligning agent comprising polyimide resin prepared from the dianhydride | |
| CN102241990B (en) | Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display element, polyamide acids and polyimides | |
| JP5359029B2 (en) | Acid dianhydride, liquid crystal alignment film, and liquid crystal display element | |
| CN102732262A (en) | Liquid crystal aligning agent | |
| JP5873529B2 (en) | Siloxane dianhydride, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| CN102171604A (en) | Liquid crystal aligning agent and liquid crystal display element using same | |
| JP5833698B2 (en) | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element thereof | |
| TWI591097B (en) | Liquid crystal alignment agent | |
| JP6974800B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element | |
| JP4152986B2 (en) | Diamine compound having dendron side chain and liquid crystal alignment material produced using the same | |
| TWI798503B (en) | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, liquid crystal display using the same | |
| CN109970975B (en) | High-voltage-holding-ratio polyimide and preparation method and application thereof | |
| JP6247180B2 (en) | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element | |
| JP5894566B2 (en) | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using the same | |
| JP5865423B2 (en) | Diamine compound, liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element | |
| JP5919411B2 (en) | Siloxane-containing dianhydride, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device | |
| KR101108611B1 (en) | Composition for liquid crystal aligning, liquid crystal aligning film manufactured by the same, and liquid crystal display comprising the same | |
| CN113583241A (en) | Liquid crystal orientation agent and application thereof | |
| JP2004075944A (en) | Polyimide of which orientation is regulated, liquid crystal-oriented film using the same and liquid crystal display element | |
| CN104448298B (en) | Polymer, liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display module | |
| CN114058384A (en) | Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box | |
| TW202405140A (en) | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal element using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150226 |
|
| 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: 20150917 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20150918 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20151029 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5833698 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 |