TW201125896A - Liquid crystal aligning agents, liquid crystal aligning layers and liquid crystal display devices - Google Patents

Liquid crystal aligning agents, liquid crystal aligning layers and liquid crystal display devices Download PDF

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TW201125896A
TW201125896A TW100102716A TW100102716A TW201125896A TW 201125896 A TW201125896 A TW 201125896A TW 100102716 A TW100102716 A TW 100102716A TW 100102716 A TW100102716 A TW 100102716A TW 201125896 A TW201125896 A TW 201125896A
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liquid crystal
crystal alignment
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diamines
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Yuko Katano
Fumitaka Kondo
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Chisso Corp
Chisso Petrochemical Corp
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56Aligning agents
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723Polyimide, polyamide-imide

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

A liquid crystal alignment agent containing a polyamic acid is used to form a liquid crystal alignment layer having a small residual DC, wherein the polyamic acid is obtained by reacting an amine of formula (P), or a mixture of an amine of formula (P) and other amine, with a tetracarboxylic dianhydride. An LCD device without occurrence of burn-in can be obtained by suitably using the liquid crystal alignment layer. The ring P is pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine- 2,5-diyl or pyrazine-2,5-diyl, and k is 0 or 1; but when k=0, the ring P is pyridine-2,5-diyl or pyrimidine-2,5-diyl. The bonding position of amino is position-5 in these rings.

Description

201125896 六、發明說明: 【發明所屬之技術領域】 本發明關於一種含有如下聚醯胺酸或其衍生物的液晶 配向劑,此聚醯胺酸是使具有含1或2個氮原子的芳香環 的二胺與四羧酸二酐反應而得的。本發明並關於一種由此 液晶配向劑而得的液晶配向膜,以及具有此液晶配向膜的 液晶顯示元件。 【先前技術】 液晶顯示元件從筆電或桌上型電腦的顯示器開始,用 於攝影機的觀景窗、投影顯示器等各種液晶顯示裝置中, 最近也開始作為電視用顯示元件而被大量使用。另外,還 可以用作光學印頭、光學傅立葉轉換元件、光學閥(light valve)等光電子相關元件。先前液晶顯示元件的主流是使 用向列型液晶的顯示元件,而扭轉9〇。的扭轉向列(TN) 型液晶顯示元件,通常扭轉18〇。以上的超扭轉向列(stn) 型液晶顯示元件,使用薄膜電晶體的薄膜電晶體(TFT) 型液晶顯示元件已經實用化。 然而,這些液晶顯示元件具有如下的缺點:可適當視 認影像的視角窄,且當自斜方向觀看時,產生亮度或對比 度降低,以及半色調的亮度反轉。近年來,關於該視角問 題’有利用如下技術進行改良:使用光學補償膜的TN型 液晶顯示元件、並應用垂直配向與突起結構物的技術的多 (Multi-domain Vertical Alignment » MVA) 型液晶顯示元件,或者橫向電場方式的共面切換(Ιη·ρ_ 201125896201125896 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent containing a polyglycine or a derivative thereof, which is an aromatic ring having 1 or 2 nitrogen atoms The diamine is reacted with a tetracarboxylic dianhydride. The present invention relates to a liquid crystal alignment film obtained by the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. [Prior Art] The liquid crystal display element has been widely used as a display element for televisions, and has recently been used as a display element for televisions, starting from a display of a notebook or a desktop computer, and for various liquid crystal display devices such as a viewing window and a projection display of a video camera. In addition, it can also be used as an optoelectronic related component such as an optical head, an optical Fourier transform element, or a light valve. The mainstream of the prior liquid crystal display elements was a display element using nematic liquid crystal, and the twist was 9 Å. A twisted nematic (TN) type liquid crystal display element, usually twisted 18 turns. The above-described super twisted nematic (stn) type liquid crystal display element has been put into practical use as a thin film transistor (TFT) type liquid crystal display element using a thin film transistor. However, these liquid crystal display elements have disadvantages in that the viewing angle of the image can be appropriately recognized, and when viewed from the oblique direction, luminance or contrast is lowered, and luminance inversion of halftones is generated. In recent years, the problem of the viewing angle has been improved by the following techniques: a TN type liquid crystal display element using an optical compensation film, and a multi-domain vertical Alignment (MVA) type liquid crystal display using a vertical alignment and protrusion structure. Coplanar switching of components, or transverse electric field methods (Ιη·ρ_ 201125896

Switching,IPS)型液晶顯示元件等,這些改良的技術正 在實用化(例如參照專利文獻1〜3 )。 液晶顯示元件技術的發展不僅是其驅動方式和元件結 構的改良,還可藉由顯示元件所使用的構成部件的改良來 達成。在顯示元件所使用的構成部件中,特別是液晶配向 膜是關係到元件顯示品質的重要因素之一,隨著液晶顯示 元件的高品質化,液晶配向膜的作用逐年變得重要起來。 作為為提高液晶顯示元件的顯示品質而對液晶配向膜 要求的重要特性,例如殘留直流電位(Residual DC)。如果 殘留DC大,則即使在施加電壓後關閉(〇FF)電壓亦會 殘留消去的圖像,產生所謂的「殘像(residuaHmage)」。曰 θ為嘗試解決殘像’提出了使用含有硫晴的聚酿亞胺 而提供儲存電荷(stC)red eh啡)少的液晶_元件的液晶 配向劑(例如參照專利文獻4)。 另提出了紫外光照射與液晶配向劑的組合,此液晶配 向劑含有含射骨架的㈣胺酸(例如參照專利文獻5)。 這些先前技術,對於作為需要進一步改良的如今液晶 形成用的液晶配向劑’用以獲得所得液晶配向膜 =乳特性或者用以獲得所期望的電氣特性的材料方面, 尚存在進一步研究的餘地。 [先前技術文獻]:[專利文獻]: 專利文獻1:日本專利特公昭63_21907號公報 專利文獻2:日本專利特開平6_16〇878號公報 專利文獻3:曰本專利特開平9_1565〇號公報 201125896 f利文獻4:日本專利特開平Mao77號公報 【發Sir:日本專利特開平6·7號公報 [發明欲解決的問題] 1發明目的在提供一種殘留DC小的液晶配向膜,以 可形成所述液晶配向膜的聚醯胺酸及聚醯亞胺系聚合 物’使用所述聚合物而形成的配向膜,以及適用該配向膜 而不產生燒入(bura-in)的液晶顯示元件。 [解決問題的手段] ^發明者等發現,在液晶配向劑中使用含有聚醯胺酸 (以分子内具有含1或2個氮的芳雜環的二胺為原料)或其 衍生物的組成物時,具有由此液晶配向劑形成的液晶配向 膜的液晶顯示元件可達成低殘留DC,從而完成本發明。 本發明的液晶配向劑如以下第[1]項所述。 Π].—種液晶配向劑’其含有選自由如下聚醯胺酸及其 衍生物所構成的群組的至少一種聚合物,其中聚酿胺酸是 由式(P)表示的二胺,或者式(P)表示的二胺和其他二胺之混 合物與四羧酸二酐反應而得的:These improved technologies are being put into practical use (for example, refer to Patent Documents 1 to 3). The development of the liquid crystal display element technology is not only an improvement of its driving method and component structure, but also an improvement of the constituent components used for the display element. Among the constituent members used for the display element, in particular, the liquid crystal alignment film is one of the important factors related to the display quality of the element. With the improvement of the quality of the liquid crystal display element, the role of the liquid crystal alignment film has become important year by year. An important characteristic required for the liquid crystal alignment film to improve the display quality of the liquid crystal display element is, for example, a residual DC potential (Residual DC). If the residual DC is large, even if the voltage is turned off (〇FF) after the voltage is applied, the erased image remains, and a so-called "residuaHmage" is generated.曰 θ is a liquid crystal alignment agent which provides a liquid crystal element having a small storage charge (stC) red eh morphine by using a sulphur-containing melamine to solve the afterimage (see, for example, Patent Document 4). Further, a combination of ultraviolet light irradiation and a liquid crystal alignment agent containing a (tetra)amine acid containing a shot skeleton is proposed (for example, refer to Patent Document 5). These prior art have room for further research as a material for obtaining a liquid crystal alignment film for liquid crystal formation which is required to be further improved to obtain the obtained liquid crystal alignment film = milk characteristics or to obtain desired electrical characteristics. [Prior Art Document]: [Patent Document] Patent Document 1: Japanese Patent Publication No. Sho 63_21907, Patent Document 2: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei. No. Hei. No. Hei. A polyphthalamide and a polyimine-based polymer of a liquid crystal alignment film 'an alignment film formed using the polymer, and a liquid crystal display element to which the alignment film is applied without causing a bura-in. [Means for Solving the Problem] The inventors found that a composition containing polylysine (a diamine having an aromatic heterocyclic ring having 1 or 2 nitrogens as a raw material) or a derivative thereof is used in a liquid crystal alignment agent. In the case of the liquid crystal display element having the liquid crystal alignment film formed by the liquid crystal alignment agent, low residual DC can be achieved, thereby completing the present invention. The liquid crystal alignment agent of the present invention is as described in the item [1] below. a liquid crystal alignment agent which contains at least one polymer selected from the group consisting of polylysines and derivatives thereof, wherein the poly-aracine is a diamine represented by the formula (P), or A mixture of a diamine and another diamine represented by the formula (P) and a tetracarboxylic dianhydride are obtained by reacting:

其中% P 為〇比咬-2,5-二基、塔°秦-3,6-:S(pyridazin-3,6-diyl )、嘧啶-2,5-二基或吡嗪-2,5-二基(pyrazin_ 2,5-diyl) ; k為0或1 ;當k=0時,環P為π比咬_2,5_二基 或嘧啶-2,5-二基,且這些環中氨基的鍵結位置為5位。 201125896 [發明的效果] 利用本發明,可提供—種殘留j)C低,適用於各種驅 動方式的液晶顯示元件。 【實施方式】 首先說明本說明書中所使用的術語。Wherein % P is a bismuth-2,5-diyl, tahe-3,6-:S (pyridazin-3,6-diyl), pyrimidine-2,5-diyl or pyrazine-2,5 -pyridin_ 2,5-diyl; k is 0 or 1; when k=0, ring P is π than bite 2,5-diyl or pyrimidine-2,5-diyl, and these rings The bonding position of the amino group is 5 bits. [Effect of the Invention] According to the present invention, it is possible to provide a liquid crystal display element which is low in residual j) C and is applicable to various driving methods. [Embodiment] First, terms used in the present specification will be described.

有時將式(P)表示的二胺簡稱為二胺(p)。其他式所表示 的二胺也同樣地簡稱。有時將式(1)表示的四羧酸二酐簡稱 p為酸酐(1)。其他式所表示的四羧酸二酐也同樣地簡稱。 (甲基)丙烯醯氧基」是丙烯醯氧基及曱基丙烯醯氧基的總 稱,「(曱基)丙烯酸酯」是丙烯酸酯及曱基丙烯酸酯的總 稱,「(曱基)丙烯酸」是丙烯酸及曱基丙烯酸的總稱。 說月化予結構式時使用的術語「任意的」表示不僅位 置任意而且個數也任意。而且,例如「任意的A可被B、 C或D取代」的表達意指:至少一個a可被b取代、至少 個A可被C取代、至少—個A可被D取代,或者多個 ^可被B〜D的至少2個取代。然巾,於任意的_Ch2_可被 j基取辦’並^;包料_乡個偶被洲的基取代 的情況°Ph表示亞苯基,Me表示甲基。 並未與構成_韻任意__確地之取代基表 置在並無化學性問題的範_是自由的。於化 P) 下,矣土 < )在夕個式中使用相同記號的情況 :義ΪΓΓΪ所表示的環、結合基或末端基具有相同的 疋義㈣’但並不表示在所有式中必須同時是奴義範圍 201125896 内的相同的基。在多個式中可以是相同的基’也可以是每 個式中不同的基。 本發明由所述第[1]項和如下第[2]〜[21]項而構成。 [2].如第[1]項所述之液晶配向劑’其中式(p)表示的二 胺為式(P-1)〜(P-10)表示的二胺的至少一種:The diamine represented by the formula (P) is sometimes simply referred to as a diamine (p). The diamine represented by the other formula is also abbreviated as such. The tetracarboxylic dianhydride represented by the formula (1) may be abbreviated as p (anhydride). The tetracarboxylic dianhydride represented by the other formula is also abbreviated as such. (Meth) propylene oxime is a general term for acryloxy and decyl propylene oxime. "(Mercapto) acrylate" is a general term for acrylate and methacrylate, "(fluorenyl) acrylate" It is a general term for acrylic acid and mercaptoacrylic acid. The term "arbitrary" as used in the description of the structural formula means that the position is arbitrary and the number is arbitrary. Moreover, the expression "arbitrary A may be substituted by B, C or D" means that at least one a may be substituted by b, at least one A may be replaced by C, at least one A may be replaced by D, or a plurality of ^ It can be substituted by at least 2 of B~D. However, in the case where any _Ch2_ can be taken as a base and replaced by a base of the _Ch 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is not free from the fact that there is no chemical problem with the substituents that constitute the _ rhyme arbitrary __. In the case of P), bauxite <) uses the same notation in the evening formula: the ring, the binding group or the terminal group represented by the scorpion has the same ambiguity (four) 'but does not mean that it must be in all formulas At the same time, it is the same base within the scope of slavery 201125896. It may be the same base in a plurality of formulas or may be a different base in each formula. The present invention is constituted by the above item [1] and the following items [2] to [21]. [2] The liquid crystal alignment agent according to the item [1] wherein the diamine represented by the formula (p) is at least one of the diamines represented by the formulae (P-1) to (P-10):

[3] .如第[2]項所述之液晶配向劑’其中式(P)表示的二 胺為式(P-5)及(P-8)表示的二胺的至少一種。 [4] .如第[1]〜[3]項中任一項所述之液晶配向劑,其中其 他二胺為選自式(VIII)及(X)〜(XIII)表示的具有側鏈基的二 胺的群組的至少一種二胺: R1[3] The liquid crystal alignment agent according to [2], wherein the diamine represented by the formula (P) is at least one of the diamines represented by the formulae (P-5) and (P-8). [4] The liquid crystal alignment agent according to any one of [1] to [3] wherein the other diamine is selected from the group consisting of the formula (VIII) and (X) to (XIII) having a side chain group. At least one diamine of the group of diamines: R1

式(VIII)中,A3 為單鍵、_〇_、_c〇_、c〇〇_、_〇c〇_、_c〇nh-、 201125896 -CH2O-、-CF^O-或碳數1〜6的亞烧基,該亞烧基中任意的 -CH2_可被-0-、-CH=CH-或-OC-取代;R1為具有類固醇 骨架的基、碳數3〜30的烷基、具有碳數1〜30的烷基或碳 數1〜30的烷氧基作為取代基的苯基,或式(IX)表示的基, 該碳數3〜30的烷基中任意的-CH2-可被-Ο-、-CH = CH-或 -OC-取代;In the formula (VIII), A3 is a single bond, _〇_, _c〇_, c〇〇_, _〇c〇_, _c〇nh-, 201125896-CH2O-, -CF^O- or carbon number 1~ a mercapto group of 6, wherein any -CH2_ in the alkylene group may be substituted by -0, -CH=CH- or -OC-; R1 is a group having a steroid skeleton, an alkyl group having 3 to 30 carbon atoms, a phenyl group having an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms as a substituent, or a group represented by the formula (IX), and any -CH2- of the alkyl group having 3 to 30 carbon atoms. Can be replaced by -Ο-, -CH = CH- or -OC-;

式(IX)中,A4 及 A5 獨立為單鍵、-0-、-COO-、-0C0-、 •CONH-、碳數1〜4的亞烷基、碳數1〜3的氧亞烷基,或 碳數1〜3的亞烷氧基;環B及環c獨立為1,4-亞苯基或1,4-亞環己基;R2及R3獨立為氟或曱基,f及g獨立為〇、1 或2 ; c、d及e獨立為〇〜2的整數,c、d及e的合計為1 以上;當c為2時,2個環B可相同也可以不同,2個A4 可為相同的結合基也可以為不同的結合基;當d為2時,2 個A5可為相同的結合基也可以為不同的結合基;當e為2 時,2個環C可相同也可以不同;R4為碳數1〜30的烷基、 碳數1〜30的烷氧基,或碳數2〜30的烷氧烷基,於這些烷 基、院氧基及烷氧烷基中,任意的氫可被氟取代;In the formula (IX), A4 and A5 are independently a single bond, -0-, -COO-, -0C0-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and an oxyalkylene group having 1 to 3 carbon atoms. Or an alkyleneoxy group having a carbon number of 1 to 3; the ring B and the ring c are independently a 1,4-phenylene group or a 1,4-cyclohexylene group; R2 and R3 are independently a fluorine or a fluorenyl group, and f and g are independently 〇, 1 or 2; c, d and e are independent integers of 〇~2, and the total of c, d and e is 1 or more; when c is 2, 2 rings B may be the same or different, 2 A4 The same binding group may also be a different binding group; when d is 2, 2 A5 may be the same binding group or different bonding groups; when e is 2, 2 rings C may be the same R4 may be an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an alkoxyalkyl group having 2 to 30 carbon atoms, among these alkyl groups, the alkoxy group and the alkoxyalkyl group. Any hydrogen can be replaced by fluorine;

0-A6 (X) 2011258960-A6 (X) 201125896

式(X)及(XI)中’ R5獨立為氫或甲基;R6為氫、碳數1〜20 的烷基或碳數2〜20的烯基;R7及R8獨立為碳數1〜20的 烷基’或苯基;A6獨立為單鍵、-CO-或-CH2-;In the formulae (X) and (XI), 'R5 is independently hydrogen or methyl; R6 is hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms; and R7 and R8 are independently a carbon number of 1 to 20 Alkyl' or phenyl; A6 is independently a single bond, -CO- or -CH2-;

式(XII)及(XIII)中,R9為曱基或碳數2〜30的烷基,該烷基 中任意的-CH2-可被-〇-、_CH = CH-或-OC-取代;R1Q為碳 數6〜22的烧基;R11為碳數1〜22的烧基;A7獨立為-0-或 碳數1〜6的亞烷基;A8為單鍵或碳數1〜3的亞烷基;環T 為1,4-亞本基或1,4-亞環己基;h為0或1。 [5].如第[4]項所述之液晶配向劑,其中其他二胺為選 自式(VIII-2)、(νΐΙΙ-4)〜(νΐΠ-6)、(ΧΠ-2)、(XII-4)及(XII-6) 表示的二胺的至少一種: 201125896In the formulae (XII) and (XIII), R9 is a fluorenyl group or an alkyl group having 2 to 30 carbon atoms, and any -CH2- of the alkyl group may be substituted by -〇-, _CH=CH- or -OC-; R1Q a carbon number of 6 to 22; R11 is a carbon number of 1 to 22; A7 is independently -0- or an alkylene group having 1 to 6 carbon atoms; and A8 is a single bond or a carbon number of 1 to 3 Alkyl; ring T is 1,4-subunit or 1,4-cyclohexylene; h is 0 or 1. [5] The liquid crystal alignment agent according to [4], wherein the other diamine is selected from the group consisting of formula (VIII-2), (νΐΙΙ-4)~(νΐΠ-6), (ΧΠ-2), ( At least one of the diamines represented by XII-4) and (XII-6): 201125896

(XII-6) 這些式中,R23、R29及R30獨立為碳數1〜30的烷基’或碳(XII-6) In the formula, R23, R29 and R30 are independently an alkyl group having a carbon number of 1 to 30 or carbon.

數1〜30的烷氧基。 [6].如第[1]〜[3]項中任一項所述之液晶配向劑’其中其 他二胺為如下二胺的混合物:選自第[4]項所述之具有側鏈 基的二胺的群組的至少一種,以及選自式(I)〜(VII)及(XV) 表示的不具侧鏈基的二胺的群組的至少一種; H2N—X—NH2 /h h2n ^nh2 (Η) 11 201125896Alkoxy groups having a number of from 1 to 30. [6] The liquid crystal alignment agent according to any one of [1] to [3] wherein the other diamine is a mixture of diamines having a side chain group selected from the group [4]. At least one of the group of diamines, and at least one selected from the group consisting of diamines having no side chain groups represented by formulas (I) to (VII) and (XV); H2N-X-NH2 /h h2n ^ Nh2 (Η) 11 201125896

H2NH2N

ΝΗ·ΝΗ·

H2N Ο (III) (IV) h2n nh2H2N Ο (III) (IV) h2n nh2

(V) h2n nh2(V) h2n nh2

(VI) nh2 h2n(VI) nh2 h2n

R33 I Si—O I R34 (VII)R33 I Si-O I R34 (VII)

H2N——A3H2N - A3

R33 Si-A3-NH2 I R34 (XV)R33 Si-A3-NH2 I R34 (XV)

這些式中,X為碳數2〜12的直鏈亞烷基;Y獨立為單鍵、 -0-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-C(CH3)2-、 -C(CF3)2-、-0_(CH2)t-0-、-S-、-S-S-、-S02-、-S-(CH2)t-S-或碳數1〜12的直鏈亞烷基,t為1〜12的整數;Z1及Z2為 氫,但當 Y 為-NH-、-N(CH3)-、-CH2-、-C(CH3)2-或-C(CF3)2-時也可以相互鍵結而形成單鍵;環D為亞笨基或1,4-二氮 雜亞環己基;R33及R34獨立為碳數1〜3的烷基,或苯基;. A3獨立為碳數1〜6的亞烷基、亞苯基或被烷基取代的亞笨 基,in為1〜10的整數,環己炫*壞或本ί哀上任意的氫可被 氟、曱基、三氟曱基、-OH、-COOH、-S03H、-Ρ〇3Η2、 苄基或羥基爷基取代。 [7].如第[6]項所述之液晶配向劑,其中其他二胺為如 12 201125896 下二胺的混合物:選自式(VIII-2)、(VIII-4)〜(VIII-6)、 (XII-2)、(XII-4)及(XII-6)表示的具有側鏈基的二胺的至少 一種,以及選自式(IV-1)、(IV-2)、(IV-15)〜(IV-17)、(V-1)〜 (V-12)、(V-33)、(V-35)〜(V-37)、(VI-7)、(VII-2)及(XV-1) 表示的不具側鏈基的二胺的至少一種;In these formulas, X is a linear alkylene group having 2 to 12 carbon atoms; Y is independently a single bond, -0-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO- , -C(CH3)2-, -C(CF3)2-, -0_(CH2)t-0-, -S-, -SS-, -S02-, -S-(CH2)tS- or carbon number a linear alkylene group of 1 to 12, t is an integer of 1 to 12; Z1 and Z2 are hydrogen, but when Y is -NH-, -N(CH3)-, -CH2-, -C(CH3)2- Or -C(CF3)2- may also be bonded to each other to form a single bond; ring D is a strepto or 1,4-diazacyclohexylene; and R33 and R34 are independently an alkyl group having 1 to 3 carbon atoms. , or phenyl; A3 is independently an alkylene group having 1 to 6 carbon atoms, a phenylene group or a sub-phenyl group substituted by an alkyl group, and an in 1 to 10 integer, which is a ring or a sorrowful Any hydrogen may be substituted by fluorine, sulfhydryl, trifluoromethyl, -OH, -COOH, -S03H, -3,2, benzyl or hydroxy. [7] The liquid crystal alignment agent according to [6], wherein the other diamine is a mixture of diamines such as 12 201125896: selected from the group consisting of formula (VIII-2), (VIII-4) to (VIII-6) And at least one of a diamine having a side chain group represented by (XII-2), (XII-4) and (XII-6), and selected from the group consisting of formula (IV-1), (IV-2), (IV) -15)~(IV-17), (V-1)~(V-12), (V-33), (V-35)~(V-37), (VI-7), (VII-2 And at least one of the diamines having no side chain groups represented by (XV-1);

(VIII-2) (VIH-4)(VIII-2) (VIH-4)

(VIII-5) (VIII-6)(VIII-5) (VIII-6)

這些式中,R23、R29及R3G獨立為碳數1〜30的烷基,或碳 數1〜30的烷氧基。 H2N—nh2 (IV-1)In the above formula, R23, R29 and R3G are independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. H2N-nh2 (IV-1)

(IV-16) 13 201125896(IV-16) 13 201125896

(V-4) (V-5) (V-β)(V-4) (V-5) (V-β)

(V-10)(V-10)

(V-11)(V-11)

(V-12)(V-12)

h2nH2n

(V-36) (V-35)(V-36) (V-35)

(V-37) (VI-7) H2N-H〇/VN0^CH2^0/X〇_NH2 H2N-C3H6-Si-〇-Si-C3H6-NH2 ch3 ch3 [8]·如第[1]項所述之液晶配向劑,其中該聚合物是如 下化合物的混合物:使選自第[2]項所述之式(P-UKpqo) 表示的二胺的群組的至少一種及選自第[4]項所述之具有 側鏈基的二胺的群組的至少一種的混合物與四羧酸二酐反 應而得的聚醯胺酸或其衍生物;以及使選自第[6]項所述之 不具側鏈基的二胺的群組的至少—種與讀酸三酐反應而 得的聚醯胺酸或其衍生物。 201125896 [9].如第[1]項所述之液晶配向劑,其中該聚合物是如 下化合物的混合物:使選自第[2]項所述之式(P-1)〜(P_10) 表示的二胺的群組的至少一種及選自第[4]項所述之具有 側鏈基的二胺的群組的至少一種的混合物與四羧酸二針反 應而得的聚醯胺酸或其衍生物;以及使選自第[6]項所述之 不具側鏈基的二胺的群組的至少一種及選自式(P_1)〜 (P-10)表示的二胺的群組的至少一種的混合物與四叛酸二 酐反應而得的聚醯胺酸或其衍生物。 ’ [10].如第[1]項所述之液晶配向劑,其中該聚合物是如 下化合物的混合物:使由選自第[2]項所述之式(P-l)~(p-10) 表示的二胺的群組的至少一種及選自第[4]項所述之具有 側鏈基的二胺的群組的至少一種以及選自第[6]項所述之 不具側鏈基的二胺的群組的至少一種所構成的混合物與四 羧酸二酐反應而得的聚醯胺酸或其衍生物;以及使上述不 具側鏈基的二胺的至少一種與四羧酸二酐反應而得的聚醯 胺酸或其衍生物。 _ [11].如第[1]項所述之液晶配向劑,其中該聚合物是如 下化合物的混合物:使由選自第[2]項所述之式(p-1)〜(P-10) 所表示的二胺的群組的至少一種及選自第[4]項所述之具 有側鏈基的二胺的群組的至少一種以及選自第[6]頊所述 之不具側鏈基的二胺的群組的至少一種所構成的混合物與 四緩酸二針反應而得的聚醯胺酸或其衍生物;以及使選自 上述不具側鏈基的二胺的群組的至少一種及選自式(P-1)〜 (P-10)表示的二胺的群組的至少一種的混合物與四辣酸一 15 201125896 針反應而得的聚醯胺酸或其衍生物。 [12] .如第[1]項所述之液晶配向劑,其中該聚合物是如 下化合物的混合物:使選自第[2]項所述之式(P-1)〜(P-10) 表示的二胺的群組的至少一種及選自第[6]項所述之不具 側鏈基的二胺的群組的至少一種的混合物與四羧酸二酐反 應而得的聚醯胺酸或其衍生物;以及使選自第[4]項所述之 具有侧鏈基的二胺的群組的至少一種與四羧酸二酐反應而 得的聚醯胺酸或其衍生物。 [13] .如第[1]項所述之液晶配向劑,其中該聚合物是如 下化合物的混合物:使選自第[2]項所述之式(ρ_ι)〜(p_1〇) 表示的二胺的群組的至少一種及選自第[6]項所述之不具 侧鏈基的二胺的群組的至少一種的混合物與四羧酸二酐反 應而得的聚醯胺酸或其衍生物;以及使由選自第[4]項所述 之具有側鏈基的二胺的群組的至少一種及選自所述不具侧 鏈基的二胺的群組的至少一種所構成的混合物與四羧酸二 軒反應而得的聚醯胺酸或其衍生物。 Π4].如第[1]〜[13]項中任一項所述之液晶配向劑,其中 四羧酸二酐為芳香族四羧酸二酐之至少一種,或者芳香族 四羧酸二酐之至少一種與芳香族以外的四羧酸二酐的至少 一種的混合物。 [15]·如第[1]〜[13]項中任一項所述之液晶配向劑,其中 四 $酸二酐為式(H-1)、(H-5)、(H 8)〜(H1〇)及(H 22)表示 的芳香族四羧酸二酐之至少一種: 201125896(V-37) (VI-7) H2N-H〇/VN0^CH2^0/X〇_NH2 H2N-C3H6-Si-〇-Si-C3H6-NH2 ch3 ch3 [8]·Article [1] The liquid crystal alignment agent, wherein the polymer is a mixture of at least one selected from the group consisting of diamines represented by the formula (P-UKpqo) described in the item [2] and selected from the group [4] a polyamido acid or a derivative thereof obtained by reacting a mixture of at least one of the group of diamines having a side chain group and a tetracarboxylic dianhydride; and the selected from the item [6] At least one of the group of diamines having no side chain groups is a polylysine or a derivative thereof obtained by reacting with a reading acid anhydride. The liquid crystal alignment agent according to the item [1], wherein the polymer is a mixture of the following compounds: (P-1) to (P_10) represented by the item [2] a mixture of at least one of the group of diamines and a mixture of at least one selected from the group consisting of diamines having a side chain group described in the item [4] and a poly-proline which is reacted with two needles of tetracarboxylic acid or a derivative thereof; and at least one selected from the group consisting of diamines having no side chain group described in the item [6] and a group selected from the group consisting of diamines represented by the formulae (P_1) to (P-10) Polylysine or a derivative thereof obtained by reacting at least one mixture with tetra-baric acid dianhydride. [10] The liquid crystal alignment agent according to [1], wherein the polymer is a mixture of the following compounds: (Pl) to (p-10) selected from the item [2] At least one selected from the group consisting of diamines and at least one selected from the group consisting of diamines having a side chain group described in Item [4] and selected from the group [6] having no side chain groups Polylysine or a derivative thereof obtained by reacting at least one of a mixture of diamines with a tetracarboxylic dianhydride; and at least one of the above diamine having no side chain group and tetracarboxylic dianhydride The polylysine or its derivative obtained by the reaction. The liquid crystal alignment agent according to the item [1], wherein the polymer is a mixture of compounds obtained by the formula (p-1) to (P-) selected from the item [2]. 10) at least one selected from the group consisting of diamines and at least one selected from the group consisting of diamines having a side chain group described in the item [4] and not having a side selected from the group [6] a polyglycine or a derivative thereof obtained by reacting at least one of a group of diamines of a chain group with a two-needle acid; and a group selected from the group of diamines having no side chain group described above At least one and a polyglycine or a derivative thereof obtained by reacting a mixture of at least one selected from the group consisting of diamines represented by the formulae (P-1) to (P-10) with a tetrahydro acid- 15 201125896 needle. [12] The liquid crystal alignment agent according to [1], wherein the polymer is a mixture of the following compounds: (P-1) to (P-10) selected from the item [2] Polylysine obtained by reacting a mixture of at least one selected from the group consisting of diamines and at least one selected from the group consisting of diamines having no side chain groups described in item [6] with tetracarboxylic dianhydride Or a derivative thereof; and a polyamic acid or a derivative thereof obtained by reacting at least one selected from the group consisting of diamines having a side chain group described in the item [4] with a tetracarboxylic dianhydride. [13] The liquid crystal alignment agent according to [1], wherein the polymer is a mixture of the following compounds: a formula selected from the formula (ρ_ι) to (p_1〇) described in the item [2] Polylysine obtained by reacting at least one of a group of amines and at least one selected from the group consisting of diamines having no side chain group described in item [6] with a tetracarboxylic dianhydride or a derivative thereof And a mixture of at least one selected from the group consisting of diamines having a side chain group described in the item [4] and at least one selected from the group consisting of the diamines having no side chain groups; Polylysine or a derivative thereof obtained by reacting with a tetracarboxylic acid. The liquid crystal alignment agent according to any one of [1] to [13] wherein the tetracarboxylic dianhydride is at least one of aromatic tetracarboxylic dianhydride or aromatic tetracarboxylic dianhydride. A mixture of at least one of at least one of tetracarboxylic dianhydrides other than aromatic. [15] The liquid crystal alignment agent according to any one of [1] to [13] wherein the four acid dianhydrides are of the formula (H-1), (H-5), (H8)~ At least one of aromatic tetracarboxylic dianhydrides represented by (H1〇) and (H 22): 201125896

[16]·如第[1]〜[π]項中任一項所述之液晶配向劑,其中 四敌酸二肝為式(H-1)表示的芳香族四敌酸二酐: 0 0[16] The liquid crystal alignment agent according to any one of [1] to [[pi]], wherein the dihydro acid is an aromatic tetrahydro acid dianhydride represented by the formula (H-1): 0 0

Ο 0Ο 0

[17].如第[1]〜[13]項中任一項所述之液晶配向劑,其中 四羧酸二酐為如下化合物的混合物:式(Η-1)、(Η-5)、(Η-8)〜 (H-10)及(H-22)表示的芳香族四羧酸二酐之至少一種;以及 式(S-l)、(S-6)、(S-9)〜(S-10)、(S-21)〜(S-22)、(S-30)、(S-43)〜 (S-45)、(S-48)及(S-52)表示的芳香族以外的四羧酸二酐的 至少一種。The liquid crystal alignment agent of any one of [1] to [13], wherein the tetracarboxylic dianhydride is a mixture of the following compounds: formula (Η-1), (Η-5), (Η-8)~ at least one of aromatic tetracarboxylic dianhydrides represented by (H-10) and (H-22); and formula (S1), (S-6), (S-9) to (S) -10), (S-21) to (S-22), (S-30), (S-43) to (S-45), (S-48), and (S-52) At least one of tetracarboxylic dianhydrides.

Ο 〇 r\Ο 〇 r\

(H-10) (H-22) 17 201125896 - · - r(H-10) (H-22) 17 201125896 - · - r

, (S-48) w [18].如第[17]項所述之液晶配向劑,_中芳香族以外 的四羧酸二 為式(S-1)'(s_6)、(s_9)、(s_45)、(S-48;^(s、5 表示的化合物的至少一種。 [19] ·如第[17]項所述之液晶配向劑,其中芳香族四羧 酸二酐為式(H-1)表示的化合物,芳香族以外的四羧酸二酐 為式(S-1)及(S-48)表示的化合物的至少一種。 [20] . —種液晶配向膜,其藉由對第υΗθ]項中任一項 所述之液晶配向劑的塗膜進行加熱而形成。 [21] ·—種液晶顯示元件’其具有:一對基板、形成於 該對基板之間的液晶層、對液晶層施加電壓的電極,以及 第[20]項所述之液晶配向膜。 本發明的液晶配向劑是含有選自聚酿胺酸與其衍生物 所構成的群組的至少一種聚合物的組成物。聚醯胺酸的衍 生物例如:1)使聚醯胺酸進行完全脫水閉環反應而得的聚 酿亞胺、2)使聚醯胺酸進行部分脫水閉環反應而得的部分 201125896 使 酿亞胺化聚臨胺酸、3)聚酿胺酸g旨、4)將四幾 一部分換成二羧酸而得的聚醯胺酸_聚醯胺共聚物、5酐的 該聚醯胺酸-聚醯胺共聚物之一部分或全部進行脫水 反應而得的聚醯胺-醯亞胺。這些化合物中較佳者為聚二= 胺及部力酿亞胺化聚酿胺酸,更佳為聚酿亞胺。^除了實 例的以下說明中’若無特別限定,則使用「聚醯胺酸」作 為聚酿胺酸及其衍生物的總稱。[S-48] w [18]. The liquid crystal alignment agent according to [17], wherein the tetracarboxylic acid other than the aromatic group is the formula (S-1)' (s_6), (s_9), (S_45), (S-48; ^ (s, 5), at least one of the compounds of the formula [17]. The liquid crystal alignment agent according to [17], wherein the aromatic tetracarboxylic dianhydride is of the formula (H) The compound represented by the formula -1), the tetracarboxylic dianhydride other than the aromatic compound is at least one of the compounds represented by the formulae (S-1) and (S-48). [20] . A liquid crystal alignment film by which The coating film of the liquid crystal alignment agent according to any one of the above-mentioned items, wherein the liquid crystal display element has a pair of substrates, a liquid crystal layer formed between the pair of substrates, An electrode for applying a voltage to a liquid crystal layer, and a liquid crystal alignment film according to item [20]. The liquid crystal alignment agent of the present invention is a composition containing at least one polymer selected from the group consisting of polyacrylic acid and a derivative thereof. A derivative of polylysine, for example, 1) a polyanilin obtained by subjecting polylysine to a complete dehydration ring-closure reaction, 2) a part obtained by partially dehydrating a ring closure reaction of polylysine 201125896 The polyamidonic acid-polyamine copolymer and the 5-anhydride of the polyaniline obtained by replacing the four amines with the dicarboxylic acid A polyamido-imine which is obtained by partially or completely dehydrating one of the amine acid-polyamide copolymer. Preferred among these compounds are polydiamines and leucovorized polyamines, more preferably polyamidiamines. In the following description of the examples, 'polyamine' is used as a general term for poly-aracine and its derivatives unless otherwise specified.

而且,該聚合物為使選自式(P)表示的二胺的群組的至 少一種二胺’或者該(些)二胺和不以式(P)表示的其他二 胺的混合物與四羧酸二針反應得的聚醯胺酸或其衍生物。Further, the polymer is a mixture of at least one diamine selected from the group consisting of diamines represented by formula (P) or a mixture of the diamine(s) and other diamines not represented by formula (P) with tetracarboxylic acid Poly-proline or its derivative obtained by the reaction of acid two needles.

(P) 環P為吡啶-2,5-二基、β荅嗪_3,6-二基、嘧啶-2,5-二基或吡 噃-2,5-二基’較佳為η比咬_2,5_二基或塔嗪-3,6-二基。而且’ k為0或1。即,二胺(ρ)為2環成3環化合物,但於為2 環時,環P為在5位與氨基鍵姑的吨啶-2,5·二基、或者在 5位與氨基鍵結的嘧咬_2 5-二基。 二胺(Ρ)的較佳例如下所示。這些二胺中更佳者為二胺 (Ρ-5)及(Ρ-8) 〇(P) Ring P is pyridine-2,5-diyl, β-pyridazine_3,6-diyl, pyrimidine-2,5-diyl or pyridin-2,5-diyl' preferably η ratio Bite _2,5-diyl or tazin-3,6-diyl. And 'k is 0 or 1. That is, the diamine (ρ) is a 2-ring compound, but when it is a 2-ring, the ring P is a toluidine-2,5·diyl group at the 5-position with an amino bond, or an amino bond at the 5-position. The knot of pyrimidine _2 5-diyl. Preferred examples of the diamine (oxime) are shown below. More preferred of these diamines are diamines (Ρ-5) and (Ρ-8) 〇

νη2 (Ρ-2) (Ρ-4)Ηη2 (Ρ-2) (Ρ-4)

(P-6) ΝΗ2 201125896(P-6) ΝΗ 2 201125896

一胺(p)可以已知方法製造。例如,可利用CN1733736A 公報或CN101338462A公報中記載的方法。 製造本發明的液晶配向劑所用的聚醯胺酸時的原料二 胺可僅是選自二胺(P)的群組的至少一種二胺,亦可進一步 含有這些二胺以外的其他二胺的至少一種。亦即,關於選 自一fec(P)的群組的二胺的使用比例,如以在聚醯胺酸製造 時所用二胺原料中所佔比例來看,較佳為1〇〜咖m〇1%, ^佳為30〜100 m〇l%。藉由設為所述使用比例,即可於液 晶顯示元件中實現所期望的殘留DC。 所述其他二胺依其結構不同可分為2種。亦即,將連 結2個氨基的骨架視為主鏈時,為具有自主鏈分支的基(即 =鏈基)的二胺和不具側鏈基的二胺。使具有側鏈基的二 ,與四羧酸二酐進行反應,即可獲得相對於聚合物主鏈而 η有許多側鏈基的聚醯胺酸。使用此種相對於聚合物主鏈 而言有側鏈基㈣_断,由含有該聚合物的液晶配向 劑形成的液晶配向膜可增大液晶顯示元件的預傾角。即’ 該側鏈基具有增大刪肖的效果。具有雜絲的侧鍵基 肩為碳數3以上的基,具體例如:碳數3以上的烷基、破 數3以上的烷氧基、碳數3以上的烷氧基烷基,以及具有 類固醇骨架的基。具有—個以上環,且其末端的環具有碳 數1以上的烷基、碳數丨以上的烷氧基及碳數2以上的烷 20 201125896 具有側鍵基的效果。 這些側鏈基的二胺稱為二型=了^中右有時將具有 具側鏈基的二胺稱為非側鏈型二胺。,有時將此種不 而且,將側鏈型二胺與非側鏈 :=上:=示元件各自所需要的Γ於 乂 TN或VA方式為代表的縱向電場方式需要The monoamine (p) can be produced by a known method. For example, the method described in CN1733736A or CN101338462A can be used. The raw material diamine in the case of producing the polyamic acid used in the liquid crystal alignment agent of the present invention may be at least one diamine selected from the group consisting of diamines (P), and may further contain other diamines other than these diamines. At least one. That is, the ratio of use of the diamine selected from the group of fec(P), for example, in the proportion of the diamine raw material used in the production of polylysine, is preferably 1 〇 to 咖 m〇 1%, ^ good for 30~100 m〇l%. By setting the use ratio, the desired residual DC can be achieved in the liquid crystal display element. The other diamines can be classified into two types depending on their structures. That is, when the skeleton in which two amino groups are bonded is regarded as a main chain, it is a diamine having a radical (i.e., a chain group) and a diamine having no side chain group. By reacting a dimer having a side chain group with a tetracarboxylic dianhydride, a polylysine having a plurality of side chain groups relative to the polymer main chain can be obtained. By using such a side chain group (four) with respect to the polymer main chain, the liquid crystal alignment film formed of the liquid crystal alignment agent containing the polymer can increase the pretilt angle of the liquid crystal display element. That is, the side chain group has an effect of increasing the splaying. The side bond shoulder having a heterofilament is a group having 3 or more carbon atoms, and specifically, for example, an alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, an alkoxyalkyl group having 3 or more carbon atoms, and a steroid having a steroid The base of the skeleton. The ring having one or more rings and having a terminal having a carbon number of 1 or more, an alkoxy group having a carbon number of 丨 or more, and an alkane having a carbon number of 2 or more 20 201125896 have an effect of having a side bond group. The diamines of these side chain groups are referred to as di-types. In the right, the diamine having a side chain group is sometimes referred to as a non-side chain type diamine. In some cases, it is necessary to combine the side chain type diamine with the non-side chain: = upper: = each element requires a vertical electric field as represented by the 乂 TN or VA mode.

=,因此主要使用側鏈型二胺。此時為進—步控制預傾角, =可以併用非側鏈型二胺。非側鏈型二胺與側鏈型二胺的 調配比例可依目標預傾角的大小來決定。#然藉 配向劑 選擇侧鏈基’也可以僅使關鏈型二贿對應。^橫向& 場方式中’預傾角小,且需要高的液晶配向性,因此可使 用非側鏈型二胺的至少一種。由此,本發明的液 可適用於任意種類的液晶顯示元件中。 侧鏈基的具體例如下所述。 首先,可例舉:烷基、烷氧基、烷氧烷基、烷羰基、 烷羰氧基、烷氧羰基、烷氨羰基、烯基、烯氧基、烯羰基、 烯羰氧基、烯氧羰基、烯氨羰基、炔基、炔氧基、炔羰基、 炔羰氧基、炔氧羰基、炔氨羰基等。而且,這些基中的烧 基、烯基以及炔基均為碳數為3以上的基。然而,於烧氧 基烷基中,整體的碳數為3以上即可。而且,這些基可為 直鏈狀,也可以為分支鏈狀。 其次,以末端的環具有碳數1以上的烷基、碳數1以 上的烷氧基或碳數2以上的烷氧烷基作為取代基為條件, 21 201125896 可例舉:笨基、苯烷基、苯烷氧基、苯氧基、苯羰基、苯 叛氧基、苯氧羰基、笨氨羰基、苯基環己基氧基、碳數為 3以上的環烷基、環己基烷基、環己基氧基、環己基氧羰 基、環己基苯基、環己基苯烷基、環己基苯氧基、雙(環己 基)氧基、雙(環己基)烧基、雙(環己基)苯基、雙(環己基) 苯烷基、雙(環己基)氧羰基、雙(環己基)苯氧羰基,以及環 己基雙(苯基)氧羰基等環狀結構基。 另亦可例舉集合環基,其為具有2個以上苯環的基、 具有2個以上環己烷環的基,或由苯環以及環己烷環所構 成的2環以上的基’且結合基獨立為單鍵、_〇---c〇0-、 •OCO-、-CONH-或碳數為1〜3的亞烷基,末端的環具有碳 數1以上的烷基、碳數1以上的氟取代烷基、碳數丨以上 的烷氧基,或碳數2以上的烷氧烷基作為取代基。這些取 代基的碳數上限並無特別限制,考慮製造成本和物性來決 定即可。具有類固醇骨架的基也可以有效地作為側鏈基。 側鏈型二胺的較佳例為式(νιΙΙα (χ)〜(ΧΠΙ)表示者。= Therefore, a side chain type diamine is mainly used. At this time, the pretilt angle is controlled in advance, and the non-side chain type diamine can be used in combination. The ratio of the non-side chain type diamine to the side chain type diamine can be determined depending on the target pretilt angle. #然借配剂 Selecting the side chain base ' can also only make the chain type bribe. In the lateral & field mode, the pretilt angle is small and a high liquid crystal alignment property is required, so that at least one of non-side chain type diamines can be used. Thus, the liquid of the present invention can be applied to any type of liquid crystal display element. Specific examples of the side chain group are as follows. First, an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkenyl group, an alkenyloxy group, an alkenecarbonyl group, an alkenecarbonyl group, an alkene group can be exemplified. Oxycarbonyl, enaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylcarbonyl, and the like. Further, the alkyl group, the alkenyl group and the alkynyl group in these groups are each a group having a carbon number of 3 or more. However, in the alkyl group, the total carbon number is preferably 3 or more. Further, these groups may be linear or branched. Next, the terminal ring has an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms as a substituent, and 21 201125896 may, for example, be a stupid group or a benzene group. Base, phenylalkoxy, phenoxy, phenylcarbonyl, phenyloxyl, phenoxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, ring Hexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenoxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkyl, bis(cyclohexyl)phenyl, A cyclic structural group such as bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenoxycarbonyl, or cyclohexylbis(phenyl)oxycarbonyl. Further, a collection ring group which is a group having two or more benzene rings, a group having two or more cyclohexane rings, or a group having two or more rings of a benzene ring and a cyclohexane ring is also exemplified. The binding group is independently a single bond, _〇---c〇0-, •OCO-, -CONH- or an alkylene group having a carbon number of 1 to 3, and the terminal ring has an alkyl group having 1 or more carbon atoms and a carbon number. 1 or more of a fluorine-substituted alkyl group, an alkoxy group having a carbon number of 丨 or more, or an alkoxyalkyl group having 2 or more carbon atoms is used as a substituent. The upper limit of the carbon number of these substituents is not particularly limited, and may be determined in consideration of manufacturing cost and physical properties. A group having a steroid skeleton can also be effectively used as a side chain group. A preferred example of the side chain type diamine is represented by the formula (νιΙΙα (χ)~(ΧΠΙ).

式(VIII)中,Α3 為單鍵、-〇-、-CO-、-coo-、-OCO-、 、-CH20-、-CF2〇-或碳數1〜6的亞烧基,該亞燒 基中任意的-CHr·可被-0·、-CH=CH-或-OC-取代。A3的 較佳例為單鍵、-〇 COO-、-0C0-、-CH20-及碳數1〜3 22 201125896 的亞烷基,特佳例為單鍵、c〇〇_、_〇c〇-、_CH2〇_、 -CH2-及·CH2CHr。!^為具有類有^ 3〜30的烷基、碳數沁孙的烷基或碳數卜川的烷氧基作為 取代基的笨基’或者式(Ιχ)表示的基,該碳數3〜3〇的烧基 中任意的-CHr可被_〇_、取代。Rl的較 佳例為具有碳數3〜30的烷基、碳數卜川的烷基或碳數 1〜3〇3的烷氧基作為取代基的笨基,以及式(ιχ)表示的基。 於Α3的鍵結位置為i位時,2個氨基的與苯環的鍵結位置 較佳為3位與5位,或者2位與5位。In the formula (VIII), Α3 is a single bond, -〇-, -CO-, -coo-, -OCO-, -CH20-, -CF2〇- or a mercapto group having a carbon number of 1 to 6, the sub-sinter Any -CHr· in the group may be substituted by -0, -CH=CH- or -OC-. Preferred examples of A3 are a single bond, -〇COO-, -0C0-, -CH20-, and an alkylene group having a carbon number of 1 to 3 22 201125896, and a particularly preferred example is a single bond, c〇〇_, _〇c〇 -, _CH2〇_, -CH2- and ·CH2CHr. ! ^ is a group represented by an alkyl group having an alkyl group having 3 to 30 carbon atoms, an alkyl group having a carbon number, or an alkoxy group having a carbon number as a substituent, or a formula (Ιχ), the carbon number 3~ Any -CHr in the 3-inch alkyl group can be replaced by _〇_. A preferred example of R1 is a styl group having an alkyl group having 3 to 30 carbon atoms, an alkyl group having a carbon number of SiO 2 or an alkoxy group having 1 to 3 〇 3 as a substituent, and a group represented by the formula (ι) . When the bonding position of the indole 3 is the i position, the bonding position of the two amino groups to the benzene ring is preferably 3 or 5 or 2 or 5.

式(IX)中,A4及A5獨立為單鍵、_〇…c〇〇-、-〇CO-、 -CONH-、碳數1〜4的亞烷基、碳數丨〜3的氧亞烷基,或 碳數1〜3的亞烷氧基,較佳為單鍵或碳數丨〜4的亞烷基。 環B及環C獨立為1,4-亞苯基或L4-亞環己基。R2及r3 _ 獨立為氟或甲基。f及g獨立為0、1或2,較佳為0。c、 d及e獨立為〇〜2的整數’且c、d及e合計為1以上。另 當c為2時,2個環B可相同也可以不同,2個A4可為相 同的結合基也可以為不同的結合基。當d為2時,2個A5 可為相同的結合基也可以為不同的結合基。而且,當e為 2時,2個環C可相同也可以不同。R4為碳數卜川的烷基、 碳數1〜30的烷氧基,或碳數2〜30的烷氧烷基,於這些烷 基、烷氧基及烷氧烷基中,任意的氫可被氟取代。R4的較 佳例為碳數1〜30的烷基及碳數1〜3〇的烷氧基。 23 201125896In the formula (IX), A4 and A5 are independently a single bond, _〇...c〇〇-, -〇CO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and an oxyalkylene having a carbon number of 丨3. The group, or an alkyleneoxy group having 1 to 3 carbon atoms, is preferably a single bond or an alkylene group having a carbon number of 丨4. Ring B and Ring C are independently 1,4-phenylene or L4-cyclohexylene. R2 and r3 _ are independently fluorine or methyl. f and g are independently 0, 1, or 2, preferably 0. c, d and e are independently an integer 〇~2 and c, d and e are 1 or more in total. When c is 2, the two rings B may be the same or different, and the two A4 may be the same binding group or different bonding groups. When d is 2, two A5 groups may be the same binding group or different binding groups. Moreover, when e is 2, the two rings C may be the same or different. R4 is an alkyl group of a carbon number, an alkoxy group having 1 to 30 carbon atoms, or an alkoxyalkyl group having a carbon number of 2 to 30, and any hydrogen in the alkyl group, the alkoxy group and the alkoxyalkyl group. Can be replaced by fluorine. A preferred example of R4 is an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. 23 201125896

式(X)及(XI)中’ R5獨立為氫或曱基。R6為氫、碳數 1〜20的烧基或碳數2〜20的稀基。R7及R8分別獨立為碳數 1〜20的烷基或苯基。A6獨立為單鍵、-C0_或_CHr。式(X) 中,較佳2個“NH2_Ph-A6-0-”中的一個鍵結於類固醇骨架 的3位上,另一個鍵結於6位上。而且,2個氨基的與笨 環的鍵結位置均較佳相對於A6的鍵結位置而言為間位或 對位。式(XI)中,2個“NH2_(R8-)Ph-A6-〇-,,的與苯環的鍵結 位置均較佳為相對於類固醇骨架所鍵結之碳而言為間位或 對位。而且,2個氨基的與苯環的鍵結位置均較佳相對於 A6的鍵結位置而言為間位或對位。 、In the formulae (X) and (XI), 'R5 is independently hydrogen or a fluorenyl group. R6 is hydrogen, a carbon group having 1 to 20 carbon atoms or a rare carbon group having 2 to 20 carbon atoms. R7 and R8 are each independently an alkyl group having 1 to 20 carbon atoms or a phenyl group. A6 is independently a single key, -C0_ or _CHr. In the formula (X), preferably one of the two "NH2_Ph-A6-0-" is bonded to the 3-position of the steroid skeleton, and the other is bonded to the 6-position. Further, the bonding positions of the two amino groups and the stupid ring are preferably meta or para position with respect to the bonding position of A6. In the formula (XI), the bonding positions of the two "NH2_(R8-)Ph-A6-〇-, and the benzene ring are preferably meta or opposite to the carbon bonded to the steroid skeleton. Further, the bonding positions of the two amino groups to the benzene ring are preferably meta or para position relative to the bonding position of A6.

〇nh2 ⑽) 24 201125896 R1〇 R11 H2N-r〇nh2 (10)) 24 201125896 R1〇 R11 H2N-r

式(XII)及(XIII)中’ R為碳數1〜3〇的烧基,該烷基中 任意的-CH2·可被-Ο-、-CH=CH-或-esc-取代。R10為碳數 6〜22的烧基’ R"為碳數μ的燒基。八7獨立為_〇或破 數姚基。A8為單鍵或碳數1〜3的魏基。環T為 1,4-亞本基或Μ_亞環己基。h為 氨基的與苯環的鍵结位詈始祕去/1 而言為間錢騎。晴於A7的鍵結位置 結位置均巍為相肺2個祕的與苯環的鍵 -士;a的鍵結位置而言為間位或對位。 - Mviii)的具_如下所示。 • 121^ (Vlll-2)In the formulae (XII) and (XIII), R is a decyl group having 1 to 3 carbon atoms, and any -CH2· in the alkyl group may be substituted by -Ο-, -CH=CH- or -esc-. R10 is a carbon group having a carbon number of 6 to 22, and R" is a carbon atom-based alkyl group. Eight 7 independent for _ 〇 or broken number Yao Ji. A8 is a single bond or a Wei group having a carbon number of 1 to 3. Ring T is a 1,4-subunit or a fluorene-cyclohexylene group. h is the bond between the amino group and the benzene ring, and it is a secret ride. The junction position of A7 is clearer. The knot position is the key of the phase lung and the bond of the benzene ring. The bond position of a is meta or para. - Mviii) has the following _. • 121^ (Vlll-2)

(VMM) H2N(VMM) H2N

(VIII-3) H2N0"c"OKX>r23 R23 h2n(VIII-3) H2N0"c"OKX>r23 R23 h2n

25 201125896 h2n h2n \ > ^R23 y h2n (VIII-9) h2n (VIII-10) ) > -R23 h2n (VIII-11) 式(VIII-l)〜(VIII-ll)中,R23為碳數1〜30的烷基或碳 數1〜30的烷氧基,較佳為碳數3〜25的烷基或碳數3〜25 的院氧基。 r2525 201125896 h2n h2n \ > ^R23 y h2n (VIII-9) h2n (VIII-10) ) > -R23 h2n (VIII-11) In the formula (VIII-l)~(VIII-ll), R23 is carbon The alkyl group having 1 to 30 carbon atoms or the alkoxy group having 1 to 30 carbon atoms is preferably an alkyl group having 3 to 25 carbon atoms or a tertiary alkyl group having 3 to 25 carbon atoms. R25

R25 /R25 /

'c=〇'c=〇

R25 0=CR25 0=C

5 XX JL X LI H2N' ^ΆνΗ2 HzN-^^NHz h2n^^nh2 η2ν^^νη2 (VIII-12) (VIII-13) (VIII-14) (VIII-15) r26 〇〆 R26 u.NH2 uNH2 (VIII-16) (VIII-17) 式(VIII-12)〜(VIII-17)中,R25為碳數4〜30的烷基,較 佳為碳數6〜25的烷基。R26為碳數6〜30的烷基,較佳為 碳數8〜25的烷基。 h2n h2n 0^\>27 0^K>27 H2N (VIII-19) h2n -r28 h2N (VI11-21) (VIII-18) H2N ,w"…、 H2N A/III_1Q\ H2N h2n H2N (VIII-20) H2N (VIM-21) 26 2011258965 XX JL X LI H2N' ^ΆνΗ2 HzN-^^NHz h2n^^nh2 η2ν^^νη2 (VIII-12) (VIII-13) (VIII-14) (VIII-15) r26 〇〆R26 u.NH2 uNH2 (VIII-16) (VIII-17) In the formulae (VIII-12) to (VIII-17), R25 is an alkyl group having 4 to 30 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms. R26 is an alkyl group having 6 to 30 carbon atoms, preferably an alkyl group having 8 to 25 carbon atoms. H2n h2n 0^\>27 0^K>27 H2N (VIII-19) h2n -r28 h2N (VI11-21) (VIII-18) H2N ,w"..., H2N A/III_1Q\ H2N h2n H2N (VIII- 20) H2N (VIM-21) 26 201125896

h2nH2n

(VIII-23)(VIII-23)

R27 (VIII-28) R·R27 (VIII-28) R·

27 (VIII-31) (VIII-32)27 (VIII-31) (VIII-32)

R‘ 27R‘ 27

CH3 ch3 I I Si-O-Si-R27 I I ch3 ch3 (VIII-37) 式(VIII-18)〜(VIII-37)中,R27為碳數1〜30的烷基或碳 數1〜30的烷氧基,較佳為碳數3〜25的烷基或碳數3〜25 27 201125896 的烷氧基。R28為氫、氟、碳數1〜30的烷基、碳數1〜30 的烷氧基、-ON、-OCH2F、-OCHF2或-OCF3,較佳為碳 數3〜25的烷基,或碳數3〜25的烷氧基。CH3 ch3 II Si-O-Si-R27 II ch3 ch3 (VIII-37) In the formula (VIII-18) to (VIII-37), R27 is an alkyl group having 1 to 30 carbon atoms or an alkyl group having 1 to 30 carbon atoms. The oxy group is preferably an alkyl group having a carbon number of 3 to 25 or an alkoxy group having a carbon number of 3 to 25 27 201125896. R28 is hydrogen, fluorine, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -ON, -OCH2F, -OCHF2 or -OCF3, preferably an alkyl group having 3 to 25 carbon atoms, or Alkoxy group having a carbon number of 3 to 25.

上述二胺(VIII-1)〜(VIII-43)中,較佳為二胺(VIII-1)〜 (VIII-11),更佳為二胺(VIII-2)及(νΐΠ_4)〜(νΐΙΙ-6)。 二胺(X)的具體例如下所示。 28 201125896Among the above diamines (VIII-1) to (VIII-43), preferred are diamines (VIII-1) to (VIII-11), more preferably diamines (VIII-2) and (νΐΠ_4) to (νΐΙΙ). -6). Specific examples of the diamine (X) are shown below. 28 201125896

29 20112589629 201125896

30 20112589630 201125896

R23 R29 二胺(XII)的具體例如下所示。Specific examples of the R23 R29 diamine (XII) are shown below.

R29R29

31 201125896 R3031 201125896 R30

式(XII-1)〜(XII-3)中,R29為碳數1〜30的烷基或碳數 1〜30的烷氧基,較佳為碳數3〜30的烷基或碳數3〜30的烷 氧基。式(XII-4)〜(XII-8)中,R3Q為碳數1〜30的烷基或碳數 32 201125896 1〜30的烷氧基’較佳為碳數3〜30的烷基或碳數3〜3〇的烷 氧基。 疋 一胺(XIII)的具體例如下所示。 h2nIn the formulae (XII-1) to (XII-3), R29 is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 3 to 30 carbon atoms or a carbon number of 3 ~30 alkoxy groups. In the formula (XII-4) to (XII-8), R3Q is an alkyl group having 1 to 30 carbon atoms or a carbon number of 32. 201125896 1 to 30 alkoxy group is preferably an alkyl group having 3 to 30 carbon atoms or carbon. Alkoxy groups of 3 to 3 Å. Specific examples of the monoamine (XIII) are shown below. H2n

nh2 nh2 h2nNh2 nh2 h2n

(XIII-3)(XIII-3)

式(XIII-I)〜(xiii-3)中’ r31為碳數6〜22的烷基,較佳 為碳數6〜20的烧基。R32為碳S 1〜22的燒基,較佳為碳 數1〜10的烷基。 上述側鏈型二胺的具體例中,較佳者為二胺(VIII_2)、 (VIII-4)〜(VIII-6)、(XII-2)、(χΠ-4)及(ΧΙΙ·6)。 ,於為了在液晶顯示元件中表現出大預傾角的情況下, 在製造本發明的液晶配向劑所使用的聚合物時,較佳將上 述側鏈型二胺於二胺總量中的比例設為m〇1%,更佳 為 5〜70 mol%。 上述不具側鏈基的二胺,即非側鏈型二胺的較佳例可 例舉式(I)〜(VII)及(XV)所表示的化合物。 h2n—X—nh2 (I) H2n n/ NH2 (")In the formula (XIII-I) to (xiii-3), r31 is an alkyl group having 6 to 22 carbon atoms, preferably a carbon group having 6 to 20 carbon atoms. R32 is a carbon group of carbon S1 to 22, preferably an alkyl group having 1 to 10 carbon atoms. In the specific examples of the above-mentioned side chain type diamine, preferred are diamines (VIII_2), (VIII-4) to (VIII-6), (XII-2), (χΠ-4), and (ΧΙΙ·6). . In order to exhibit a large pretilt angle in the liquid crystal display element, in the case of producing the polymer used in the liquid crystal alignment agent of the present invention, it is preferred to set the ratio of the above-mentioned side chain type diamine to the total amount of the diamine. It is m〇1%, more preferably 5~70 mol%. Preferred examples of the above diamine having no side chain group, i.e., a non-side chain type diamine, may be exemplified by the compounds represented by the formulae (I) to (VII) and (XV). h2n—X—nh2 (I) H2n n/ NH2 (")

h2n αΝ, (III) (IV) 33 201125896 z1 z2H2n αΝ, (III) (IV) 33 201125896 z1 z2

這些式中,X為碳數2〜12的直鏈亞烷基。Y獨立為單 鍵、-0-、-CO-、-NH-、-N(CH3)-、-CONH-、-NHCO-、 -C(CH3)2-、-C(CF3)2-、-0-(CH2)t-0-、-S-、-S-S-、-S02-、 -S-(CH2)t-S-或碳數1〜12的直鏈亞烷基,且t為1〜12的整 數。Z1 及 Z2 為氫,但於 Y 為-NH-、-N(CH3)-、-CH2-、-C(CH3)2-或-C(CF3)2-時也可以相互鍵結形成單鍵。環d為亞苯基或 1,4-二氮雜亞環己基。R33及R34分別獨立為碳數丨〜3的烷 基或苯基。A3獨立為碳數卜6的亞烷基、亞苯基或被烷基 取代的亞苯基。m為1〜1〇的整數。環己烷環或笨環的任 意氫可被氟、甲基、三氟曱基、_0H、_C00H、_s〇3h、 -P〇3H2、苄基或經基苄基取代。 二胺(I)的例子如下所示。 H2N(CH2)2NH2 H2N(CH2)4NH2 H2N(CH2)6NH2 (M) ㈣ (1-3) 一胺(II)的具體例如下所示。 34 201125896 H2N~{^NH2 H2N~Q-h (11-1) H2N—Γ ^|—NH2 (II-2)二胺(III)的具體例如下所示In these formulas, X is a linear alkylene group having 2 to 12 carbon atoms. Y is independently a single bond, -0-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-,- 0-(CH2)t-0-, -S-, -SS-, -S02-, -S-(CH2)tS- or a linear alkylene group having 1 to 12 carbon atoms, and t is 1 to 12 Integer. Z1 and Z2 are hydrogen, but when Y is -NH-, -N(CH3)-, -CH2-, -C(CH3)2- or -C(CF3)2-, they may be bonded to each other to form a single bond. Ring d is a phenylene group or a 1,4-diazacyclohexylene group. R33 and R34 are each independently an alkyl group having a carbon number of 丨3 or a phenyl group. A3 is independently an alkylene group having a carbon number of 6, or a phenylene group substituted by an alkyl group. m is an integer of 1 to 1 。. Any hydrogen of the cyclohexane ring or the acyclic ring may be substituted by fluorine, methyl, trifluoromethyl, -OH, -C00H, _s〇3h, -P〇3H2, benzyl or benzyl. An example of the diamine (I) is shown below. H2N(CH2)2NH2 H2N(CH2)4NH2H2N(CH2)6NH2 (M) (IV) (1-3) Specific examples of the monoamine (II) are shown below. 34 201125896 H2N~{^NH2 H2N~Q-h (11-1) H2N-Γ ^|—NH2 (II-2) Diamine (III) Specific examples are shown below

二胺(IV)的具體例如下所示 H2N—nh2 CH,Specific examples of the diamine (IV) are as follows: H2N-nh2 CH,

(IV-3) H2N-//-NH2 (IV-1) (IV-2) ch3 h2N—nh2 h3c (IV-4)(IV-3) H2N-//-NH2 (IV-1) (IV-2) ch3 h2N-nh2 h3c (IV-4)

OH H〇 COOH h2nH^nh2 η2ν,v、nh: (IV-6) (IV-7) h2n ▽、νη9 (IV-8) HOOC h2n—^ -nh2 (IV-9)OH H〇 COOH h2nH^nh2 η2ν,v,nh: (IV-6) (IV-7) h2n ▽, νη9 (IV-8) HOOC h2n—^ -nh2 (IV-9)

ho3s>Ho3s>

PO3H2PO3H2

h2n—e v—nh2 2 H2hT V、NH2 (IV-11) (IV-12)H2n-e v-nh2 2 H2hT V, NH2 (IV-11) (IV-12)

CF3 h2n nh2CF3 h2n nh2

(IV-17)二胺(v)的具體例如下所示 35 201125896Specific examples of (IV-17) diamine (v) are shown below. 35 201125896

H2NH2N

(V-10)(V-10)

(V-11)(V-11)

(V-12) h2nh〇-°'sQ-nh2 h2n^Q-°'>0-nh2 (V-13)(V-12) h2nh〇-°'sQ-nh2 h2n^Q-°'>0-nh2 (V-13)

(V-15) (V-14)(V-15) (V-14)

(V-17) (V-16)(V-17) (V-16)

(V-20) (V-21) H2n-〇~s_sh〇_nh2 ^~^ys^s^y~m2 (V-22) (V-23) 36 (V-24) 201125896 H2n-^s^s^Knh2 (V-25)(V-20) (V-21) H2n-〇~s_sh〇_nh2 ^~^ys^s^y~m2 (V-22) (V-23) 36 (V-24) 201125896 H2n-^s^ s^Knh2 (V-25)

Η2Ν-〇"8'ν^/"8^^_ΝΗ2 (V-26)Η2Ν-〇"8'ν^/"8^^_ΝΗ2 (V-26)

h3c ch3 h2nH3c ch3 h2n

NH, (V-29) O h2n- h2n H2N~^~^~S〇2~^ (V-31) (V-32) HV /0H OH OH I I* ^^NH2 H2N^V^~C (V-33) (V-34) -nh2 (V-27) f3c h2niNH, (V-29) O h2n- h2n H2N~^~^~S〇2~^ (V-31) (V-32) HV /0H OH OH II* ^^NH2 H2N^V^~C (V -33) (V-34) -nh2 (V-27) f3c h2ni

(V-(V-

二胺(νι)的具體例如下所示 -nh2 h2nSpecific examples of the diamine (νι) are shown below -nh2 h2n

(VI-2) l·1 nh2 PF3(VI-2) l·1 nh2 PF3

30)30)

NHo (VI-1) 分 〇#nh2 h2N 令 〇'NHo (VI-1) 分 〇#nh2 h2N 〇 〇'

(VI-4)(VI-4)

NH〇 (VI-3) 37 201125896 H3C CH3H3C CH? (VI-5)NH〇 (VI-3) 37 201125896 H3C CH3H3C CH? (VI-5)

HzN /~NH, (VI-6) (VI-7) 胺(VII)的具體例如下戶斤示 Η^Λ// (VII-3) h3c ch; (VII-4)HzN /~NH, (VI-6) (VI-7) The specifics of the amine (VII) are as follows: Η^Λ// (VII-3) h3c ch; (VII-4)

叫 M~QrQr\QrQr^ (VII-8) (VII-9) (VIMO) (VU-11)M~QrQr\QrQr^ (VII-8) (VII-9) (VIMO) (VU-11)

h^°^ch^〇^NH2 HiLw〇^_N (VIM2) H3C ch3_~〇^〇^〇^〇~叫 „2(^^〇^〇分 NH2 (VIM3) f3c cf3 (VII-14) ^^°'OxO^°'〇-nhj (VIM 5)二胺(XV)的具體例如下所示。 (VII-16) nh2 38 201125896 ?h3 ch3 H2N-C3H6-Si—〇-Si-C3H6~N|-|, CH3 CH3 2 (XV-1) 上述非側鏈型二胺中’較佳者為二胺(ιν·ιΗιν·5)、 IV-WdV-n)、〇m)〜(v_12)、 ' : :;3)、(V-35HV·37)、(㈣ (VH-5)及(謂),更佳者為二卿ν ι)、(ιν_2)、(ιν ι5)〜 (IV 17)、(V-1)〜(V-12)、(V-33)、(ν-3 5)〜(ν-3 7)、(VI-7)、(VII-2)H^°^ch^〇^NH2 HiLw〇^_N (VIM2) H3C ch3_~〇^〇^〇^〇~called „2(^^〇^〇分NH2 (VIM3) f3c cf3 (VII-14) ^^ The specific details of °'OxO^°'〇-nhj (VIM 5) diamine (XV) are shown below. (VII-16) nh2 38 201125896 ?h3 ch3 H2N-C3H6-Si-〇-Si-C3H6~N| -|, CH3 CH3 2 (XV-1) Among the above non-side chain type diamines, 'the preferred ones are diamines (ιν·ιΗιν·5), IV-WdV-n), 〇m)~(v_12), ' : :; 3), (V-35HV·37), ((4) (VH-5), and (predicate), the better is the second ν ι), (ιν_2), (ιν ι5) ~ (IV 17), (V-1)~(V-12), (V-33), (ν-3 5)~(ν-3 7), (VI-7), (VII-2)

及(XV-1) 〇 若考慮將液晶顯示元件的離子密度等電氣特性調整為 較佳範圍内,則此種非側鏈型二胺於本發明的液晶配向劑 中作為聚酿胺酸的原料的二胺總量中以莫耳百分比計較佳 含有1〜98% ’更佳含有10〜95%,且再更佳含有20〜80%。 本發明所使用的二胺可使用所述二胺(I)〜(VIH)、(X)〜 (XIII)及(XV)以外的二胺。此種二胺例如為具有苐環的第 系二胺以及二胺(VIII)〜(XII)以外的側鏈型二胺。And (XV-1) 〇 When the electrical characteristics such as the ion density of the liquid crystal display element are adjusted to a preferred range, such a non-side chain type diamine is used as a raw material of poly-branched acid in the liquid crystal alignment agent of the present invention. The total amount of the diamine is preferably from 1 to 98% by weight of the mole percent, more preferably from 10 to 95%, and still more preferably from 20 to 80%. As the diamine used in the present invention, diamines other than the diamines (I) to (VIH), (X) to (XIII) and (XV) can be used. Such a diamine is, for example, a diamine having an anthracene ring and a side chain diamine other than the diamines (VIII) to (XII).

二胺(VIII)〜(XII)外的側鏈型二胺之例為二胺(1,)〜(g,)。 R35 h2nExamples of the side chain type diamines other than the diamines (VIII) to (XII) are diamines (1,) to (g,). R35 h2n

(2*)(2*)

(1·)(1·)

39 20112589639 201125896

、士此Γ 及心分別獨立為碳數3〜3〇的狀。 =二扣於製造本發明的液晶配向劑中的聚醯胺二 ;不知及本發明的效果的程度的範圍内使用。 ° =聚ϋ麟時亦可於二胺中添加單胺。藉由添加 步的Κι成聚醯胺酸時的聚合反應’而可抑制更進- =或其衍生物)的分子量,且例如可不損及本= ^果地改善液晶配向劑的塗布特性4胺的添加比例 ^標聚__分子量㈣宜調整。若不損及本發明的 节,則可添加二種以上的單胺。單胺的例子是苯胺、4_ 羥基苯胺、環己胺、正丁胺、正戊胺、正己胺、正庚胺、 正辛,、正壬胺、正癸胺、正十_烧基胺、正十二燒胺、 ^十三絲胺、正十四絲胺、正十五絲胺、正十六烧 基胺、正十七絲胺、正十人烧基胺、以及正二十絲胺。 於本發明中’使二胺與四幾酸二酐反應而得聚酿胺酸 時,可如上述使用選自二胺(P)的群組的二胺和其他二胺的 混合物。此時,其他二胺的較佳例之一是選自二胺(VIII) 及(X)〜(xm)的群組的側鏈型二胺的至少一種。其他二胺的 另一較佳例是選自二胺(vm)及(Χ)〜(ΧΙΙΙ)的群組的側鏈型 201125896 二胺的至少-種和選自二胺(Ι)〜(νπ)及(χ v)的群組的非側 鏈t 一胺的至:>、種的混合物。上述第[4]〜[7]項即是選自 一胺(P)的群組的二胺、側鏈型二胺及非側鏈型二胺的組合 的較佳例。 於本發明中,可將上述那樣使混合二胺與四羧酸二酐 反應而得的聚醯胺酸作為聚合物成分,也可以將原料不同 的聚醯胺酸的混合物作為聚合物成分。聚醯胺酸的混合物 的較佳例之一是如下的聚醯胺酸的混合物:使選自二胺(p) 的群組的二胺的至少一種和選自二胺(Vm)及(χ)〜(χπι)的 群組的側鏈型二胺的至少一種的混合物,或者於該二胺混 合物中進一步添加有選自二胺⑴〜(VII)及(χ V)的群組的非 側鏈型二胺的至少一種的混合物與四羧酸二酐反應而得的 聚醯胺酸;以及使所述非側鏈型二胺的至少一種或者該非 側鏈型二胺的至少一種和選自二胺(Ρ)的群组的二胺的至 少一種的混合物與四羧酸二酐反應而得的聚醯胺酸。上述 第[8]〜[11]項所示的聚合物即相當於這些聚醯胺酸混合物。 % 聚醯胺酸的混合物的另一個較佳例是如下的聚醯胺酸 的混合物:使選自二胺(Ρ)的群組的二胺的至少一種和選自 一胺(I)〜(VII)及(XV)的群組的非側鏈型二胺的至少一種的 混合物與四羧酸二酐反應而得的聚醯胺酸;以及使選自二 胺(VIII)及(X)〜(XIII)的群組的側鏈型二胺的至少一種或者 該些側鏈型二胺的至少一種和上述非側鏈型二胺的至少一 種的混合物與四羧酸二酐反應而得的聚醯胺酸。上述第 [12]及[13]項所示的聚合物即相當於這些聚醯胺酸混合物。 41 201125896 本發明中所用的四羧酸二酐可為一種化合物’也可以 為2種以上化合物的混合物。四羧酸二酐可例舉芳 竣酸二酐及芳香族以外的四羧酸二酐。芳香族以 矢四 酸二酐的例子是脂環族四羧酸二酐及脂肪族四羧萨的四羧 另外,芳香族四羧酸二酐表示與芳香基鍵結的二軒。 水而件的化合物。脂環族四叛酸二針表示與環狀於緣基脫 鍵結的4個羧基脫水而得的化合物。脂肪族四緩^訪姨基 不與鍵狀脂肪族基鍵結的4個羧基脫水而得的化軒表 务香族四叛酸二針的例子如下所示。The sputum and the heart are each independently a carbon number of 3 to 3 inches. The second derivative is used in the production of the polyamine 2 in the liquid crystal alignment agent of the present invention; it is used within the range of the degree of the effect of the present invention. ° = Polyurethane can also be added to the diamine in the monoamine. The molecular weight of the further-- or its derivative can be inhibited by adding the polymerization reaction of the step to the poly-proline, and the coating property of the liquid crystal alignment agent can be improved, for example, without losing the coating property. The addition ratio ^ __ molecular weight (four) should be adjusted. Two or more kinds of monoamines may be added without damaging the knot of the present invention. Examples of monoamines are aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octyl, n-decylamine, n-decylamine, n-decylamine, positive Dodecylamine, tridecylamine, tetrahedralamine, n-pentadecylamine, n-hexadecylamine, n-heptadesamine, n-dodecylamine, and tetradecylamine. In the present invention, when a diamine is reacted with a tetrabasic acid dianhydride to obtain a poly-branched acid, a mixture of a diamine selected from the group of diamines (P) and another diamine can be used as described above. In this case, one of the preferable examples of the other diamine is at least one selected from the group consisting of diamines (VIII) and (X) to (xm). Another preferred embodiment of the other diamine is at least one of the side chain type 201125896 diamine selected from the group consisting of diamines (vm) and (Χ)~(ΧΙΙΙ) and selected from the group consisting of diamines (Ι)~(νπ And (χ v) a group of non-side chain t-amines to: >, a mixture of species. The above items [4] to [7] are preferred examples of the combination of a diamine, a side chain type diamine and a non-side chain type diamine selected from the group consisting of monoamines (P). In the present invention, a polyglycine which is obtained by reacting a mixed diamine with a tetracarboxylic dianhydride as described above may be used as a polymer component, or a mixture of polyamic acids having different raw materials may be used as a polymer component. One of the preferred examples of the mixture of polyaminic acids is a mixture of polyaminic acids: at least one selected from the group consisting of diamines (p) and selected from the group consisting of diamines (Vm) and (χ) a mixture of at least one of the side chain type diamines of the group of ~(χπι), or a non-side of the group of diamines (1) to (VII) and (χ V) further added to the diamine mixture a polyamic acid obtained by reacting a mixture of at least one of a chain diamine with a tetracarboxylic dianhydride; and at least one of the non-side chain type diamine or at least one of the non-side chain type diamines and selected from the group consisting of Polylysine obtained by reacting a mixture of at least one of diamines of a group of diamines with tetracarboxylic dianhydride. The polymers shown in the above items [8] to [11] correspond to these polyaminic acid mixtures. Another preferred example of the mixture of polylysine is a mixture of polylysines: at least one of the diamines selected from the group consisting of diamines (oxime) and one selected from the group consisting of monoamines (I)~( a polylysine obtained by reacting a mixture of at least one of a non-side chain type diamine of VII) and (XV) with a tetracarboxylic dianhydride; and a selected from the group consisting of diamines (VIII) and (X) At least one of a side chain type diamine of the group (XIII) or a mixture of at least one of the side chain type diamines and at least one of the above non-side chain type diamines and a tetracarboxylic dianhydride Proline. The polymers shown in the above items [12] and [13] correspond to these polyamido acid mixtures. 41 201125896 The tetracarboxylic dianhydride used in the present invention may be a compound ' or a mixture of two or more compounds. The tetracarboxylic dianhydride may, for example, be an aromatic dianhydride or a tetracarboxylic dianhydride other than an aromatic compound. Examples of the aromatic ortho-tetracarboxylic dianhydride are an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic acid tetracarboxylic acid. Further, the aromatic tetracarboxylic dianhydride represents a divalent bond bonded to an aromatic group. a compound of water. The alicyclic four-reactive acid two-pin represents a compound obtained by dehydration of four carboxyl groups which are debonded from the rim group. Aliphatic sulphate sulphate sulphate The sulphate sulphate is not shown in the following.

(H-12) (H-13) 鲁 42 201125896(H-12) (H-13) Lu 42 201125896

ο (Η-22) Οο (Η-22) Ο

上述芳香族四羧酸二酐中,較佳者為酸酐(Η-1) (Η-5)、(Η-8)〜(Η-10)及(Η-22),特佳為酸酐(Η-1)。 脂環族四羧酸二酐的例子如下所示。Among the above aromatic tetracarboxylic dianhydrides, preferred are anhydrides (Η-1) (Η-5), (Η-8)~(Η-10) and (Η-22), particularly preferably anhydrides (Η). -1). Examples of the alicyclic tetracarboxylic dianhydride are shown below.

(S-3) Ο 0 Ο Ρ 0 0(S-3) Ο 0 Ο Ρ 0 0

〇 (S-1) (S, 43 201125896 ch3 CHa 0 ch3 ch3〇 (S-1) (S, 43 201125896 ch3 CHa 0 ch3 ch3

y 0 1 / V Q: X 0 Ϊ ll 0 Λ) (S-8) (S-9) 0 〆0 0 、0y 0 1 / V Q: X 0 Ϊ ll 0 Λ) (S-8) (S-9) 0 〆0 0 , 0

0· r o (S-12) 0 X)C° °U S (S-15) 0 r 0 (S-16)0· r o (S-12) 0 X)C° °U S (S-15) 0 r 0 (S-16)

o o 0 (S-14) 0 c° π 0 (S-17) 0 Λo o 0 (S-14) 0 c° π 0 (S-17) 0 Λ

(S-19)(S-19)

0 (S-18) O0 (S-18) O

O OO O

(S-25)(S-25)

00

<0<0

(S-20) O O(S-20) O O

(S-29)(S-29)

(S-35)(S-35)

ΌΌ

•0 0• 0 0

0 44 201125896 〇0 44 201125896 〇

〇 〇〇 〇

〇 V 〇 π〇Χίπ Λ Ο 〇〇 V 〇 π〇Χίπ Λ Ο 〇

(S-41)(S-41)

(S-42)(S-42)

上述脂環族四羧酸二酐中,較佳者為酸酐(S-1)〜 (S-5)、(S-8)〜(S-30)及(S-35)〜(S-46),更佳者為酸酐(S-1)。 脂肪族四羧酸二酐的例子如下所示。Among the above alicyclic tetracarboxylic dianhydrides, preferred are anhydrides (S-1) to (S-5), (S-8) to (S-30) and (S-35) to (S-46). More preferably, it is an acid anhydride (S-1). Examples of the aliphatic tetracarboxylic dianhydride are shown below.

45 20112589645 201125896

(S-53) 及(S-52) =脂肪族四麟二时,較佳者為着㈣、(s_48)(S-53) and (S-52) = aliphatic four-two, preferably (four), (s_48)

明的效果地改善液晶配向劑的塗布特性 於製造聚醯胺酸時,也可以於四驗二針中添加二叛 酉夂酐而使用。由此可終止生成聚酿胺酸時的聚合反應,而 可抑制更進-步的聚合反應的進行。g卩,可容易地控制所 得的聚合物(聚酿胺酸)的分子量,且例如可不損及本發 ‘羧酸酐的添永 比例可考慮目標聚醯胺酸的分子量而適宜調整。而且,# 不損及本發明的效果’則添加的二緩酸酐的種類亦可為 種以上。二羧酸酐之例是馬來酸酐、鄰笨二曱酸軒、;2 酸酐、正癸基琥珀酸酐、正十二烷基琥珀酸軒、正十四^ 基琥珀酸酐、正十六烷基琥珀酸酐以及1,2-環己燒二酸^ 46 201125896 發明巾’於製造聚祕酸時,亦可進—步添加單 二物。藉由添加單異氰酸§旨化合物,所得聚醯 改到改性’分子量得到調節。#由使用該末端 =醯胺酸,例如可不損及本發明的效果地改善液晶 配:的塗布特性。自上述觀點,單異氮酸醋化合物的添 ί罝較佳相對於二胺及四細H的總量為wo m〇1%。 單異氰化合物例如為異氰酸笨_及異氰酸萘醋。The coating properties of the liquid crystal alignment agent are improved by the effect of the invention. When the polyamic acid is produced, it is also possible to add the two retinoids to the four test needles. Thereby, the polymerization reaction in the formation of the poly-aracine can be terminated, and the progress of the further progress of the polymerization can be suppressed. That is, the molecular weight of the obtained polymer (polyaracine) can be easily controlled, and for example, the ratio of the addition of the carboxylic acid anhydride can be appropriately adjusted without considering the molecular weight of the target polyglycolic acid. Further, # does not impair the effect of the present invention, and the type of the bis-alkaliic acid to be added may be more than one type. Examples of the dicarboxylic anhydride are maleic anhydride, o-arsenic acid, 2 anhydride, n-decyl succinic anhydride, n-dodecyl succinate, n-tetradecyl succinic anhydride, n-hexadecyl amber Anhydride and 1,2-cyclohexanoic acid ^ 46 201125896 Inventive towel 'in the manufacture of poly-acid, can also be added step by step. By adding a compound of monoisocyanate, the resulting polypyrene is modified to a modified 'molecular weight. # By using the terminal = proline, for example, the coating properties of the liquid crystal can be improved without impairing the effects of the present invention. From the above viewpoint, the addition amount of the monoisoxamic acid compound is preferably 1% relative to the total amount of the diamine and the tetrafine H. The mono-isocyanate compound is, for example, isocyanuric acid and naphthalene isocyanate.

本發明中所使用的聚醢胺酸可與聚酿亞胺膜的形成中 所用的已知聚醯胺酸同樣地製造。四麟二酐的總裝入量 較佳與一㈣總莫耳數大致等莫耳(莫耳比⑽〜丨」左右)。 以聚苯乙烯換算的重量平均分子量(Mw)計,聚酿 胺酸的分子量較佳A 10,_〜·,_,更佳為2〇〇〇〇〜 2〇〇,〇〇〇。聚酿胺酸的分子量可根據凝膠穿透層析法⑽C) 的測定值而求出。 聚醯胺酸可藉由如下方式確認其存在:以大量貧溶劑 使其沉殿而得固形物,再用IR、NMR分析此固形物。用 KOH或NaOH等強鹼的水溶液將聚醯胺酸分解後,用 GC、HPLC或GC-MS對該分解物的利用有機溶劑所萃取 的萃取物進行分析,由此可確認所使用的原料。 本發明的液晶配向劑還可以進一步含有上述聚醯胺酸 以外的其他成分。其他成分可以是一種也可以是2種以上。 例如,自使液晶顯示元件的電氣特性長期穩定的觀點 考慮,本發明的液晶配向劑還可以進一步含有烯基取代的 奈迪酿亞胺(Nadi imide)化合物。添加烯基取代的奈迪醯 201125896 亞胺化合物時的含量,以相對於液晶配向劑中的聚酿胺酸 的重量比計,較佳為0.01〜0.50。 上述稀基取代的奈迪醯亞胺化合物較佳為可溶於本發 明用來溶解聚醯胺酸或其衍生物的溶劑中的化合物。此種 烯基取代的奈迪醯亞胺化合物的特佳例為式(lna_l)表示的 雙{4-(烯丙基二環[2.2.1]庚-5-稀-2,3-二叛基醮亞胺)苯基} 曱烷、式(Ina-2)表示的N,N’-間苯二曱基-雙(烯丙基二環 [2.2.1]庚-5-烯-2,3-二叛基醯亞胺)及式(Ina-3)所表n,N,-六 亞曱基-雙(稀丙基二環[2.2.1]庚-5-稀-2,3-二羧基醯亞胺)。The polyglycolic acid used in the present invention can be produced in the same manner as the known polyaminic acid used in the formation of the polyimide film. The total loading amount of tetralin is preferably about the same as that of one (four) total molars (mole ratio (10) ~ 丨). The molecular weight of the polyaraminic acid is preferably A 10, _~·, _, more preferably 2 Å to 2 Å, in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the poly-aracine can be determined from the measured values of the gel permeation chromatography (10) C). Polylysine can be confirmed by the presence of a large amount of a poor solvent to form a solid, which is then analyzed by IR or NMR. The polylysine is decomposed by an aqueous solution of a strong alkali such as KOH or NaOH, and the extract obtained by the organic solvent is analyzed by GC, HPLC or GC-MS to confirm the raw materials used. The liquid crystal alignment agent of the present invention may further contain other components than the above polyamic acid. The other components may be one type or two or more types. For example, the liquid crystal alignment agent of the present invention may further contain an alkenyl-substituted Nadiimide compound from the viewpoint of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The content of the alkenyl-substituted nadir oxime 201125896 is preferably 0.01 to 0.50 based on the weight ratio of the poly-aracine in the liquid crystal alignment agent. The above-mentioned dilute-substituted nadirimine compound is preferably a compound which is soluble in a solvent for dissolving polyglycine or a derivative thereof of the present invention. A particularly preferred example of such an alkenyl-substituted nadirimine compound is a double {4-(allylbicyclo[2.2.1]hept-5-rare-2,3-dual rebellion represented by the formula (lna-1). N,N'-m-phenylenedifluoryl-bis(allylbicyclo[2.2.1]hept-5-ene-2, represented by the formula (Ina-2). 3-, direindolimine) and formula (Ina-3), n, N,-hexaindolyl-bis(dipropylbicyclo[2.2.1]hept-5-rare-2,3- Dicarboxy quinone imine).

此種烤基取代的奈迪酿亞胺化合物例如可如日本專利 第2729565號公報所述般使用如下的化合物:將經稀基取 代的奈迪酸酐衍生物與二胺在80〜220。〇的溫度下保持 0.5〜20小時’使其反應而得的化合物,或者市售的化合物。 而且,例如自使液晶顯示元件的電氣特性長期穩定的 觀點考慮,本發明的液晶配向劑亦可進一步含有烯基取代 的奈迪醯亞胺化合物以外的具有自由基聚合性不飽和雙鍵 48 201125896 的化合物。使用該具自由基聚合性不飽和雙鍵的化合物時 的含量’以相對於聚醯胺酸的重量比計,較佳為〇〇1〜〇5〇。 具有自由基聚合性不飽和雙鍵的化合物可例舉(甲基) 丙烯酸酯、(甲基)丙烯醯胺等(曱基)丙烯酸衍生物,以及雙 馬來醯亞胺,更佳者為具有2個以上自由基聚合性不飽和 雙鍵的(甲基)丙婦酸衍生物》 而且,例如自液晶顯示元件的電氣特性的長期穩定性 的觀點考慮,本發明的液晶配向劑亦可進一步含有噁嗪化 合物。添加噁嗪化合物時的含量,以相對於聚醯胺酸的重 量比計,較佳為0.01〜0 20。 °惡嘻化合物可例舉下述通式(a)〜(f)所表示的化合物。Such a baked-substituted nadir-enamine compound can be used, for example, as described in Japanese Patent No. 2729565, wherein the diazide-substituted nadicarboxylic anhydride derivative and the diamine are in the range of 80 to 220. A compound obtained by reacting at a temperature of hydrazine for 0.5 to 20 hours or a commercially available compound. Further, for example, from the viewpoint of stabilizing the electrical properties of the liquid crystal display device for a long period of time, the liquid crystal alignment agent of the present invention may further contain a radically polymerizable unsaturated double bond other than the alkenyl-substituted nadirimine compound 48 201125896 compound of. The content of the compound having a radically polymerizable unsaturated double bond is preferably from 〇〇1 to 〇5〇, based on the weight ratio of the polyglycolic acid. The compound having a radically polymerizable unsaturated double bond may, for example, be a (meth) acrylate, a (meth) acrylamide derivative or the like, and a bismaleimide, and more preferably have a Further, the (meth) propyl acid derivative of the two or more radically polymerizable unsaturated double bonds, and the liquid crystal alignment agent of the present invention may further contain, for example, from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display device. Oxazine compound. The content of the oxazine compound to be added is preferably from 0.01 to 20% by weight based on the weight ratio of polyamic acid. The compound represented by the following formula (a) to (f) is exemplified by the oxime compound.

上述式中’ R1及R2表示碳數1〜30的有機基。R3〜R6 表示氫或碳數1〜6的烴基。χ表示單鍵、_〇_、_s_、_s s_、 -S02-、-CO-、-CONH-、-NHCO-、-C(CH3)2-、-C(CF3)2-、 _(CH2)m·、_〇-(cH2)m-〇-、或-S-(CH2)m-S-。此處,m 為 1〜6 的整數。Y獨立表示單鍵、_〇_、_s_、_c〇-、-c(ch3)2-、 49 201125896 ---—r -C(CF3)2-或碳數1〜3的亞烷基。苯環及萘環的任意氫可被 氟、甲基、-OH、-COOH、-S03H、或-P〇3h2 取代。 . 所述噁嗪化合物可使用與國際公開2004/009708號說 明書、曰本專利特開平11-12258號公報、日本專利^開 2004-352670號公報中記載的方法相同的方法而製造。In the above formula, 'R1 and R2' represent an organic group having 1 to 30 carbon atoms. R3 to R6 represent hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. χ denotes a single bond, _〇_, _s_, _s s_, -S02-, -CO-, -CONH-, -NHCO-, -C(CH3)2-, -C(CF3)2-, _(CH2) m·, _〇-(cH2)m-〇-, or -S-(CH2)mS-. Here, m is an integer from 1 to 6. Y independently represents a single bond, _〇_, _s_, _c〇-, -c(ch3)2-, 49 201125896 ----r-C(CF3)2- or an alkylene group having 1 to 3 carbon atoms. Any hydrogen of the benzene ring and the naphthalene ring may be substituted by fluorine, methyl, -OH, -COOH, -S03H, or -P〇3h2. The oxazine compound can be produced by the same method as the method described in the publication of the Japanese Patent Publication No. 2004-009708, the Japanese Patent Publication No. Hei.

另外’自液晶顯示元件的電氣特性的長期穩定性的觀 點考慮’也可以進一步含有具有下述噁唑啉結構的嗯唾琳 化合物。而且,也可以添加具有環氧乙烷基的化合物,且 也可以添加聚醯胺酸以外的聚合物。另外,也可以添加各 種添加劑,例如:1)當希望提高塗布性時可添加用來實現 相關目的之表面活性劑,2)當必須提高抗靜電時可添加抗 靜電劑’ 3)當希望提高與基板的密著性或耐摩擦性時可^ 加矽烷偶聯劑或鈦系偶聯劑,而且4)當於低溫下進行^ 亞胺化的情況下可添加醯亞胺化觸媒等。 而且,例如自調整液晶配向劑的塗布性或所述聚醯胺 酸濃度的觀點考慮’本發明的液晶配向劑也可以進一步含 有溶劑。該溶劑若為具有溶解聚合物成分能力的溶劑 並無特別限制地使用。即,可自以聚醯胺酸、可溶性聚醯 亞胺等聚合物成分的製造步驟或用途方面所通常使用的溶 劑為首的眾多溶劑中,根據使用目的而適宜選擇。該溶劑 可單獨使用,也可以將多種溶劑混合使用。 對於聚醯胺酸而言為母液的非質子性極性有機溶劑可 列舉:N-甲基-2-吡咯烷酮、二甲基咪唑啉酮、N_f基已内 50 201125896 醯胺、N1基丙醯胺、N,N•二甲基乙 N,N-二甲基甲酿胺、N 二”石風 γ-丁内醋等内酿。 6基甲酿胺、二乙基乙醯胺、 美r以=塗Γ生等為目的之其他溶劑的例子為··乳酸烧 氧基丁醇、萘滿、異佛_、乙二醇單 丁醚專乙二醇魏細、二乙二醇單⑽等 二醇單絲喊乙酸钱、三乙項料細、Further, the term "consideration from the viewpoint of long-term stability of electrical characteristics of the liquid crystal display element" may further contain a sulphur compound having the following oxazoline structure. Further, a compound having an oxirane group may be added, and a polymer other than polyamine may be added. In addition, various additives may also be added, for example: 1) a surfactant for achieving a related purpose may be added when it is desired to improve the coating property, 2) an antistatic agent may be added when antistatic is necessary to be improved '3) when it is desired to improve When the adhesion or the abrasion resistance of the substrate is increased, a decane coupling agent or a titanium coupling agent may be added, and 4) when imidization is carried out at a low temperature, a ruthenium-based catalyst or the like may be added. Further, for example, from the viewpoint of self-adjusting the coatability of the liquid crystal alignment agent or the concentration of the polyamic acid, the liquid crystal alignment agent of the present invention may further contain a solvent. The solvent is not particularly limited as long as it has a solvent capable of dissolving a polymer component. In other words, a plurality of solvents, such as a solvent which is usually used in the production step or use of a polymer component such as polyamic acid or a soluble polyimine, can be appropriately selected depending on the purpose of use. The solvent may be used singly or in combination of a plurality of solvents. Examples of the aprotic polar organic solvent which is a mother liquor for polyamic acid include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N_f-based 50 201125896 decylamine, N1-propionamide, N, N • dimethyl ethyl N, N-dimethyl ketoamine, N two “stone γ-butane vinegar and other internal fermentation. 6 base armenamine, diethyl acetamide, US r = Examples of other solvents for the purpose of coating, such as lactic acid, oxybutanol, tetralin, isophora, ethylene glycol monobutyl ether, ethylene glycol, and glycols such as diethylene glycol mono(10) Monofilament shouted acetic acid, three items, fine

丙一轉早甲H醇單頂等丙二醇單烧基醚、丙二酸 -乙醋等丙二酸二院基g旨、二丙二醇單㈣等二丙二醇單 烷基醚、這些化合物的乙酸酯類等酯化合物。 這些溶劑中特佳的溶劑是N甲基·2吻各細、N,N_ 二曱基乙醯胺、二曱基咪唾偏、γ_τ_、乙二醇單丁 _、二乙二醇單乙趟、两二醇單丁趟、丙二醇單甲鍵、及 二丙二醇單曱趟。 於本發明中,液晶配向劑中的包含上述聚醯胺酸的聚 合物成分的濃度並無特別限定,較佳為〇 。於將 該液晶配向劑塗布於基板上時,有時需要為了調整膜厚而 將所含的聚合物成分預先用溶劑加以稀釋的操作。此時, 自將液晶配向劑的黏度調整為適於將溶劑容易地混合於液 晶配向劑中的黏度的觀點考慮,較佳所述聚合物成分的浪 度為40 wt%以下。 而且,還可依液晶配向劑的塗布方法調整液晶配向劑 中上述聚合物成分的濃度。液晶配向劑的塗布方法為旋塗 法或印刷法時,為良好地保持膜厚,多數情況下使所述聚 51 201125896 合物成分的濃度為10 wt%以下。也可以用其他塗布方法, 如浸潰法或喷墨法進一步降低濃度。另一方面,如果聚合 物成分濃度為〇·1 wt%以上,則所得液晶配向膜的膜厚容 易最佳化。因此,所述聚合物成分的濃度在通常的旋塗法 或印刷法等中為0.1 wt%以上,較佳為〇·5〜1〇 wt%。然而, 亦可根據液晶配向劑的塗布方法而以更低的濃度使用。 另外,在液晶配向膜的製作中使用的情況下,本發明 的液晶配向劑的黏度可以根據形成該液晶配向劑的膜的手 段或方法而決定。例如,在使用印刷機形成液晶配向劑的 膜時,自得到充分的膜厚的觀點考慮,較佳為5 mPa,s以 上’且自抑制印刷不均的觀點考慮較佳為1〇〇 mpa.s以下, 更佳為10〜80 mPa.s。在利用旋塗法塗布液晶配向劑而形成 液晶配向劑的膜的時,自同樣的觀點考慮,較佳為5〜2〇〇 mPa.s ’更佳為10〜1〇〇 mpa.s。液晶配向劑的黏度可以藉由 利用溶劑進行稀釋或者伴隨著攪拌的熟化而減小。 本發明的液晶配向膜是藉由對上述本發明的液晶配向 劑的塗膜進行加熱而形成的膜。本發明的液晶配向膜可利 用由液晶配向劑製作液晶配向膜的通常方法而得,例如本 發明的液晶配向膜可以如下步驟而得:形成本發明的液晶 配向劑的塗膜的步驟,對其進行加熱而假燒的步驟。關於 本發明的液晶配向膜,還可以視需要對藉由所述煆燒步驟 而獲得的膜進行摩擦處理。 所述塗膜可以與通常的液晶配向膜的製作同樣地將本 發明的液晶配向劑塗布於液晶顯示元件的基板上而形成。 52 201125896 所述基板可例舉:也可以設置氧化銦錫(IT〇)電極等 極或彩色濾光片等的破璃制基板。 將液晶配向劑塗布於基板上的方法通常已知有旋塗 法、印刷法、浸潰法、滴下法、喷墨法等。這些方法也可 以同樣地適用於本發明中。 所述塗膜的煆燒可在上述聚醯胺酸呈現脫水、閉環反 應所需的條件下進行。所述塗臈的煆燒通常已知供 或紅外爐巾進行加熱處㈣方法、在加熱板上進行加献處 理的方法等。這些方法也可以同樣適用於本發明中 較佳在150〜300°C左右的溫度下進行1分鐘〜3小時。 所述摩擦處理可與通常用於液晶配向膜配向處理的麾 2處理同樣地進行,只要是可使本發明晶配向膜辞得 f延遲的條件即可。特佳條件是毛壓人量Q 2〜〇 8二、 、移動速度為5〜250 mm/sec、輥旋轉速度為5〇〇〜2,_ _ °液晶配向膜的配向處理方法除了摩擦法以外 =知有光配向法或轉印法等。在得到本㈣的效果的範圍 可以於所述摩擦處理中並用這些其他配向處理方法。 牛挪i發明的液晶配向膜可利用更含上述步驟以外的其他 =的方法㈣宜獲得。此種其他步驟例如:使塗膜乾^ 者料缝清洗雜處理錢_的步驟等 乾燥频與所咖齡_樣崎t已 中進行加熱處理的方法’在加熱板上進行 這些方法也可以同樣適用於所述乾燥步驟。 乾無步驟較佳在溶财蒸發的溫度下實施,更佳 53 201125896 在相對於所述假燒步驟巾的溫度而言較低的溫度下實施。 配向處理前後的液晶配向膜的利用清洗液的清洗方法 可例舉:刷洗(brushing)、喷霧(jetspray)、訊清洗或 超聲波清料。㈣方法可單獨進行,亦可併用。清洗液 可,用純水,或者曱醇、乙醇、異丙醇等各種醇類,苯、 曱本、二甲笨等㈣族烴類,二氣曱料岐系溶劑丙 明、丁_等_ ’但並不限於這些清洗液。當然,這些清 洗液需使驗充分純化祕質較彡的清歧。此種清洗方 法還可適祕形成本發明的液晶配向膜時的清洗步驟中。 本發明的液晶配向膜的膜厚並無特別限定,較佳為1〇 〜30〇nm,更佳為30〜15〇nm。本發明的液晶配向膜的膜厚 可以使用輪賴(pn)filGmetei·)或樹錄(elHpsGmeter) 等已知的膜厚測定裝置進行測定。 本發明的液晶顯示元件具有:一對基板、含有液晶分 子且形成於該對基板間的液晶層、對液晶層施加電壓的電 極,及使液晶分子配向於蚊㈣的本發明的液晶配向膜。 基板可使用在本發明的液晶配向膜中所述的玻璃制基 板,電極可以使用如本發明的液晶配向膜中所述的形成在 玻璃制基板上的ITO電極。液晶層由被密封在使液晶配向 膜面為内側的基板間的液晶組成物而形成。 所使用的液晶組成物並無特別限制,可使用介電各向 異性為正或負的各種液晶組成物。介電各向異性為正的較 佳的液晶組成物可例舉:在日本專利第3086228號公報、 曰本專利第2635435號公報、曰本專利特表平5_5〇1735號 54 201125896 公報、日本專利制平8·157826私報、 ㈣腳號公報、曰本專利特開平&鳩44 ^開平 (ΕΡ885272Α1說明書)、日本專利特開平9 ^報 (ΕΡ806466Α1制書)、日本專利特開平819 ,公報Propylene glycol, propylene glycol monoalkyl ether, malonic acid-ethyl vinegar, etc., dipropylene glycol monoalkyl ether, dipropylene glycol mono (tetra), etc., acetates of these compounds Equivalent ester compounds. Particularly preferred solvents among these solvents are N methyl·2 kisses, N,N-dimercaptoacetamide, dimercaptopurine, γ_τ_, ethylene glycol monobutyl, and diethylene glycol monoethyl hydrazine. , two diol monobutyl hydrazine, propylene glycol monomethyl bond, and dipropylene glycol monoterpene. In the present invention, the concentration of the polymer component containing the polylysine in the liquid crystal alignment agent is not particularly limited, and is preferably 〇. When the liquid crystal alignment agent is applied onto a substrate, it may be necessary to previously dilute the polymer component contained in the solvent in order to adjust the film thickness. In this case, the viscosity of the polymer component is preferably 40 wt% or less from the viewpoint of adjusting the viscosity of the liquid crystal alignment agent to a viscosity suitable for mixing the solvent in the liquid crystal alignment agent. Further, the concentration of the above polymer component in the liquid crystal alignment agent can be adjusted according to the method of applying the liquid crystal alignment agent. When the method of applying the liquid crystal alignment agent is a spin coating method or a printing method, the film thickness is favorably maintained, and in many cases, the concentration of the polysiloxane composition is 10 wt% or less. It is also possible to further reduce the concentration by other coating methods such as dipping or ink jet. On the other hand, when the concentration of the polymer component is 〇·1 wt% or more, the film thickness of the obtained liquid crystal alignment film is easily optimized. Therefore, the concentration of the polymer component is 0.1% by weight or more, preferably 〇5 to 1% by weight, in a usual spin coating method or printing method. However, it can also be used at a lower concentration depending on the coating method of the liquid crystal alignment agent. Further, in the case of use in the production of a liquid crystal alignment film, the viscosity of the liquid crystal alignment agent of the present invention can be determined depending on the means or method of forming the film of the liquid crystal alignment agent. For example, when a film of a liquid crystal alignment agent is formed by using a printing machine, it is preferably 5 mPa or more from the viewpoint of obtaining a sufficient film thickness, and is preferably 1 μmpa from the viewpoint of suppressing printing unevenness. Below s, more preferably 10 to 80 mPa.s. When the liquid crystal alignment agent is applied by a spin coating method to form a film of a liquid crystal alignment agent, from the same viewpoint, it is preferably 5 to 2 Å mPa.s' or more preferably 10 to 1 Å mpa.s. The viscosity of the liquid crystal alignment agent can be reduced by dilution with a solvent or aging with stirring. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can be obtained by the steps of forming a coating film of the liquid crystal alignment agent of the present invention. The step of heating and simmering. Regarding the liquid crystal alignment film of the present invention, the film obtained by the calcination step may be subjected to a rubbing treatment as needed. The coating film can be formed by applying the liquid crystal alignment agent of the present invention to a substrate of a liquid crystal display element in the same manner as in the production of a normal liquid crystal alignment film. 52 201125896 The substrate may be a glass-breaking substrate such as an indium tin oxide (IT〇) electrode or a color filter. A method of applying a liquid crystal alignment agent onto a substrate is generally known by a spin coating method, a printing method, a dipping method, a dropping method, an ink jet method, or the like. These methods are equally applicable to the present invention. The calcination of the coating film can be carried out under the conditions required for the polyphosphonic acid to exhibit dehydration and ring closure reaction. The simmered simmering is generally known as a method of heating (IV) for heating or infrared sniffer, a method of adding treatment on a hot plate, and the like. These methods are also applicable to the present invention, preferably at a temperature of about 150 to 300 ° C for 1 minute to 3 hours. The rubbing treatment can be carried out in the same manner as the 麾 2 treatment which is generally used for the alignment treatment of the liquid crystal alignment film, as long as the conditions for retarding the crystal of the present invention are delayed. The special condition is that the hair pressure is Q 2 to 〇 8 2, the moving speed is 5 to 250 mm/sec, the rotation speed of the roller is 5 〇〇 2, and the alignment treatment method of the liquid crystal alignment film is in addition to the rubbing method. = Knowing that there is a photo-alignment method or a transfer method. In the range in which the effect of the present invention (4) is obtained, these other alignment treatment methods can be used in combination in the rubbing treatment. The liquid crystal alignment film invented by Niu Mi can be obtained by a method (IV) which further includes other than the above steps. Such other steps are, for example, a method in which the drying frequency of the coating film is cleaned and the like, and the method of heat treatment is performed in the aging process. Suitable for the drying step. The dry step-free operation is preferably carried out at a temperature at which the solvent is evaporated, more preferably 53 201125896 is carried out at a lower temperature relative to the temperature of the simmering step towel. The cleaning method using the cleaning liquid for the liquid crystal alignment film before and after the alignment treatment may, for example, be brushing, spraying, jet cleaning or ultrasonic cleaning. (4) The method can be carried out separately or in combination. The cleaning solution may be pure water, or various alcohols such as decyl alcohol, ethanol, isopropanol, benzene, sulfonate, dimethyl strepene, etc., hydrocarbons, dioxins, bismuth solvents, propylene, etc. 'But it is not limited to these cleaning solutions. Of course, these cleaning fluids need to be thoroughly cleaned up. This cleaning method can also be applied to the cleaning step in forming the liquid crystal alignment film of the present invention. The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably from 1 Å to 30 Å, more preferably from 30 to 15 Å. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as pulverized (pn) filGmetei·) or tree (elHpsGmeter). The liquid crystal display device of the present invention comprises a pair of substrates, a liquid crystal layer containing liquid crystal molecules formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film of the present invention for aligning the liquid crystal molecules with the mosquito (4). As the substrate, the glass substrate described in the liquid crystal alignment film of the present invention can be used, and the electrode can be an ITO electrode formed on a glass substrate as described in the liquid crystal alignment film of the present invention. The liquid crystal layer is formed of a liquid crystal composition sealed between substrates which are inside the liquid crystal alignment film surface. The liquid crystal composition to be used is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. A preferred liquid crystal composition having positive dielectric anisotropy is exemplified by Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei No. 5_5〇1735, No. 54 201125896, Japanese Patent Ping Ping 8·157826 private newspaper, (4) Foot Bulletin, Sakamoto Patent Special Kaiping & 44 44 Kaiping (ΕΡ885272Α1 manual), Japanese Patent Special Kaiping 9 ^ Newspaper (ΕΡ806466Α1 book), Japanese Patent Special Kaiping 819, Bulletin

LmAi制書)、日本料―平9·235552 = 報、日本專利特開平9_255956號公報、 遽> 9- 241643號公報(EP885271A1說明蚩 寺開平 10- 204016號公報(EP844229A1說^金 $特開平 平取_6號公報、日本專利特開平=二專1 特開 日本專利㈣2000-087040號公報 =報、 綱中所揭示的液晶組成物本專利特開 本專利= 號公報、曰本專利特=;4報8^^^ I ITnn^'9 ^-104869 冬專利特開平10_1ό 0 士击報、日 1(Μ_3號公報、日本真刹^報、日本專利特開平 本專利特開平1Q_2 ^^1()·236989號公報、日 1〇-23_號公報、日本專利^么報、日本專利特開平 本專利特開平财賴=平1G·236993號公報、日 1〇切_號公報、曰本專利、曰本專利特開平 本專利特開平购7(^4 Γ謂綱號公報、日 10切035號公報、 ^報、曰本專利特開平 本專利特開平1〇-237〇t6,平Μ·5號公報、曰 唬公報、曰本專利特開平 55 201125896 =3期號公報(EP967261A1說明書)、日 平1〇-287874號公報、日本專利特開平㈣期號公f 日本專利特開平㈣1945號公報、日本專利特 11-029581號公報、日本專利特開平㈣獅49號公報 本專利特開2000_256307號公報、曰本專利特 2001-019965號公報、日本專利特開2〇〇1〇72626號公報、 日本專利特開纖㈣奶號等中揭示的液晶組成物。 即使於所述介電各向異性為正或負的液晶組成物中添 加一種以上光學活性化合物而使用也都可以。 一本發明的液晶顯示元件可形成各種電場方式用液晶顯 示元件。此種電場方式用液晶顯示元件可例舉:所述電極 在相對於所述基板的表面而言為水準方向上對所述液晶層 施加電壓的橫向電場方式用液晶顯示元件,或者所述電極 在相對於所述基板的表面而言為垂直方向上對所述液晶層L 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 _6 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 4报8^^^ I ITnn^'9 ^-104869 Winter patent special Kaiping 10_1ό 0 Shi baobao, Japanese 1 (Μ_3 bulletin, Japan Zhenzhan ^ newspaper, Japanese patent special open patent patent special Kaiping 1Q_2 ^^1 ( ) · 236989 bulletin, Japanese 1〇-23_ bulletin, Japanese patent ^ 报 newspaper, Japanese patent special open flat patent special open flat financial Lai = Ping 1G · 236993 bulletin, Japanese 1 〇 cut _ bulletin, 曰本 patent曰 专利 专利 专利 专利 专利 专利 专利 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Bulletin No. 5, 曰唬 曰唬 曰, 曰 专利 特 55 55 55 201125896 = No. 3 bulletin (EP967261A1 manual), day Japanese Laid-Open Patent Publication No. Hei. No. 2000-256307, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. The liquid crystal composition disclosed in Japanese Laid-Open Patent Publication No. 2001-019965, Japanese Patent Application Laid-Open No. Hei. Or a negative liquid crystal composition may be used by adding one or more optically active compounds. The liquid crystal display element of the present invention can form various liquid crystal display elements for electric field mode. a liquid crystal display element for applying a voltage to the liquid crystal layer in a horizontal direction with respect to a surface of the substrate, or the electrode is perpendicular to a surface of the substrate The liquid crystal layer

施加電壓的縱向電場方式用液晶顯示元件。A vertical electric field mode in which a voltage is applied is used for a liquid crystal display element.

橫向電場方式用液晶顯示元件亦可不表現出較大的預 傾角。因此,於橫向電場方式用液晶顯示元件中適宜使用 由含有非侧鏈型聚酿胺酸的液晶配向劑所形成的液晶配向 膜,所述非側鍵型聚醯胺酸是使用非側鏈型二胺而得的。 縱向電場方式用液晶顯示元件需要表現出較大的預傾 角。因此,於縱向電場方式用液晶顯示元件中適宜使用由 含有侧鏈型聚醯胺酸的液晶配向劑所形成的液晶配向膜, 所述側鏈型聚醯胺酸是使用側鏈型二胺或含有所述側鏈型 二胺的二胺混合物而得的。 56 201125896 如上所述’由本發明的液晶配向劑所形成的液晶配向 膜可以藉由適宜選擇作為其原料的聚合物,而適用於各種 顯不驅動方式的液晶顯示元件中。 本發明的液晶顯示元件還可更具有上述構成要素以外 的要素。作為此種其他構成要素,本發明·晶顯示元件 中還可安裝偏統(偏光膜)、波片(wave plate)、光散射The liquid crystal display element for the transverse electric field mode may not exhibit a large pretilt angle. Therefore, in the liquid crystal display device for a transverse electric field method, a liquid crystal alignment film formed of a liquid crystal alignment agent containing a non-side chain type polyacrylic acid is used, which is a non-side chain type. Derived from diamines. The liquid crystal display element for the longitudinal electric field mode needs to exhibit a large pretilt angle. Therefore, in the liquid crystal display device for a vertical electric field method, a liquid crystal alignment film formed of a liquid crystal alignment agent containing a side chain type polyamic acid, which is a side chain type diamine or A mixture of diamines containing the side chain type diamine. 56 201125896 As described above, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be suitably used in liquid crystal display elements of various displayless driving modes by suitably selecting a polymer as a raw material thereof. The liquid crystal display element of the present invention may further have elements other than the above-described constituent elements. As such other constituent elements, a polarizing film (polarizing film), a wave plate, and light scattering can be mounted in the crystal display element of the present invention.

膜、驅動電路等在液晶顯示元件巾通常使㈣構成要素。 [實例] ’、 以下藉由實例來說明本發明,其中所用的化合物如下。 &lt;四羧酸二酐&gt; 酸酐(H-1):均笨四曱酸二酐 酉夂酐(S-l) . 1,2,3,4-環丁烧四曱酸二針: 酸酐(S_48) ··乙二胺四乙酸二酐: &lt;二胺&gt; 二胺(1&gt;_5) : 2,5_雙(4_氨基苯基)吼咬 二胺心8) : 2,5_雙⑷氨基苯基)啦咬 二胺(^4):4,4,_二氨基二苯甲烷 ^胺(V-7) : 4,4,_二氨基 二苯乙烧 -7) · 雙⑷氨基苯基)_1,4·二氮雜環己烧 4 St) ( R29==正庚基)· U·雙(4普氨基笨基曱 基)本基)-4-正庚基環己烷 苯基•卿氨基笨氧基) 胺(ΧΠ·6-1) (R30二正庚基):U ·雙(4_(4_氨基苯氧基) 57 201125896 苯基)-4-(2-(正庚基環己基)乙基)環己烷 DAPY : 2,6-二氨基。比啶 DAPM : 2,4_二氨基嘧啶 PPD 2氣基_5_(4_氨基苯基)嘲u定 &lt;溶劑&gt; NMP:N-甲基_2_吼咯烷酮 BC : 丁基溶纖劑(乙二醇單丁醚) &lt;聚醯胺酸的合成&gt; [合成例1] 於具有溫度計、攪拌機、原料投入口及氮氣導入口的 100mL的四口燒瓶中加入二胺(P-5)1.673 g以及脫水NMP 3〇.〇 g ’於乾燥氮氣流下進行攪拌溶解。接著,加入酸酐 (H-l)0.6984 g、酸酐(s-l) 0.6280 g 以及脫水 NMP 70.0 g, 於室溫環境下反應15小時。於反應中反應溫度上升的情況 下’將反應溫度抑制於約70。〇以下而反應。於所得的溶 液中添加BC 1〇_〇 g,獲得濃度為6 wt%的聚醯胺酸溶液。 將聚醯胺酸作為PA1,其重量平均分子量為27300。 聚醯胺酸的重量平均分子量是以如下方式求出:用碟 酸-DMF混合溶液(磷酸/DMF = 0.6/100,重量比)稀釋所 得的聚醯胺酸以使其濃度約為2 wt%,使用2695 Sepamticm Module · 2414示差折射儀(Waters公司製),將上述混合 溶液作為展開劑而以GPC法測定,並進行聚苯乙稀換算。 另外’管柱使用HSPgel RT MB-M ( Waters公司製),在管 柱溫度50°C、流速0.40 mL/min的條件下進行測定。 201125896 [合成例2〜12] 以表1所示的方式變更四羧酸二酐及二胺,除此以外 基於合成例1而調製聚醯胺酸溶液(PA2)〜(PA12)。將包括 合成例1的結果匯總於表1。 &lt;表1&gt; 合成例 聚醯胺酸溶液 No. 酸酐 二胺 重量平均分子量 化合物 mol% 化合物 mol% 1 PA1 H-1 S-1 50 50 P-5 100 27,300 2 PA2 H-1 S-1 50 50 P-5 XII-4-1 90 10 27,600 3 PA3 H-1 S-1 50 50 P-5 V-l XII-4-1 50 40 10 31,000 4 PA4 H-1 S-1 60 40 P-5 V-l XII-4-1 50 40 10 30,400 5 PA5 H-1 S-48 50 50 P-5 V-l XII-4-1 50 40 10 39,200 6 PA6 H-1 S-1 50 50 P-5 V-7 XII-4-1 50 40 10 27,000 7 PA7 H-1 S-1 50 50 P-5 VI-7 XII-4-1 50 40 10 28,200 8 PA8 H-1 S-1 50 50 P-5 V-l XII-6-1 50 40 10 29,400 9 PA9 H-1 S-1 50 50 P-5 V-l 30 70 35,500 10 ΡΑΙΟ H-1 S-1 50 50 P-5 V-l XII-2-1 30 60 10 32,400 11 ΡΑ11 H-1 S-1 50 50 P-8 100 29,000 12 PA12 H-1 S-1 50 50 P-8 XII-4-1 90 10 25,100 [比較合成例1〜9] 59 201125896 以表1中所示的方式變更四羧酸二酐及二胺,除此以 外基於合成例1而調製聚醯胺酸溶液(PA13)〜(PA21)。將結 果匯總於表2中。 〈表2&gt; 比較合 成例 聚醯胺酸溶 液No. 酸劍 二胺 重量平均 分子量 化合物 mol% 化合物 mol% 1 PA13 S-1 ~~ 50 50 V-1 100 38,300 2 PA14 S-1 50 50 V-7 100 45,000 3 PA15 H-1 S-1 35 65 V-1 100 40,200 4 PA16 H-1 S-1 50 50 DAPY 100 5,500 5 PA17 H-1 S-1 50 50 DAPM 100 2,000 6 PA18 H-1 S-1 50 50 PPD 100 2,400 7 PA19 H-1 S-1 50 50 V-1 DAPY 70 30 44,200 8 PA20 H-1 S-1 50 50 V-1 DAPM 70 30 35,700 9 PA21 H-1 S-1 50 50 V-1 PPD 80 20 33,900The film, the driver circuit, and the like generally have (4) constituent elements in the liquid crystal display element. [Examples] The present invention will be illustrated by way of examples in which the compounds used are as follows. &lt;tetracarboxylic dianhydride&gt; Anhydride (H-1): both stearic acid dianhydride phthalic anhydride (Sl). 1,2,3,4-cyclobutane tetracarboxylic acid two-needle: acid anhydride (S_48 ··Ethylenediaminetetraacetic acid dianhydride: &lt;Diamine&gt; Diamine (1&gt;_5) : 2,5_bis(4-aminophenyl) 吼diamine core 8) : 2,5_double (4) Aminophenyl) diced diamine (^4): 4,4,-diaminodiphenylmethaneamine (V-7): 4,4,-diaminodiphenylethene-7) ·bis(4)amino group Phenyl)_1,4·diazacyclohexane 4 St) ( R29==n-heptyl)· U·bis(4 phenylaminophenyl)benzyl)-4-n-heptylcyclohexanebenzene • 卿 amino phenyloxy) amine (ΧΠ·6-1) (R30 di-n-heptyl): U · bis (4_(4-aminophenoxy) 57 201125896 phenyl)-4-(2-(正Heptylcyclohexyl)ethyl)cyclohexane DAPY: 2,6-diamino. Bipyridine DAPM : 2,4-diaminopyrimidine PPD 2 gas group _5_(4_Aminophenyl) mocking &lt;solvent&gt; NMP: N-methyl_2_pyrrolidone BC : butyl cellosolve (Ethylene glycol monobutyl ether) &lt;Synthesis of poly-proline acid&gt; [Synthesis Example 1] A diamine (P-5) was placed in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet. 1.673 g and dehydrated NMP 3〇.〇g 'dissolved under a dry nitrogen stream. Next, 0.6984 g of an acid anhydride (H-1), 0.6280 g of an acid anhydride (s-1), and 70.0 g of a dehydrated NMP were added, and the mixture was reacted at room temperature for 15 hours. In the case where the reaction temperature rises during the reaction, the reaction temperature is suppressed to about 70. 〇 The following reaction. BC 1 〇 〇 g was added to the obtained solution to obtain a polyglycine solution having a concentration of 6 wt%. Polylysine was used as PA1 and its weight average molecular weight was 27,300. The weight average molecular weight of polylysine was determined by diluting the obtained polylysine with a dish of a disc acid-DMF (phosphoric acid/DMF = 0.6/100, weight ratio) to a concentration of about 2 wt%. Using a 2695 Sepamticm Module · 2414 differential refractometer (manufactured by Waters Co., Ltd.), the mixed solution was measured as a developing solvent by a GPC method, and converted to polystyrene. Further, the column was measured using HSPgel RT MB-M (manufactured by Waters Co., Ltd.) under the conditions of a column temperature of 50 ° C and a flow rate of 0.40 mL / min. 201125896 [Synthesis Examples 2 to 12] The polyamic acid solutions (PA2) to (PA12) were prepared based on Synthesis Example 1 except that the tetracarboxylic dianhydride and the diamine were changed in the manner shown in Table 1. The results including Synthesis Example 1 are summarized in Table 1. &lt;Table 1&gt; Synthesis Example Polyamine Acid Solution No. Anhydride Diamine Weight Average Molecular Weight Compound mol% Compound mol% 1 PA1 H-1 S-1 50 50 P-5 100 27,300 2 PA2 H-1 S-1 50 50 P-5 XII-4-1 90 10 27,600 3 PA3 H-1 S-1 50 50 P-5 Vl XII-4-1 50 40 10 31,000 4 PA4 H-1 S-1 60 40 P-5 Vl XII -4-1 50 40 10 30,400 5 PA5 H-1 S-48 50 50 P-5 Vl XII-4-1 50 40 10 39,200 6 PA6 H-1 S-1 50 50 P-5 V-7 XII-4 -1 50 40 10 27,000 7 PA7 H-1 S-1 50 50 P-5 VI-7 XII-4-1 50 40 10 28,200 8 PA8 H-1 S-1 50 50 P-5 Vl XII-6-1 50 40 10 29,400 9 PA9 H-1 S-1 50 50 P-5 Vl 30 70 35,500 10 ΡΑΙΟ H-1 S-1 50 50 P-5 Vl XII-2-1 30 60 10 32,400 11 ΡΑ11 H-1 S -1 50 50 P-8 100 29,000 12 PA12 H-1 S-1 50 50 P-8 XII-4-1 90 10 25,100 [Comparative Synthesis Examples 1 to 9] 59 201125896 Change four in the manner shown in Table 1. The polyaminic acid solutions (PA13) to (PA21) were prepared based on Synthesis Example 1 except for the carboxylic acid dianhydride and the diamine. The results are summarized in Table 2. <Table 2> Comparative Synthesis Polylysine Solution No. Sodium diamine Weight average molecular weight Compound mol% Compound mol% 1 PA13 S-1 ~~ 50 50 V-1 100 38,300 2 PA14 S-1 50 50 V- 7 100 45,000 3 PA15 H-1 S-1 35 65 V-1 100 40,200 4 PA16 H-1 S-1 50 50 DAPY 100 5,500 5 PA17 H-1 S-1 50 50 DAPM 100 2,000 6 PA18 H-1 S -1 50 50 PPD 100 2,400 7 PA19 H-1 S-1 50 50 V-1 DAPY 70 30 44,200 8 PA20 H-1 S-1 50 50 V-1 DAPM 70 30 35,700 9 PA21 H-1 S-1 50 50 V-1 PPD 80 20 33,900

將合成例7中調製的濃度為6 wt%的聚醯胺酸溶液 (PA7)與比較合成例1〜3中調製的濃度為6 wt%的聚醯胺酸 溶液(PA13〜PA15)以20/80 (前者/後者,溶液1/溶液2)的 重量比加以混合,製成液晶配向劑(PA22〜PA24 )。將 PA22〜PA24的組成比匯總於表3中。 〈表3&gt; 聚醯胺酸溶液No. 溶液1 溶液2 混合比(溶液1/溶一' PA22 PA7 PA13 20/80 — PA23 PA7 PA14 20/80 PA24 PA7 PA15 20/80 ~~-~ --*-- 60 201125896 於合成例7中調製的濃度為6 wt%的聚醯胺酸溶液 (PA7)中’分別以相對於聚合物的重量而言為1〇加%的量 添加雙{4_(烯丙基二環[2.2.1]庚-5-稀-2,3-二叛基醯亞胺)苯 基}曱坑、2-(3,4-環氧基環己基)乙基三曱氧基石夕烷、4,4_ 亞甲基雙(Ν,Ν·二縮水甘油基苯胺)或N,N_(1,2_二經基亞乙 基)雙丙烯醯胺’製成液晶配向劑(PA25〜PA28 )。將 PA25〜PA28的組成比匯總於表4。 〈表4&gt; 聚醯胺酸 溶液No. 灰醯胺酸 溶液No. 添加劑 添加量 Wt% rA25 PA3 ,{4-(稀丙基二環[2.2.1]庚-5-稀-2,3-二羧基醯亞胺)」 苯基}曱烧 10 PA26 PA3 2-(3,4-環氧基環己基)乙基=曱氧基矽烷 10 rA27 PA3 甲基雙(N,N-二縮水甘油基苯胺) 10 PA28 PA3 \&gt;1-(1,2-二羥基亞乙某)彆丙嬙醯胗 10 [實例1] &lt;液晶顯示元件的製作&gt; 將合成例1中合成的濃度為6 Wt%的聚醢胺酸溶液 (PA1),藉由添加NMP/BC==1/1 (重量比)的混合溶劑而 將整體稀釋為4 wt%,製成液晶配向劑。使用所得的液晶 配向劑’以如下所示那樣製作液晶顯示元件。 〈液晶顯示元件的製作方法&gt; 用旋塗法將液晶配向劑塗布於二牧附有ΠΌ電極的玻 璃基板上’形成膜厚為100 nm的膜。於塗膜後,於8〇〇c 下加熱乾燥約1分鐘,然後於210。(:下進行15分鐘的加 熱處理,形成液晶配向膜。使用飯沼機器製作所公司 (Iinuma Gauge Manufacturig Co.)製造的摩擦處理裝置, 201125896 於配向布(毛長1 8nim:人造絲)的毛壓入量為〇仙咖、 平臺移動速度為mm/see、觀旋轉速度為丨,_啊的條 件下對所得的液晶配向麟行轉處理。紐,將液晶配 向膜於超純水中進行5分鐘的超聲波清洗後,於 12〇°C下乾燥30分鐘。 Ί 於其中一個玻璃基板上散佈4 μιη的間隙材料,將形 成有液晶配向膜的面作為關而以摩擦方向成為反平行的 方式進行對向Si置,紐用環氧硬化劑進行密封 =4㈣的反平行單元。於料元巾注场下所^的二 曰曰組成物,將注入口用光硬化劑加以密封。接著,於ii〇〇C 下進行30分鐘的加熱處理,製作液晶顯示元件。A polyglycine solution (PA7) having a concentration of 6 wt% prepared in Synthesis Example 7 and a polyglycine solution (PA13 to PA15) having a concentration of 6 wt% prepared in Comparative Synthesis Examples 1 to 3 were 20/. The weight ratio of 80 (the former/the latter, solution 1 / solution 2) was mixed to prepare a liquid crystal alignment agent (PA22 to PA24). The composition ratios of PA22 to PA24 are summarized in Table 3. <Table 3> Polyproline solution No. Solution 1 Solution 2 Mix ratio (solution 1 / dissolve one' PA22 PA7 PA13 20/80 - PA23 PA7 PA14 20/80 PA24 PA7 PA15 20/80 ~~-~ --* -- 60 201125896 In a polyglycine solution (PA7) having a concentration of 6 wt% prepared in Synthesis Example 7, 'double {4_(ene is added in an amount of 1% by weight relative to the weight of the polymer, respectively) Propylbicyclo[2.2.1]hept-5-rare-2,3-dioxabenzimimine)phenyl}anthraquinone, 2-(3,4-epoxycyclohexyl)ethyltrioxene Liquid crystal alignment agent (PA25) based on sulphate, 4,4-methylene bis(indene, hydrazine diglycidyl aniline) or N,N_(1,2-di-diethylidene) bis acrylamide ~PA28). The composition ratio of PA25 to PA28 is summarized in Table 4. <Table 4> Poly-proline solution No. lysine solution No. Additive amount Wt% rA25 PA3, {4-(Lactyl propyl Ring [2.2.1]hept-5-rare-2,3-dicarboxyindenine)"phenyl}oxime 10 PA26 PA3 2-(3,4-epoxycyclohexyl)ethyl=decyloxy Decane 10 rA27 PA3 methyl bis(N,N-diglycidyl aniline) 10 PA28 PA3 \&gt; 1-(1,2-dihydroxy-ethylidene)-propionate 10 [ Example 1] &lt;Production of Liquid Crystal Display Element&gt; A polyglycine solution (PA1) having a concentration of 6 Wt% synthesized in Synthesis Example 1 was added by adding NMP/BC = 1/1 (weight ratio). The solvent was mixed and the whole was diluted to 4 wt% to prepare a liquid crystal alignment agent. A liquid crystal display element was produced as follows using the obtained liquid crystal alignment agent. <Method for Producing Liquid Crystal Display Element> Liquid crystal alignment by spin coating method The agent was applied to a glass substrate with a ruthenium electrode attached to Ermu' to form a film having a film thickness of 100 nm. After coating, it was dried by heating at 8 ° C for about 1 minute, and then at 210. (: 15 minutes under: Heat treatment to form a liquid crystal alignment film. Using a friction treatment device manufactured by Iinuma Gauge Manufacturig Co., 201125896, the amount of hair in the alignment cloth (hair length 18 nim: rayon) is 〇仙咖, The moving speed of the platform is mm/see, the viewing rotation speed is 丨, and the obtained liquid crystal alignment is processed under the condition of _ ah. New Zealand, after the liquid crystal alignment film is ultrasonically cleaned in ultrapure water for 5 minutes, at 12 Dry at 〇 ° C for 30 minutes. 于4 μιη of the gap material is spread on one glass substrate, and the surface on which the liquid crystal alignment film is formed is turned off, and the anti-parallel unit is sealed in the opposite direction so that the rubbing direction is antiparallel. . The composition of the crucible is placed under the field of the material, and the injection port is sealed with a light hardener. Next, heat treatment was performed for 30 minutes under ii 〇〇 C to produce a liquid crystal display element.

c5h” 17wt. %C5h” 17wt. %

F 16wt.«F 16wt.«

F 10wt. % 5wt.%F 10wt. % 5wt.%

6wt.% 62 201125896 ---C---6wt.% 62 201125896 ---C---

[實例2〜19] 將表1、表3及表4中記載的濃度為6 wt%的聚醯胺 酸溶液(PA2〜PA12及j&gt;a22〜PA28 ) ’藉由添加NMP/BC = l/i (重量比)的混合溶劑而將整體稀釋為4wt%,製成液 晶配向劑。使用所得的液晶配向劑,與實例丨同樣地製作 液晶顯示元件。 [比較例1〜9] 將表2中所記載的濃度為6 wt%的聚醯胺酸溶液 (PA13〜PA21 ),藉由添加nmP/BC= 1/1 (重量比)的混合 溶劑而將整體稀釋為4 wt%,製成液晶配向劑。使用所得 的液晶配向劑,與實例1同樣地製作液晶顯示元件。 &lt;電氣特性的評價&gt; 對實例1〜19以及比較例丨〜9中所製作的液晶顯示元 件’以如下方式進行殘留DC的測定。 1)殘留DC的測定 於30 Hz、3 V的矩形波上重疊3 v的直流電壓30分 鐘後’測定10分鐘後的閃變消去電壓,將該值的絕對值作 為殘留DC。另外,於本發明的實例的試驗方法中,若殘 留DC為1〇 mv以下的值,則可以說良好。 63 201125896 〈表5&gt; 試驗No. 聚醯胺酸溶液No. 10分鐘後的殘留DC (mV) 實例1 PA1 6 實例2 PA2 1 實例3 PA3 0 實例4 PA4 2 實例5 PA5 3 實例6 PA6 3 實例7 PA7 1 實例8 PA8 4 實例9 PA9 2 實例10 ΡΑΙΟ 1 實例11 ΡΑ11 5 實例12 ΡΑ12 1 比較例1 ΡΑ13 38 ___ 比較例2 PAH 55 比較例3 PA15 35 ____ 比較例4 PA16 *無法測定 —.__比較例5 PA17 *無法測定 --比較例6 PA18 *無法測定 __比較例7 PA19 34 —.___比較例8 PA20 19 __比較例9 PA21 38 -__實例13 PA22 9 --實例14 ~ PA23 4 ~~X實例15 PA24 5 —實例16 PA25 6 實例Π PA26 9 —^實例18 PA27 3 實例19 ] PA28 0 *無法測定:聚醯胺酸溶液的黏度低,因此產生摩擦傷痕,無法測定殘留DC。 如表5所示’可知:原料使用二胺(P)而製造聚醢胺酸, 調製含有該聚醯胺酸的液晶配向劑時,在具有由該液晶配 向劑所得的液晶配向膜的液晶顯示元件中,使殘留DC降 低的致果顯著。 【圖式簡單說明】 64 201125896 無。 【主要元件符號說明】 無0[Examples 2 to 19] Polyhexyl acid solutions (PA2 to PA12 and j&gt;a22 to PA28) having a concentration of 6 wt% as described in Table 1, Table 3 and Table 4 were added by adding NMP/BC = l/ The mixed solvent of i (weight ratio) was diluted to 4 wt% as a whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced in the same manner as in the example. [Comparative Examples 1 to 9] The polyglycine solution (PA13 to PA21) having a concentration of 6 wt% as described in Table 2 was added by adding a mixed solvent of nmP/BC = 1/1 (weight ratio). The overall dilution was 4 wt%, and a liquid crystal alignment agent was prepared. A liquid crystal display element was produced in the same manner as in Example 1 using the obtained liquid crystal alignment agent. &lt;Evaluation of electrical characteristics&gt; The liquid crystal display elements produced in Examples 1 to 19 and Comparative Examples 丨 to 9 were subjected to measurement of residual DC as follows. 1) Measurement of residual DC After the DC voltage of 3 v was superimposed on a rectangular wave of 30 Hz and 3 V for 30 minutes, the flash-eliminating voltage after 10 minutes was measured, and the absolute value of this value was taken as residual DC. Further, in the test method of the example of the present invention, it can be said that the residual DC is a value of 1 〇 mv or less. 63 201125896 <Table 5> Test No. Polyamine acid solution No. Residual DC (mV) after 10 minutes Example 1 PA1 6 Example 2 PA2 1 Example 3 PA3 0 Example 4 PA4 2 Example 5 PA5 3 Example 6 PA6 3 Example 7 PA7 1 Example 8 PA8 4 Example 9 PA9 2 Example 10 ΡΑΙΟ 1 Example 11 ΡΑ 11 5 Example 12 ΡΑ 12 1 Comparative Example 1 ΡΑ 13 38 ___ Comparative Example 2 PAH 55 Comparative Example 3 PA15 35 ____ Comparative Example 4 PA16 * Unable to measure -._ _Comparative Example 5 PA17 * Unable to measure - Comparative Example 6 PA18 * Unable to measure __Comparative Example 7 PA19 34 -.___Comparative Example 8 PA20 19 __Comparative Example 9 PA21 38 -__Example 13 PA22 9 -- Example 14 ~ PA23 4 ~~X Example 15 PA24 5 - Example 16 PA25 6 Example Π PA26 9 -^ Example 18 PA27 3 Example 19 ] PA28 0 * Unable to measure: Polyurethane solution has low viscosity, so it can cause friction scars. The residual DC was measured. As shown in Table 5, it can be seen that when a polyamine is produced by using a diamine (P) as a raw material, and a liquid crystal alignment agent containing the polyamic acid is prepared, a liquid crystal display having a liquid crystal alignment film obtained from the liquid crystal alignment agent is obtained. In the element, the result of lowering the residual DC is remarkable. [Simple description of the map] 64 201125896 None. [Main component symbol description] No 0

Claims (1)

201125896 —f 七、申請專利範圍: ^ L種液晶配向劑,其含有選自由如下聚醯胺酸及其 何生物所構成的群組的至少—種聚合物,該聚醯胺酸是由 式(P)表示的二胺,或者式(P)表示的二胺和其他二胺之混合 物與四叛酸二酐反應而得的:201125896—f 7. Patent application scope: ^ L type liquid crystal alignment agent containing at least one polymer selected from the group consisting of polylysine and any other organism thereof, the polyglycolic acid is of the formula ( The diamine represented by P) or the mixture of the diamine represented by the formula (P) and another diamine is reacted with tetrahydro acid dianhydride: 其中% P為吡啶-2,5-二基、嗒嗓_3,6-二基、嘧啶_2,5·二基 或吡嗪-2,5-二基;k為〇或1;當k=〇時,環p為吡啶_2,5_ 二基或嘧啶-2,5-二基,且該些環中氨基的鍵結位置為5位。 2.如申請專利範圍第1項所述之液晶配向劑,其中式 (P)表示的二胺為式(Ρ-1)〜(Ρ-1〇)表示者的至少一種:Wherein % P is pyridine-2,5-diyl, 嗒嗓_3,6-diyl, pyrimidine_2,5.diyl or pyrazine-2,5-diyl; k is hydrazine or 1; When 〇, ring p is pyridine-2,5-diyl or pyrimidine-2,5-diyl, and the bonding position of the amino group in these rings is 5 positions. 2. The liquid crystal alignment agent according to claim 1, wherein the diamine represented by the formula (P) is at least one of those represented by the formula (Ρ-1) to (Ρ-1〇): 3. 如申請專利範圍第2項所述之液晶配向劑,其中式 (P)表示的二胺為式(P_5)及(P_8)表示者的至少一種。 4. 如申請專利範圍第1〜3中任一項所述之液晶配向 66 201125896 劑’其中該其他二胺為選自式(VIII)及(X)〜(XIII)表示的具 有側鍵基的一胺的群組的至少一種二胺: R13. The liquid crystal alignment agent according to claim 2, wherein the diamine represented by the formula (P) is at least one of the formulae (P_5) and (P_8). 4. The liquid crystal alignment 66 201125896 agent according to any one of claims 1 to 3, wherein the other diamine is selected from the group consisting of formula (VIII) and (X) to (XIII) having a side bond group. At least one diamine of the group of monoamines: R1 式(VIII)中 ’ A3 為單鍵、_〇_、_c〇〜c〇〇_、〇c〇·、c〇NH_、 _αί2α、_α?2〇_或碳數1〜6的亞烷基,該亞烷基中任意的 •avuo·、_ch==CH4_CeC_取代;Rl為具有類固醇 骨架的基、碳數3〜30的烷基、具有碳數1〜30的烷基或碳 數1〜30的燒氧基作為取代基的苯基,或式(Ιχ)表示的基, 且該碳數3〜30的烷基中任意的-匚如可被…_CH = CH_ 或-OC-取代;In the formula (VIII), 'A3 is a single bond, _〇_, _c〇~c〇〇_, 〇c〇·, c〇NH_, _αί2α, _α?2〇_ or an alkylene group having a carbon number of 1 to 6, Any avuo·, _ch==CH4_CeC_ substituted in the alkylene group; R1 is a group having a steroid skeleton, an alkyl group having 3 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms or a carbon number of 1 to 30. a phenyl group having an alkyl group as a substituent, or a group represented by the formula (Ιχ), and any one of the alkyl groups having 3 to 30 carbon atoms may be substituted by, for example, —CH=CH— or —OC—; 式(IX)中 ’ A4 及 A5 獨立為單鍵、_〇_、_c〇〇_、_〇c〇_、 -CONH-、碳數1〜4的亞烷基、碳數卜3的氧亞烷基,或 碳數1〜3的亞烷氧基;環B及環c獨立為丨,4_亞苯基或1ί4_ 亞環己基;R2及R3獨立為氟或曱基,f及g獨立為〇、i 或2, 及e獨立為0〜2的整數,c、d及e合計為1以 上’當c為2時’ 2個環B可相同也可以不同,2個A4可 為相同的結合基也可以為不同的結合基;當d為2時’ 2 個A5可為相同的結合基也可以為不同的結合基;當e為2 時,2個環c可相同也可以不同;R4為碳數丨〜如的烷基、 67 201125896 碳數1〜30的烷氧基或碳數2〜30的烷氧基烷基,在這些烷 基、烷氧基及烷氧烷基中,任意的氫可被氟取代;In the formula (IX), 'A4 and A5 are independently a single bond, _〇_, _c〇〇_, _〇c〇_, -CONH-, an alkylene group having a carbon number of 1 to 4, and an oxygen group having a carbon number of 3 An alkyl group, or an alkyleneoxy group having 1 to 3 carbon atoms; a ring B and a ring c are independently a fluorene, a 4 phenylene group or a 1 4 4 _ cyclohexylene group; R 2 and R 3 are independently a fluorine or a fluorenyl group, and f and g are independently 〇, i or 2, and e are independent integers of 0 to 2, and c, d, and e total 1 or more 'when c is 2' 2 ring B may be the same or different, and 2 A4 may be the same combination The base may also be a different binding group; when d is 2, '2 A5 may be the same binding group or different bonding groups; when e is 2, 2 rings c may be the same or different; R4 is Carbon number 如~ such as alkyl group, 67 201125896 Alkoxy group having 1 to 30 carbon atoms or alkoxyalkyl group having 2 to 30 carbon atoms, in any of these alkyl groups, alkoxy groups and alkoxyalkyl groups Hydrogen can be replaced by fluorine; 式(X)及(XI)中,R5獨立為氫或曱基,R6為氫、碳數1〜20 的烷基或碳數2〜20的烯基,R7及R8獨立為碳數1〜20的In the formulae (X) and (XI), R5 is independently hydrogen or a fluorenyl group, R6 is hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and R7 and R8 are independently a carbon number of 1 to 20 of 烷基,或苯基,A6獨立為單鍵、_c〇-或-CH2-; R9Alkyl, or phenyl, A6 is independently a single bond, _c〇- or -CH2-; R9 式(XII)及(XIII)中,R9為曱基或碳數2〜30的烷基,該烷基 中任意的-CH2-可被-〇-、-CH=CH-或-C三C-取代;R10為碳 數6〜22的烷基;R11為碳數1〜22的烷基;A7獨立為-0-或 碳數1〜6的亞烷基;A8為單鍵或碳數1〜3的亞烷基;環T 68 201125896 為1,4-亞苯基或1,4-亞環己基;h為0或1。 5.如申請專利範圍第4項所述之液晶配向劑,其中該其 他二胺為選自式(VIII-2)、(VIII-4)〜(VIII-6)、(ΧΙΙ-2)、(ΧΙΙ-4) 及(ΧΙΙ-6)表示的二胺的至少一種:In the formulae (XII) and (XIII), R9 is a fluorenyl group or an alkyl group having 2 to 30 carbon atoms, and any -CH2- of the alkyl group may be -〇-, -CH=CH- or -C三C- Substituted; R10 is an alkyl group having 6 to 22 carbon atoms; R11 is an alkyl group having 1 to 22 carbon atoms; A7 is independently an alkylene group having a number of -0 or 1 to 6 carbon atoms; and A8 is a single bond or a carbon number of 1 to An alkylene group of 3; a ring T 68 201125896 is a 1,4-phenylene group or a 1,4-cyclohexylene group; h is 0 or 1. 5. The liquid crystal alignment agent according to claim 4, wherein the other diamine is selected from the group consisting of formula (VIII-2), (VIII-4) to (VIII-6), (ΧΙΙ-2), ( At least one of diamines represented by ΧΙΙ-4) and (ΧΙΙ-6): (VIII-5)(VIII-5) (VIII-6) R30(VIII-6) R30 於該些式中,R23、R29及R3G獨立為碳數1〜30的烷基,或 碳數1〜30的烷氧基。 6.如申請專利範圍第1〜3項中任一項所述之液晶配向 69 201125896 劑’其中該其他二胺為如下二胺的混合物:選自申請專利 範圍第4項所述之具有側鏈基的二胺的群組的至少一種, 以及選自式(I)〜(VII)及(XV)所表示的不具侧鏈基的二胺的 群組的至少一種; H2N——X—nh2 (I)In the above formula, R23, R29 and R3G are independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. 6. The liquid crystal alignment according to any one of claims 1 to 3, wherein the other diamine is a mixture of diamines selected from the group consisting of the side chain described in claim 4 At least one selected from the group consisting of diamines, and at least one selected from the group consisting of diamines having no side chain groups represented by formulas (I) to (VII) and (XV); H2N-X-nh2 ( I) .R33 H2N—A3—[-Si一0 (XV).R33 H2N—A3—[-Si—0 (XV) R33 Si——A3一NH2 R34 該些式中,X為碳數2〜12的直鏈亞烷基;各Y獨立為單 鍵、-0-、-CO-、-NH-、-N(CH3)-、-CONH·、-NHCO-、 -C(CH3)2-、-C(CF3)2-、-0-(CH2)t-0-、-S-、-S-S-、-S02-、 -S-(CH2)rS-或碳數1〜12的直鏈亞烷基,t為1〜12的整數; Z1 及 Z2 為氫,但於 Y 為-NH-、-N(CH3)-、·&lt;:Η2-、-C(CH3)2-或-C(CF3)2·時也可以相互鍵結而形成單鍵;環D為亞苯基 或1,4-二氮雜亞環己基;R33及R34獨立為碳數1〜3的烷基, 201125896 - · - r — 或苯基;A3獨立為碳數1〜6的亞烧基、亞苯基,或被烧基 取代的亞苯基;m為1〜10的整數;環己烧環或苯環的任 意氫可被氟、甲基、三氟曱基、-OH、-COOH、-S03H、 -P〇3H2、苄基或羥基苄基取代。R33 Si——A3—NH2 R34 In the formula, X is a linear alkylene group having 2 to 12 carbon atoms; each Y is independently a single bond, -0-, -CO-, -NH-, -N (CH3) )-, -CONH·, -NHCO-, -C(CH3)2-, -C(CF3)2-, -0-(CH2)t-0-, -S-, -SS-, -S02-, -S-(CH2)rS- or a linear alkylene group having 1 to 12 carbon atoms, t is an integer of 1 to 12; Z1 and Z2 are hydrogen, but Y is -NH-, -N(CH3)-, ·&lt;:Η2-, -C(CH3)2- or -C(CF3)2· may also be bonded to each other to form a single bond; ring D is phenylene or 1,4-diazacyclohexylene R33 and R34 are independently a C 1~3 alkyl group, 201125896 - · - r - or a phenyl group; A3 is independently a C9-C6 alkylene group, a phenylene group, or a phenylene group substituted by an alkyl group. m; m is an integer from 1 to 10; any hydrogen of the cyclohexane or benzene ring may be fluorine, methyl, trifluoromethyl, -OH, -COOH, -S03H, -P〇3H2, benzyl or hydroxy Benzyl substitution. 7.如申請專利範圍第6項所述之液晶配向劑,其中該其 他二胺為如下二胺的混合物:選自式(VIII_2)、(VIII-4)〜 (VIII-6)、(Xli_2)、(XII_4)及(XII-6)表示的具有側鏈基的二 胺的至少一種,以及選自式(ΙλΜ)、(ιν_2)、(ιν·15)〜 (IV-17)、(V-1)〜(V-12)、(V-3 3)、(V-3 5)〜(V-3 7)、(VI-7)、(VII-2) 及(XV-1)所表示的不具側鏈基的二胺的至少一種;7. The liquid crystal alignment agent according to claim 6, wherein the other diamine is a mixture of diamines selected from the group consisting of formula (VIII_2), (VIII-4) to (VIII-6), (Xli_2) And (XII_4) and (XII-6) at least one of a diamine having a side chain group, and a selected from the group consisting of a formula (ΙλΜ), (ιν_2), (ιν·15)~(IV-17), (V- 1) ~(V-12), (V-3 3), (V-3 5)~(V-3 7), (VI-7), (VII-2) and (XV-1) At least one of diamines having no side chain groups; (νΙ&quot;·2) (VIM)(νΙ&quot;·2) (VIM) 71 201125896 該些式中,R23、R29及R3Q獨立為碳數1〜30的烷基,或碳 數1〜30的烷氧基;71 201125896 In the above formula, R23, R29 and R3Q are independently an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms; 2N2N 72 201125896 t--- 入8·如申請專利範圍第1項所述之液晶配向劑,其中該聚 口物是如下化合物的混合物: ^選自申請專利範圍第丨項所述之式(p l)〜(ρ_1〇)表示 、:胺的群組的至少一種及選自申請專利範圍第4項所述 2具有側鏈基的二胺的群組的至少一種的混合物與四羧酸 一軒反應而得的聚醯胺酸或其衍生物;以及 使選自申請專利範圍第6項所述之不具側鏈基的二胺 、群組的至少一種與四羧酸二酐反應而得的聚醯胺酸 ρ 衍生物。 9.如申請專利範圍第1項所述之液晶配向劑,其中該聚 合物是如下化合物的混合物: 使選自申請專利範圍第2項所述之式(ρ·〗)〜(ρ_1〇)表示 =二胺的群組的至少-種及選自中請專利範圍第4項中所 具有側鏈基的二胺的群組的至少一種的混合物與四羧 酸二酐反應而得的聚醯胺酸或其衍生物;以及 使選自申請專利範圍第6項所述之不具纖基的二胺 • 的群組的至少一種及選自式CMHIM0)表示的二胺的群 組的至J -種的混合物與四致酸二奸反應而得的聚醯胺酸 或其衍生物。 ι〇·如申請專利範圍第1項所述之液晶配向劑,其中該 t合物是如下化合物的混合物: 使由選自申請專利範圍第2項所述之式(P—D〜(1&gt;_1〇)表 示的二胺的群_至少—種及選自中請專利範圍第 4項所 述之具有侧鏈基的二胺的群組的至少一種以及選自申請專 73 201125896 利範圍第6項中所述之不具側鏈基的二胺的群組的至少一 種所構成的混合物與四羧酸二酐反應而得的聚醯胺酸或其 衍生物;以及 使所述不具側鏈基的二胺的至少一種與四繞酸二針反 應而得的聚醯胺酸或其衍生物。 11. 如申請專利範圍第1項所述之液晶配向劑,其中該 聚合物是如下化合物的混合物: 使由選自申請專利範圍第2項所述之式(P-1)〜(p-10)表 不的二胺的群組的至少一種及選自選自申請專利範圍第4 項所述之具有側鏈基的二胺的群組的至少一種以及選自申 5青專利範圍第6項所述之不具側鏈基的二胺的群組的至少 一種所構成的混合物與四羧酸二酐反應而得的聚醯胺酸 其衍生物;以及 使選自該不具侧鏈基的二胺的群組的至少一種及選自 式(ρ-υ〜(ρ·ιο)表示的二胺的群植的至少一種的混合物與 四羧酸二酐反應而得的聚醯胺酸或其衍生物。 12. 如申請專利範圍第i項所述之液晶配向劑,其中該 聚合物是如下化合物的混合物:使選 項所述之式㈣〜(P,表示的:胺的群組的至少圍】及 =了請專利範圍第6項所述之不具側鏈基的二胺的群組 種的混合物與喊酸&quot;^應而得的輯胺酸或 其何生物;以及 74 201125896 衍生物。 13.如申請專利範圍第1項所述之液晶配向劑,其中該 聚合物是如下化合物的混合物: 使選自申請專利範圍第2項所述之式(p-ι)〜(p_10)所表 示的二胺的群組的至少一種及選自申請專利範圍第6項所 述之不具侧鏈基的二胺的群組的至少一種的混合物與四羧 酸二酐反應而得的聚醯胺酸或其衍生物;以及 A使由選自申請專利範圍第4項所述之具有側鏈基的二 ,的群組的至少—種及選自該不具側鏈基的二胺的群組的 酸;;=成的混合物與四魏二野反應而得的聚酿胺 劑,JL中H利範圍第1〜3項中任—項所述之液晶配向 或者;= 香族四_二針之至少-種, 二肝的至少二I:至少一種與芳香族以外的四緩酸 15·如申請專利範圍第^項 劑’其中該四練二軒為式 —項所述之液晶配向 表示的料族四及 \\ Ρ η 土 夕—種:The liquid crystal alignment agent of claim 1, wherein the polyposition is a mixture of the following compounds: ^ selected from the formula (pl) of the scope of the patent application. ~(ρ_1〇) represents: a mixture of at least one of the group of amines and at least one selected from the group consisting of 2 groups of diamines having a side chain group described in claim 4, and reacting with tetracarboxylic acid a polylysine or a derivative thereof; and a polyamine obtained by reacting at least one selected from the group consisting of diamines having no side chain groups as described in claim 6 and tetracarboxylic dianhydride Acid ρ derivative. 9. The liquid crystal alignment agent according to claim 1, wherein the polymer is a mixture of the following compounds: (p·) to (ρ_1〇) selected from the second item of the patent application scope. a polydecylamine obtained by reacting at least one of a group of diamines and at least one selected from the group consisting of diamines having a side chain group in the fourth aspect of the patent range with tetracarboxylic dianhydride An acid or a derivative thereof; and a group of at least one selected from the group consisting of diamines having no fiber group described in claim 6 of the patent application and a group selected from the group consisting of diamines represented by the formula CMHIM0) Polyammonic acid or a derivative thereof obtained by reacting a mixture with tetrazoic acid. The liquid crystal alignment agent of claim 1, wherein the t compound is a mixture of the following compounds: a formula selected from the second item of the patent application scope (P-D~(1&gt;). _1 〇) indicates a group of diamines _ at least one species and at least one selected from the group consisting of diamines having a side chain group described in claim 4 of the patent application, and is selected from the application for the purpose of the 2011. a polyamido acid or a derivative thereof obtained by reacting a mixture of at least one of the group of diamines having no side chain groups described in the item with a tetracarboxylic dianhydride; and the non-side chain group A poly-proline or a derivative thereof, which is obtained by reacting at least one of a diamine with a tetra-acidic acid. The liquid crystal alignment agent according to claim 1, wherein the polymer is a mixture of the following compounds: At least one selected from the group consisting of diamines represented by the formulae (P-1) to (p-10) described in the second paragraph of the patent application, and selected from the group consisting of those selected in claim 4 At least one of the group of side chain diamines and selected from the sixth item of claim 5 a derivative of a polyamido acid obtained by reacting a mixture of at least one of a group of diamines having no side chain groups with a tetracarboxylic dianhydride; and a group selected from the group consisting of the diamine having no side chain group 12. At least one selected from the group consisting of a mixture of at least one of a group of diamines represented by the formula (ρ-υ~(ρ·ιο) and a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride. The liquid crystal alignment agent of claim i, wherein the polymer is a mixture of the following compounds: (4) to (P, representing: at least a group of amine groups) and = a mixture of a group of diamines having no side chain groups as described in the sixth aspect of the patent, and an amino acid or a living organism thereof; and 74 201125896 derivatives. The liquid crystal alignment agent according to the above item 1, wherein the polymer is a mixture of the following compounds: a group selected from the group consisting of the diamines represented by the formula (p-ι) to (p_10) described in the second paragraph of the patent application. At least one of the group and two selected from the group consisting of the sixth aspect of the patent application a polyamido acid or a derivative thereof obtained by reacting a mixture of at least one of the group with a tetracarboxylic dianhydride; and A is obtained by a group having a side chain group selected from the fourth aspect of the patent application. At least one group of the group and an acid selected from the group of the diamines having no side chain group;; = a mixture of the mixture and the fermented amine agent obtained from the reaction of the four Wei and the two fields, and the range of the H in the JL range is 1~ The liquid crystal alignment as described in any of the three items, or the == at least two species of the four or two needles of the fragrant family, and at least two of the two livers of the second liver: at least one of the four acid acids other than the aromatic ones. The item "in the four practice two porch is the formula" - the liquid crystal alignment said the material family four and \\ Ρ η 夕 夕 - species: (ΗΜΟ) (Η-22) 75 201125896 '-~Γ— 劑利範園第1〜3項中任-項所述之液晶配向 f中四^酸—_為式(Η·1)表*的芳香族讀酸二針:(ΗΜΟ) (Η-22) 75 201125896 '-~Γ—The liquid crystal alignment f in the No. 1 to 3 of the agent Li Fanyuan, the tetra-acid-- is the aroma of the formula (Η·1) Family reading acid two needles: (Η-1) 1如^專利範圍第1〜3項中任-項所述之液晶配向 、中该四敌酸二酐為如下化合物的混合物: 劑,(Η-1) 1 The liquid crystal alignment according to any one of Items 1 to 3 of the patent range, wherein the tetracarboxylic acid dianhydride is a mixture of the following compounds: 式(Η-1)、(Η-5)、(Η·8)〜(Η-10)及(Η·22)表示的芳香族四 幾酸一奸之至少一種;以及 式(S-l)、(S-6)、(S-9)〜(S-10)、(S-21)〜(S-22)、(S.3〇)、 (S-43)〜(S-45)、(S-48)及(S-52)表示的芳香族以外的四綾酸 一軒的至少一種;At least one of the aromatic tetraacids represented by the formulas (Η-1), (Η-5), (Η·8)~(Η-10), and (Η·22); and the formula (S1), S-6), (S-9)~(S-10), (S-21)~(S-22), (S.3〇), (S-43)~(S-45), (S -48) and (S-52) at least one of tetradecanoic acid other than aromatic; (H-5) (H-8)(H-5) (H-8) (S-1&gt; (S-6) (S-9) (S-10)(S-1&gt; (S-6) (S-9) (S-10) (S-21)(S-21) (S-22)(S-22) (S-30) (S-43) 76 201125896(S-30) (S-43) 76 201125896 18. 如申請專利範圍第17項所述之液晶配向劑’其中該 芳香族以外的四羧酸二酐為式(S-l)、(S-6)、(S-9)、(S-45)、 (S-48)及(S-52)所表示的化合物的至少一種。18. The liquid crystal alignment agent according to claim 17, wherein the tetracarboxylic dianhydride other than the aromatic is a formula (S1), (S-6), (S-9), (S-45) At least one of the compounds represented by (S-48) and (S-52). 19. 如申請專利範圍第π項所述之液晶配向劑’其中該 芳香族四羧酸二酐為式(Η-1)表示的化合物,該芳香族以外 的四羧酸二酐為式(S-1)及(S-48)表示的化合物的至少一 種。 20. —種液晶配向膜,其藉由對申請專利範圍第1〜19 項中任一項所述之液晶配向劑的塗膜進行加熱而形成。 21.—種液晶顯示元件,包括:一對基板、形成於該對 基板之間的液晶層、對液晶層施加電壓的電極,以及申請 專利範圍第20項所述之液晶配向膜。19. The liquid crystal alignment agent according to the invention of claim π, wherein the aromatic tetracarboxylic dianhydride is a compound represented by the formula (Η-1), and the tetracarboxylic dianhydride other than the aromatic is a formula (S) At least one of the compounds represented by -1) and (S-48). 20. A liquid crystal alignment film which is formed by heating a coating film of a liquid crystal alignment agent according to any one of claims 1 to 19. A liquid crystal display device comprising: a pair of substrates; a liquid crystal layer formed between the pair of substrates; an electrode for applying a voltage to the liquid crystal layer; and the liquid crystal alignment film of claim 20. 77 201125896 四、 指定代表圖: (一) 本案指定代表圖為:無。 (二) 本代表圖之元件符號簡單說明:無。 五、 本案若有化學式時,請揭示最能顯示發明特徵 的化學式:77 201125896 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
TW100102716A 2010-01-26 2011-01-25 Liquid crystal aligning agents, liquid crystal aligning layers and liquid crystal display devices TW201125896A (en)

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Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5691610B2 (en) * 2010-04-15 2015-04-01 Jsr株式会社 Composition for forming liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element
JP2013076958A (en) * 2011-09-30 2013-04-25 Dainippon Printing Co Ltd Production method of electromagnetic wave reflection film
JP5874590B2 (en) * 2011-12-26 2016-03-02 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, polymer and compound
JP5949070B2 (en) 2012-04-03 2016-07-06 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP2014070111A (en) * 2012-09-28 2014-04-21 Nippon Zeon Co Ltd Insulator, insulating film, laminate, and method for manufacturing laminate
JP6278216B2 (en) * 2013-05-22 2018-02-14 日産化学工業株式会社 Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element using the same
JP6315182B2 (en) * 2014-03-18 2018-04-25 Jsr株式会社 Liquid crystal aligning agent and liquid crystal display element
JP6492688B2 (en) * 2014-04-23 2019-04-03 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film, manufacturing method thereof, and liquid crystal display element
CN104086750B (en) * 2014-07-28 2017-05-03 武汉工程大学 Application of curing agent 1,2-bi(2,6-dioxo-4-morpholinyl) ethane in epoxy resin system
CN104327861B (en) * 2014-09-18 2016-05-25 四川大学 Contain soluble polyimide liquid crystal vertical-tropism agent of pyridine ring and preparation method thereof and liquid crystal cell prepared therefrom
JP7319924B2 (en) * 2017-03-03 2023-08-02 ロリク・テクノロジーズ・アーゲー New photo-alignment composition for stabilizing pretilt angle in liquid crystal layer
KR102161675B1 (en) * 2017-05-22 2020-10-05 주식회사 엘지화학 Polymer for liquid crystal aligning agent, amd liquid crystal aligning agent comprising the same, and liquid crystal aligning film, liquid crystal display device using the same
KR102162502B1 (en) 2017-05-22 2020-10-06 주식회사 엘지화학 Polymer for liquid crystal aligning agent, amd liquid crystal aligning agent comprising the same, and liquid crystal aligning film, liquid crystal display device using the same
KR102020030B1 (en) 2017-08-24 2019-09-10 주식회사 엘지화학 Polymer for liquid crystal aligning agent, amd liquid crystal aligning agent composition comprising the same, and liquid crystal aligning film, liquid crystal display device using the same
KR102161673B1 (en) 2017-09-07 2020-10-05 주식회사 엘지화학 Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same
KR102162501B1 (en) 2017-09-08 2020-10-06 주식회사 엘지화학 Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same
KR102161671B1 (en) 2017-09-29 2020-10-05 주식회사 엘지화학 Copolymer for liquid crystal aligning agent, liquid crystal aligning agent comprising the same, liquid crystal aligning film, and liquid crystal display device using the same
KR102195312B1 (en) 2017-10-20 2020-12-24 주식회사 엘지화학 Liquid crystal alignment composition, process for preparing liquid crystal alignment film, and liquid crystal alignment film using the same
KR102195313B1 (en) * 2017-10-20 2020-12-24 주식회사 엘지화학 Liquid crystal alignment composition, process for preparing liquid crystal alignment film, and liquid crystal alignment film using the same
KR102236903B1 (en) 2017-11-03 2021-04-06 주식회사 엘지화학 Liquid crystal alignment composition, process for preparing liquid crystal alignment film, and liquid crystal alignment film using the same
KR102196880B1 (en) * 2017-11-03 2020-12-30 주식회사 엘지화학 Liquid crystal alignment composition, process for preparing liquid crystal alignment film, and liquid crystal alignment film using the same
WO2019093037A1 (en) 2017-11-07 2019-05-16 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal element
KR102235476B1 (en) 2018-03-30 2021-04-01 주식회사 엘지화학 Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same
KR102251401B1 (en) * 2018-11-08 2021-05-11 주식회사 엘지화학 Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, liquid crystal display using the same
KR102391473B1 (en) 2019-01-17 2022-04-26 주식회사 엘지화학 Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, liquid crystal display using the same
CN114249892B (en) * 2020-09-24 2023-05-26 中国科学院深圳先进技术研究院 Polyimide precursor resin and preparation method and application thereof
JP7512879B2 (en) 2020-12-21 2024-07-09 Jnc株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using the same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55137133A (en) * 1979-04-13 1980-10-25 Nippon Petrochem Co Ltd Polyamidic acid
JPS55137132A (en) * 1979-04-13 1980-10-25 Nippon Petrochem Co Ltd Polyimide
SU858316A1 (en) * 1979-12-17 1985-11-30 Новосибирский институт органической химии СО АН СССР 2,5-di-(n-aminophenyl)pyramidine as monomer for synthesis of polymides,method of producing same and polyimides on its base as heat resistant material
JPS62270623A (en) * 1985-12-07 1987-11-25 Daicel Chem Ind Ltd Bis(4-aminophenyl)pyrazine, its production, polyimide and its production
JP2005037920A (en) * 2003-06-24 2005-02-10 Jsr Corp Liquid crystal alignment agent, liquid crystal alignment layer, and liquid crystal display element
JP4985609B2 (en) * 2007-12-26 2012-07-25 Jnc株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2009093709A1 (en) * 2008-01-25 2009-07-30 Nissan Chemical Industries, Ltd. Liquid-crystal alignment material, liquid-crystal alignment film, and liquid-crystal display element

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