TW201005006A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Liquid crystal alignment agent and liquid crystal display element Download PDF

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TW201005006A
TW201005006A TW098120197A TW98120197A TW201005006A TW 201005006 A TW201005006 A TW 201005006A TW 098120197 A TW098120197 A TW 098120197A TW 98120197 A TW98120197 A TW 98120197A TW 201005006 A TW201005006 A TW 201005006A
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liquid crystal
group
crystal alignment
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alignment agent
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TWI460210B (en
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Kenichi Izumi
Tsubasa Abe
Eiji Hayashi
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Jsr 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
    • 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

The object of the present invention is to provide a liquid crystal display element, wherein is capable of forming a liquid crystal display element without reducing the voltage holding ratio even though applying thermal stress at long term, a liquid crystal alignment agent of a liquid crystal alignment film having high heat resistance, and the display quality does not reduce even though driving at long term. The solution of the present invention is to provide a liquid crystal alignment film, wherein said liquid crystal alignment agent comprising at least one polymer selected from the group consisting polyamic acid and polyimide, wherein in the molecule of the said polymer comprising at least one part of structure represented by following formula (A). The said liquid crystal display element has a liquid crystal alignment film forming from a liquid crystal alignment agent.

Description

201005006 六、發明說明: 【發明所屬之技術領域】 本發明涉及一種液晶配向劑和液晶顯示元件。更具體 地說,涉及能夠形成顯示優良耐熱性的液晶配向膜的液晶 配向劑以及長時間驅動顯示品質也不會降低的液晶顯示元 件。 【先前技術】 目前,作爲液晶顯示元件,具有所謂TN型(扭曲向列) e 液晶胞的TN型液晶顯示元件已廣爲人知,其在設置了透 明導電膜的基板表面上形成液晶配向膜,作爲液晶顯示元 件用的基板,將兩塊該基板相對設置,在其間隙內形成具 有正介電各向異性的向列型液晶層,構成夾層結構的胞, 液晶分子的長軸從一塊基板向另一塊基板連續地扭轉90 度。另外,還開發了與TN型液晶顯示元件相比能夠實現 更髙對比度的STN(超扭曲向列)型液晶顯示元件、視角依 賴性小的IPS (面內切換)型液晶顯示元件、改變IPS型電極 〇 結構而提高顯示元件部分的開口率以提高亮度的FFS(邊緣 場轉換)型液晶顯示元件、視角依賴性小同時視頻畫面的高 速回應性優良的〇CB(Optical Compensated Bend :光學補 償彎曲)型液晶顯示元件以及採用具有負介電各向異性的 向列型液晶的VA(垂直配向)型液晶顯示元件等。 作爲這些液晶顯示元件中的液晶配向膜的材料,已知 聚醯胺酸、聚醯亞胺、聚醯胺、聚酯等樹脂材料,特別是 由聚醯胺酸或聚醯亞胺製作的液晶配向膜,其耐熱性、機 -4- 201005006 械強度、與液晶的親和性等優良,故而在大多液晶顯示元 件中被使用(參見例如專利文獻1〜3)。 如上所述的液晶顯示元件,與以前相比要求更長時間 的驅動。例如以近年來的液晶電視機爲代表,要求長時間 (例如1 0年以上)保持良好的顯示狀態,特別是要求具有即 使由於長時間的顯示驅動而施加熱應力也能夠維持高的電 壓保持率的性能(以下也稱爲“耐熱性”)。 以前已知的液晶配向膜用樹脂材料,相比聚醯胺酸, 〇 通過使用聚醯亞胺,或者作爲其製備中所用的單體,使用 對苯二胺,來達到提高耐熱性的目的。但是,採用這種策 略對耐熱性的提高有限,採用以前已知的液晶配向膜用樹 脂材料,已不能滿足日益嚴苛的液晶顯示元件的使用環境 中所需的耐熱性。 【現有技術文獻】 【專利文獻】 【專利文獻1】日本特開平9-197411號公報 ® 【專利文獻2】日本特開2003-149648號公報 【專利文獻3】日本特開2003 - 107486號公報 【專利文獻4】日本特開平6— 222366號公報 【專利文獻5】日本特開平6-281937號公報 【專利文獻6】日本特開平5 - 107544號公報 【發明内容】 本發明是璧於上述情況而作出的,其目的是提供能夠 形成即使長時間施加熱應力電壓保持率也不會下降、具有 201005006 高的耐熱性液晶配向膜的液晶配向劑,以及即使長時間驅 動顯示品質也不會下降的液晶顯示元件。 本發明的其他目的和優點,可以由以下的說明獲悉。 根據本發明,本發明的上述目的和優點,第一,由一 種液晶配向劑達成,其含有選自聚醯胺酸和聚醯亞胺構成 的群組中的至少一種聚合物,其中上述聚合物的分子中的 至少一部分具有下述式(A)表示的結構。201005006 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, it relates to a liquid crystal display element capable of forming a liquid crystal alignment film which exhibits excellent heat resistance and a liquid crystal display element which does not deteriorate display quality for a long period of time. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN type (twisted nematic) e liquid crystal cell is widely known, and a liquid crystal alignment film is formed on a surface of a substrate on which a transparent conductive film is provided. As a substrate for a liquid crystal display element, two substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a cell of a sandwich structure, and the long axis of the liquid crystal molecules is directed from one substrate to the substrate. The other substrate is continuously twisted by 90 degrees. In addition, an STN (Super Twisted Nematic) liquid crystal display element capable of achieving a higher contrast ratio than a TN liquid crystal display element, an IPS (in-plane switching) type liquid crystal display element having a small viewing angle dependency, and an IPS type change have been developed. FFCB (Optical Compensated Bend) which is excellent in the FFS (Fringe Field Conversion) type liquid crystal display element which improves the aperture ratio of the display element portion to improve the luminance, and has excellent viewing angle dependence and high-speed response of the video picture. A liquid crystal display element and a VA (Vertical Alignment) type liquid crystal display element using nematic liquid crystal having negative dielectric anisotropy. As a material of the liquid crystal alignment film in these liquid crystal display elements, a resin material such as polyacrylic acid, polyamidiamine, polyamine, or polyester, particularly a liquid crystal made of polyamic acid or polyimine, is known. The alignment film is excellent in heat resistance, mechanical strength, affinity with liquid crystal, and the like, and is used in many liquid crystal display elements (see, for example, Patent Documents 1 to 3). The liquid crystal display element as described above requires a longer driving than before. For example, in recent years, liquid crystal televisions are required to maintain a good display state for a long period of time (for example, 10 years or more), and in particular, it is required to maintain a high voltage holding ratio even if thermal stress is applied due to long-term display driving. Performance (hereinafter also referred to as "heat resistance"). The resin material for a liquid crystal alignment film which has been known in the prior art is used for the purpose of improving heat resistance by using polyamidiamine or by using p-phenylenediamine as a monomer used in the preparation thereof. However, the use of such a strategy for the improvement of the heat resistance is limited, and the conventionally known resin material for a liquid crystal alignment film cannot satisfy the heat resistance required in the environment in which an increasingly severe liquid crystal display element is used. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2003-149. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The object of the present invention is to provide a liquid crystal alignment agent capable of forming a heat-resistant liquid crystal alignment film having a high thermal stress holding rate even if it is applied for a long period of time, and having a high heat resistance liquid crystal alignment film of 201005006, and a liquid crystal which does not deteriorate even if the display quality is driven for a long period of time. Display component. Other objects and advantages of the invention will be apparent from the description which follows. According to the present invention, the above objects and advantages of the present invention, first, are achieved by a liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polylysine and polyimine, wherein the polymer At least a part of the molecules have a structure represented by the following formula (A).

(A) 本發明的上述目的和優點,第二,由具有由上述液晶 配向劑形成的液晶配向膜的液晶顯示元件達成。 本發明的液晶配向劑能夠形成即使長時間施加熱應力 電壓保持率也不會下降的液晶配向膜。 具有這種由本發明液晶配向劑形成的液晶配向膜的本 發明液晶顯示元件,即使長時間驅動,顯示品質也不會下 降。因此,本發明的液晶顯示元件可有效地應用於各種裝 置,例如可適用於鐘錶、可檇式遊戲機、文字處理器、筆 記型電腦、汽車導航儀、攝錄像機、PDA(個人數位助理)、 數碼照相機、行動電話、各種監視器、液晶電視機等的顯 ,ϋ-f· ccet 不裝置。 【實施方式】 具體實施方式 以下,對本發明進行詳細說明》 本發明的液晶配向劑含有選自聚醯胺酸和聚醯亞胺構 201005006 成的群組中的至少一種聚合物,其中上述聚合物的分子中 的至少一部分具有上述式(A)表示的結構。以下,在本說明 書中,這種聚合物稱爲“特定聚合物”。在該特定聚合物 中,上述式(A)表示的結構可以存在於聚合物的主鏈中,也 可以存在於聚合物的側鏈中,或者在聚合物的主鏈和側鏈 兩者中均存在。 作爲上述式(A)表示的結構,較佳爲選自下述式(A - 1) 〜(A-3)各自表示的結構構成的群組中的至少一種結構,(A) The above object and advantages of the present invention, and secondly, achieved by a liquid crystal display element having a liquid crystal alignment film formed of the above liquid crystal alignment agent. The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film which does not decrease even if a thermal stress voltage holding ratio is applied for a long period of time. The liquid crystal display element of the present invention having such a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention does not deteriorate in display quality even when driven for a long period of time. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, for example, it can be applied to a timepiece, a portable game machine, a word processor, a notebook computer, a car navigation system, a video camera, a PDA (personal digital assistant), Digital cameras, mobile phones, various monitors, LCD TVs, etc., ϋ-f· ccet are not installed. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The liquid crystal alignment agent of the present invention contains at least one polymer selected from the group consisting of polylysine and polyamidiamine 201005006, wherein the above polymer At least a part of the molecules have a structure represented by the above formula (A). Hereinafter, in the present specification, such a polymer is referred to as a "specific polymer." In the specific polymer, the structure represented by the above formula (A) may be present in the main chain of the polymer, or may be present in the side chain of the polymer, or in both the main chain and the side chain of the polymer. presence. The structure represented by the above formula (A) is preferably at least one selected from the group consisting of structural configurations represented by the following formulas (A-1) to (A-3).

(式(A— 1)中的Ra爲鹵素原子、氰基、異氰基、-〇CN、 -NCO、- SCN、-NCS或疊氮(azi)基,η爲0〜3的整數, 各自表示爲連接鍵;(Ra in the formula (A-1) is a halogen atom, a cyano group, an isocyano group, -〇CN, -NCO, -SCN, -NCS or an azide group, and η is an integer of 0 to 3, each Expressed as a connection key;

式(Α— 2)和(Α-3)中的Rb和R。各自獨立地爲氫原 子、鹵素原子、氰基、異氰基、-〇CN、-NCO、-SCN、-NCS 201005006 或疊氮基,各自表示爲連接鍵)。 聚合物中上述式(A)表示的結構的含量比率,較佳爲 2.0xl0-5莫耳/g以上,更佳爲Ι.ΟχΙΟ·4〜3.0xl〇·3莫耳/g, 特佳爲 2.0xl0·4 〜1·Οχ1〇·3 莫耳/g。 分子中的至少一部分具有上述式(A)表示的結構的聚 醯胺酸’例如,可以通過使下述進行反應而製得,即、含 有具有上述式(A)表示的結構和2個羧酸酐基團的化合物的 四羧酸二酐與二胺反應,或者使四羧酸二酐與含有具有上 〇 述式(Α)表示的結構和2個胺基的化合物的二胺反應而製 得。分子中的至少一部分具有上述式(A)表示的結構的聚醯 亞胺可以通過例如將如上所述製得的聚醯胺酸進行脫水閉 環而製得。 作爲本發明液晶配向劑中包含的特定聚合物,較佳爲 選自使四羧酸二酐與含有具有上述式(A)表示的結構和2個 胺基的化合物的二胺反應而製得的聚醯胺酸以及將該聚醯 胺酸脫水閉環而得到的聚醯亞胺構成的群組中的至少一種 © 聚合物。 <四羧酸二酐> 作爲用於合成本發明液晶配向劑中的較佳的聚醯胺酸 的四羧酸二酐,可以列舉脂環式四羧酸二酐、脂肪族四羧 酸二酐和芳香族四羧酸二酐。 作爲上述脂環式四羧酸二酐的具體例子’可以列舉例 如1,2,3,4-環丁烷四羧酸二酐、1,2-二甲基-1,2,3,4-環丁院 四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、丨,3· 201005006 二氯-1,2,3,4-環丁烷四羧酸二酐、1,2,3,4-四甲基-l,2,3,4-環丁烷四羧酸二酐、l,2,3,4-環戊烷四羧酸二酐、l,2,4,5-環己烷四羧酸二酐、3,3’,4,4’-二環己基四羧酸二酐、順式 -3,7-二丁基環辛-1,5-二烯-1,2,5,6-四羧酸二酐、2,3,5-三羧 基環戊基醋酸二酐、5-(2,5-二側氧四氫-3-呋喃基)-3-甲基 -3-環己烯-1,2-二羧酸酐、3,5,6-三羧基-2-羧基降冰片烷 -2:3,5:6-二酐 、2,3,4,5-四氫呋喃四羧酸二酐、 l,3,3a,4,5,9b -六氫-5-(四氫-2,5 -二側氧-3 -呋喃基)-萘 〇 [l,2-c]-呋喃-1,3-二酮、l,3,3a,4,5,9b-六氫-5-甲基- 5-(四氫 -2,5-二側氧-3-呋喃基)-萘[l,2-c]-呋喃-1,3-二酮、 1,3,33,4,5,913-六氫-5-乙基-5-(四氫-2,5-二側氧-3-呋喃基)-萘[l,2-c]-呋喃-1,3-二酮、l,3,3a,4,5,9b-六氫-7-甲基- 5-(四 氫-2,5-二側氧-3-呋喃基)-萘[1,2-(:]-呋喃-1,3-二酮、 1,3,3&,4,5,91)-六氫-7-乙基-5-(四氫-2,5-二側氧-3-呋喃基)-萘[l,2-c]-呋喃-1,3-二酮、l,3,3a,4,5,9b-六氫-8-甲基- 5-(四 氫-2,5 -二側氧-3 -呋喃基)-萘[l,2-c] -呋喃-1,3 -二酮、 © 1,3,3&,4,5,91)-六氫-8-乙基-5-(四氫-2,5-二側氧-3-呋喃基)- 萘[l,2-c]-呋喃-1,3-二酮、1,3,3&,4,5,91>-六氫-5,8-二甲基 -5-(四氫-2,5 -二側氧-3 -呋喃基)-萘[1,2-c] -呋喃-1,3 -二 酮、5-(2,5-二側氧四氫呋喃基)-3-甲基-3-環己烯-1,2-二羧 酸酐、雙環[2.2.2]-辛-7-烯-2,3,5,6-四羧酸二酐、3-氧雜雙 環[3.2.1]辛烷-2,4-二酮-6-螺- 3’-(四氫呋喃- 2’,5’-二酮)、下 述式(T— I)和(T — II)各自表示的化合物等; 201005006Rb and R in the formulas (Α-2) and (Α-3). Each is independently a hydrogen atom, a halogen atom, a cyano group, an isocyano group, -〇CN, -NCO, -SCN, -NCS 201005006 or an azide group, each represented as a linkage). The content ratio of the structure represented by the above formula (A) in the polymer is preferably 2.0 x 10 -5 mol / g or more, more preferably Ι. ΟχΙΟ · 4 to 3.0 x l · 3 m / g, particularly preferably 2.0xl0·4 〜1·Οχ1〇·3 Moor/g. The polyamic acid having at least a part of the molecule having the structure represented by the above formula (A) can be obtained, for example, by reacting the following, that is, containing the structure represented by the above formula (A) and two carboxylic anhydrides. The tetracarboxylic dianhydride of the compound of the group is reacted with a diamine or a tetracarboxylic dianhydride is reacted with a diamine containing a compound having a structure represented by the above formula (Α) and two amine groups. The polyimine having at least a part of the molecule having the structure represented by the above formula (A) can be produced, for example, by dehydrating and blocking the polylysine obtained as described above. The specific polymer contained in the liquid crystal alignment agent of the present invention is preferably selected from the group consisting of reacting a tetracarboxylic dianhydride with a diamine containing a compound having the structure represented by the above formula (A) and two amine groups. At least one of the group consisting of polylysine and a polyamidene obtained by dehydration of the polyamic acid ring. <tetracarboxylic dianhydride> Examples of the tetracarboxylic dianhydride which is preferred for synthesizing the polyamic acid in the liquid crystal alignment agent of the present invention include alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic acid. A dianhydride and an aromatic tetracarboxylic dianhydride. Specific examples of the alicyclic tetracarboxylic dianhydride include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutylidene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, hydrazine, 3· 201005006 dichloro-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-l,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane IV Carboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cyclohexyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-di-side oxygen Tetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5: 6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3 -furyl)-naphthoquinone [l,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro- 2,5-dioxa-3-furyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,33,4,5,913-hexahydro-5-ethyl- 5- (four -2,5-di-oxo-3-furyl)-naphthalene [l,2-c]-furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-7- Methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3,3&,4 ,5,91)-hexahydro-7-ethyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-di Ketone, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c] -furan-1,3-dione, © 1,3,3&,4,5,91)-hexahydro-8-ethyl-5-(tetrahydro-2,5-di-oxo-3-furan Base)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,91>-hexahydro-5,8-dimethyl-5-(four Hydrogen-2,5-di-oxo-3-furyl)-naphthalene[1,2-c]-furan-1,3-dione, 5-(2,5-di-oxo-tetrahydrofuranyl)-3- Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[ 3.2.1] Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), the following formulas (T-I) and (T-II) Compounds, etc.; 201005006

(Τ-Ι)(Τ-Ι)

(式(Τ-Ι)和(Τ— II)中,R1和R3各自爲具有芳香環的2 價有機基團,R2和R4各自爲氫原子或烷基’存在的多個 R2和R4各自可以相同,也可以不同)。(In the formulae (Τ-Ι) and (Τ-II), each of R1 and R3 is a divalent organic group having an aromatic ring, and each of R2 and R4 is a hydrogen atom or a plurality of R2 and R4 each The same, can also be different).

作爲上述脂肪族四羧酸二酐的具體例子,可以列舉例 如丁烷四羧酸二酐等。 作爲上述芳香族四羧酸二酐的具體例子,可以列舉例 如均苯四酸二酐、3,3’,4,4’-二苯酮四羧酸二酐、3,3,,4,4’-二苯基碾四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-萘 四羧酸二酐、3,3’,4,4’-二苯基醚四羧酸二酐、3,3,,4,4’-二 甲基二苯基矽烷四羧酸二酐、3,3’,4,4,-四苯基矽烷四羧酸 二酐、1,2,3,4-呋喃四羧酸二酐、4,4,-雙(3,4-二羧基苯氧基) 二苯基硫醚二酐、4,4’-雙(3,4-二羧基苯氧基)二苯基碾二 酐、4,4’-雙(3,4-二羧基苯氧基)二苯基丙烷二酐、3,3,,4,4’-全氟異亞丙基二鄰苯二甲酸二酐、3,3’,4,4,-聯苯四殘酸二 酐、雙(鄰苯二甲酸)苯膦氧化物二酐、對亞苯基-雙(三苯基 鄰苯二甲酸)二酐、間亞苯基-雙(三苯基鄰苯二甲酸)二酐、 雙(三苯基鄰苯二甲酸)-4,4’-二苯醚二酐、雙(三苯基鄰苯二 甲酸)-4,4’-二苯基甲烷二酐、乙二醇-雙(脫水偏苯三酸 酯)、丙二醇-雙(脫水偏苯三酸酯)、i,4_丁二醇-雙(脫水偏 -10- 201005006 苯三酸酯)、1,6-己二醇-雙(脫水偏苯三酸酯)、1,8-辛二醇-雙(脫水偏苯三酸酯)、2,2-二(4-羥苯基)丙烷-雙(脫水偏苯 三酸酯)、下述式(T-1)〜(T- 4)各自表示的化合物等。Specific examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride and the like. Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, and 3,3,4,4. '-Diphenyl milled tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4 '-Diphenyl ether tetracarboxylic dianhydride, 3,3,,4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4,-tetraphenylnonane IV Carboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4,-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'- Bis(3,4-dicarboxyphenoxy)diphenyl succinic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3,,4, 4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4,-biphenyl tetraresic acid dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, pair Phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4' -diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane Anhydride, ethylene glycol-bis(hydrogen trimellitate), propylene glycol-bis(hydrogen trimellitate), i,4-butanediol-bis (dehydration partial-10-201005006 trimellitic acid ester), 1,6-hexanediol-bis(hydrogen trimellitate), 1,8-octanediol-bis(anhydrotrimellitic acid ester), 2,2-bis(4-hydroxyphenyl)propane- A compound represented by each of bis(hydrogen trimellitate) and the following formulas (T-1) to (T-4).

-11 - 201005006-11 - 201005006

-12- 201005006 這些四羧酸二酐可以一種單獨或兩種以上組合使用。 用於合成本發明液晶配向劑中的較佳的聚醯胺酸的四 羧酸二酐,較佳爲含有選自脂環式四羧酸二酐、均苯四酸 二酐和2,2’,3,3’-聯苯四羧酸二酐構成的群組中的至少一 種(以下稱爲.“特定四羧酸二酐”)的四羧酸二酐。作爲特 定四羧酸二酐,從能夠表現良好的液晶配向性的角度出 發’較佳爲選自1,2,3,4·環丁烷四羧酸二酐、1,3-二甲基 -1,2,3,4-環丁烷四羧酸二酐、l,2,3,4-四甲基-1,2,3,4-環丁 Ο 烷四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、2,3,5-三羧基 環戊基醋酸二酸酐、5-(2,5-二側氧四氫-3-呋喃基)-3-甲基 -3-環己烯-1,2-二羧酸酐、5-(2,5-二側氧四氫呋喃基)-3-甲 基-3-環己烯-1,2-二羧酸酐、順式-3,7-二丁基環辛-1,5-二烯 -1,2,5,6-四羧酸二酐、3,5,6·三羧基-2-羧基降冰片烷 -2:3,5:6 -二酐、l,3,3a,4,5,9b -六氫-5-(四氫- 2,5-二側氧- 3-肤喃基)-萘[l,2-c] -呋喃-1,3-二酮、i,3,3a,4,5,9b -六氫-8-甲基-5-(四氫-2,5-二側氧-3-呋喃基)_萘[1,2-(;]-呋喃-1,3-〇二酮、1,3,3丑,4,5,91)-六氫-5,8-二甲基_5-(四氫-2,5-二側氧 -3-呋喃基)-萘[1,2-(:]-呋喃-1,3-二酮、雙環[2.2.2]-辛-7-烯 •2,3,5,6-四羧酸二酐、3-氧雜雙環[3.2.1]辛烷-2,4-二酮-6-螺-3’-(四氫呋喃-2’,5’-二酮)、上述式(T 一 I)表示的化合物 中的下述式(T 一 5)〜(T— 7)各自表示的化合物、上述式(τ -II)表示的化合物中的下述式(T 一 8)表示的化合物、均苯 四酸二酐和2,2’,3,3’-聯苯四羧酸二酐構成的群組中的至 少一種, •13- 201005006-12- 201005006 These tetracarboxylic dianhydrides may be used alone or in combination of two or more. The tetracarboxylic dianhydride of the preferred polyamic acid for use in the synthesis of the liquid crystal alignment agent of the present invention preferably contains an alicyclic tetracarboxylic dianhydride, pyromellitic dianhydride and 2,2'. A tetracarboxylic dianhydride of at least one of the group consisting of 3,3'-biphenyltetracarboxylic dianhydride (hereinafter referred to as "specific tetracarboxylic dianhydride"). The specific tetracarboxylic dianhydride is preferably selected from the group consisting of 1,2,3,4·cyclobutane tetracarboxylic dianhydride and 1,3-dimethyl group from the viewpoint of exhibiting good liquid crystal alignment. 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2 , 3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dihydrotetrahydro-3-furanyl)-3- Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 5-(2,5-di-oxo-tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-carboxynorbornane- 2:3,5:6-dianhydride, l,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxanoxy-3-yanoyl)-naphthalene [l ,2-c]-furan-1,3-dione, i,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3 -furyl)_naphthalene [1,2-(;]-furan-1,3-indanedion, 1,3,3 ugly, 4,5,91)-hexahydro-5,8-dimethyl_ 5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, bicyclo[2.2.2]-oct-7- Alkene 2,3,5,6-tetracarboxylic acid , 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), represented by the above formula (T-I) a compound represented by the following formula (T-5) to (T-7), a compound represented by the following formula (T-8), and pyromellitic acid among the compounds represented by the above formula (τ-II); At least one of a group consisting of dianhydride and 2,2',3,3'-biphenyltetracarboxylic dianhydride, • 13-201005006

(Τ-5) σ-β)(Τ-5) σ-β)

更佳爲含有選自1,2,3,4-環丁烷四羧酸二酐、 基_1,2,3,4-環丁烷四羧酸二酐、2,3,5-三羧基環戊基 酸酐、5-(2,5-二側氧四氫-3-呋喃基)-3-甲基-3-環己 二羧酸酐、1,3,3&,4,5,91)-六氫-5-(四氫-2,5-二側氧 基)·萘[l,2-c]-呋喃-1,3-二酮、順式-3,7-二丁基環 二烯-1,2,5,6-四羧酸二酐、3,5,6-三羧基-2-羧基降 9 -2:3,5:6 -二酐、1,3,3&,4,5,91>-六氫-8-甲基-5-(四氫 側氧-3-呋喃基萘[l,2-c]-呋喃-1,3-二酮、3-氧 [3·2.1]辛烷-2,4·二酮-6-螺- 3’-(四氫呋喃- 2’,5’-二画 式(τ~5)表示的化合物、均苯四酸二酐和2,2’,3,3’ 竣酸二酐構成的群組中的至少一種的四羧酸二酐, 選自1,2,3,4-環丁烷四羧酸二酐、2,3,5-三羧基環戊 —軒、l,3,3a,4,5,9b -六氨-8-甲基- 5- (四氮- 2,5 - 一 側 喃基)-萘[1,2-c]-呋喃-1,3-二酮和均苯四酸二酐構 ,3·二甲 醋酸二 嫌-1,2 --3-呋喃 辛-1,5-冰片院 -2,5-二 雜雙環 丨)、上述 -聯苯四 特佳爲 基醋酸 氧-3-呋 成的群 -14- 201005006 組中的至少一種。 作爲可以與特定四羧酸二酐聯用的較佳的其他四竣酸 二酐,可以列舉例如丁烷四羧酸二酐、3,3’,4,4,·二苯酮四 羧酸二酐、3,3’,4,4’-二苯基楓四羧酸二酐、1,4,5,8-萘四羧 酸二酐等。 用於合成本發明液晶配向劑中的聚醯胺酸的四羧酸二 酐’較佳相對於全部四羧酸二酐,含有60莫耳%以上如上 所述的特定四羧酸二酐,更較佳含有80莫耳%以上。 © <二胺 > 用於合成本發明液晶配向劑中的較佳的聚醯胺酸的二 胺’是含有具有上述式(A)表示的結構和2個胺基的化合物 (以下稱爲“化合物(A)”)的二胺。 作爲化合物(A),較佳爲選自具有上述式(A —〗)表示的 結構和2個胺基的化合物(以下稱爲“化合物(A—!)”)、 具有上述式(A — 2)表示的結構和2個胺基的化合物(以下稱 &爲“化合物(A- 2)”)和具有上述式(a- 3)表示的結構和2 個胺基的化合物(以下稱爲“化合物(A - 3)”)構成的群組 中的至少一種。作爲上述式(A-丨)中的R»,較佳爲鹵素原 子,更佳爲氟原子。η爲〇或1»作爲上述式(a— 2)和(A — 3)中的Rb和R°’分別較佳爲氫原子或鹵素原子,更佳爲氫 原子或氟原子。 作爲上述化合物(A - 1 ),可以列舉例如下述式(a - 1 〜1)表示的化合物等, -15- 201005006More preferably, it contains a 1,2,3,4-cyclobutanetetracarboxylic dianhydride, a base 1,2,3,4-cyclobutane tetracarboxylic dianhydride, a 2,3,5-tricarboxyl group. Cyclopentyl anhydride, 5-(2,5-di-oxotetrahydro-3-furanyl)-3-methyl-3-cyclohexanedicarboxylic anhydride, 1,3,3&,4,5,91) - hexahydro-5-(tetrahydro-2,5-di-oxy)naphthalene [l,2-c]-furan-1,3-dione, cis-3,7-dibutylcyclohexane Alkene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-carboxyl-9-2:3,5:6-dianhydride, 1,3,3&,4 ,5,91>-hexahydro-8-methyl-5-(tetrahydroxyloxy-3-furylnaphthalene [l,2-c]-furan-1,3-dione, 3-oxo [3· 2.1] octane-2,4·dione-6-spiro-3'-(tetrahydrofuran-2',5'-two-drawing (τ~5) compound, pyromellitic dianhydride and 2,2 a tetracarboxylic dianhydride of at least one of the group consisting of ',3,3' phthalic acid dianhydride, selected from the group consisting of 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5- Tricarboxycyclopentanol, l,3,3a,4,5,9b-hexaamino-8-methyl-5-(tetrazo- 2,5-mono-anthranyl)-naphthalene [1,2-c ]-furan-1,3-dione and pyromellitic dianhydride structure, 3·diacetate diiso-1,2--3-furan-in-1,5-borneol-2,5- At least one of the above-mentioned 4-biphenyl fluorene-based acetoxy-3-furo-form group-14-201005006. As a preferred other four which can be used in combination with a specific tetracarboxylic dianhydride Examples of the phthalic acid dianhydride include butane tetracarboxylic dianhydride, 3,3', 4,4, benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl maple four. a carboxylic acid dianhydride, a 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. The tetracarboxylic dianhydride used for synthesizing the polyamic acid in the liquid crystal alignment agent of the present invention is preferably relative to all the tetracarboxylic acids. The dianhydride contains 60 mol% or more of the specific tetracarboxylic dianhydride as described above, and more preferably contains 80 mol% or more. © <Diamine> Preferred for synthesizing the liquid crystal alignment agent of the present invention The diamine of poly-proline is a diamine containing a compound having the structure represented by the above formula (A) and two amine groups (hereinafter referred to as "compound (A)"). As the compound (A), it is preferably A compound having a structure represented by the above formula (A-) and a compound having two amine groups (hereinafter referred to as "compound (A-!)"), a structure represented by the above formula (A-2), and two amines a compound of the group (hereinafter referred to as "the compound (A-2)") and a compound having the structure represented by the above formula (a-3) and two amine groups (hereinafter referred to as "compound (A-3)") At least one of the group formed. R + in the above formula (A-丨) is preferably a halogen atom, more preferably a fluorine atom. η is 〇 or 1», and Rb and R°' in the above formulae (a-2) and (A-3) are each preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom or a fluorine atom. The compound (A-1) may, for example, be a compound represented by the following formula (a-1 to 1), -15-201005006

(式(A— 1— 1)中,Ra和n分別與上述式(A _1)中的定 義相同,Ya爲單鍵或碳原子數爲6〜10的伸芳基)》作爲上 述式(A— 1一1)中的Ya的碳原子數爲6〜10的伸芳基,可 以列舉例如1,4-亞苯基、1,5_亞萘基等。作爲上述式(A - 1 -1)表示的化合物的具體例子,可以列舉例如2,6-二胺基 ® 苯并噻唑、2,7_二胺基苯并噻唑、2-(4-胺基苯基)-6-胺基苯 并噻唑、2-(4-胺基苯基)_7_胺基苯并噻唑等。 作爲上述化合物(A — 2)和(A - 3),可以列舉例如下述 式(A— 2-1)和(A-3 — 1)各自表示的化合物等,(In the formula (A-1 - 1), Ra and n are respectively the same as defined in the above formula (A _1), and Ya is a single bond or an extended aryl group having 6 to 10 carbon atoms)" as the above formula (A) The aryl group having 6 to 10 carbon atoms of Ya in the group 1 to 1) may, for example, be a 1,4-phenylene group or a 1,5-naphthylene group. Specific examples of the compound represented by the above formula (A-1 -1) include, for example, 2,6-diamino group benzothiazole, 2,7-diaminobenzothiazole, and 2-(4-amino group). Phenyl)-6-aminobenzothiazole, 2-(4-aminophenyl)-7-aminobenzothiazole, and the like. Examples of the compound (A-2) and (A-3) include a compound represented by the following formulas (A-2-1) and (A-3-1), and the like.

(式(A — 2 — 1)和(a — 3 — 1)中,Rb和Rc分別與上述式 (A— 2)或(A-3)中的定義相同,Yb和Yc各自獨立地爲單鍵 或碳原子數爲6〜1〇的伸芳基)。作爲上述式和 (A-3—1)中的Yb和Υ°的碳原子數爲6〜10的伸芳基,各 -16- 201005006 自可以列舉例如1,4-伸苯基、1,5-萘基等。作爲上述式(A -2_ 1)表示的化合物的具體例子,可以列舉例如2,6-二胺 基苯并[l,2-d:4,5-d’]二噻唑、2,6-雙(4·胺基苯基)苯并 [l,2-d:4,5-d’]二噻唑等;作爲上述式(A — 3 — 1)表示的化合 物的具體例子,可以列舉例如2,6·二胺基苯并[l,2-d:5,4-d’] 二噻唑、2,6-雙(4-胺基苯基)苯并[1,2-(1:5,4-(1’]二噻唑等。 作爲用於合成本發明液晶配向劑中的較佳的聚醯胺酸 的二胺,可以僅使用如上所述的化合物(A),也可以將化合 Ο 物(A)與其他二胺組合使用。 作爲這裏可以使用的其他二胺,可以列舉例如芳香族 二胺、脂肪族二胺、脂環式二胺、分子內具有2個一級胺 基以及該一級胺基以外的氮原子的二胺、單取代苯二胺、(In the formulae (A - 2 - 1) and (a - 3 - 1), Rb and Rc are respectively the same as defined in the above formula (A-2) or (A-3), and Yb and Yc are each independently a single The bond or the aryl group having a carbon number of 6 to 1 Å). Examples of the Yb and Υ° in the above formula and (A-3-1) are an aryl group having 6 to 10 carbon atoms, and each of -16 to 201005006 can be exemplified by, for example, 1,4-phenylene group, 1,5. -naphthyl and the like. Specific examples of the compound represented by the above formula (A - 2_1) include, for example, 2,6-diaminobenzo[l,2-d:4,5-d']dithiazole, 2,6-double (4. Aminophenyl)benzo[l,2-d:4,5-d']dithiazole; and the specific example of the compound represented by the above formula (A-3 - 1), for example, 2, 6. Diaminobenzo[l,2-d:5,4-d']dithiazole, 2,6-bis(4-aminophenyl)benzo[1,2-(1:5,4 -(1']dithiazole, etc. As the diamine for synthesizing the preferred polyglycolic acid in the liquid crystal alignment agent of the present invention, only the compound (A) as described above may be used, or the compound ruthenium ( A) used in combination with other diamines. As other diamines which may be used herein, for example, an aromatic diamine, an aliphatic diamine, an alicyclic diamine, two primary amino groups in the molecule, and the primary amino group may be mentioned. a diamine or a monosubstituted phenylenediamine of a nitrogen atom other than

作爲上述芳香族二胺,可以列舉例如對苯二胺、間苯 二胺、4,4,-二胺基二苯基甲烷、4,4,-二胺基二苯基乙烷、 4,4二胺基二苯基硫醚、4,4’-二胺基二苯基楓、3,3’-二甲 基-4,4’-二胺基聯苯、4,4,-二胺基苯甲醯苯胺、4,4’-二胺 基二苯醚、1,5-二胺基萘、2,2’-二甲基-4,4,-二胺基聯苯、 5-胺基-1-(4’-胺基苯基)-l,3,3-三甲基茚滿、6-胺基-卜(4’-胺基苯基)-1,3,3-三甲基茚滿、3,4,-二胺基二苯基醚、3,3’-二胺基二苯酮、3,4,-二胺基二苯酮、4,4’-二胺基二苯酮、 2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧 基)苯基]六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2·雙 [4-(4-胺基苯氧基)苯基]楓、U4_雙(4-胺基苯氧基)苯、1,3- -17- 201005006 雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、9,9-雙(4-胺基苯基)-10-氫蒽、2,7-二胺基芴、9,9-雙(4-胺基苯基) 芴、4,4’-亞甲基-二(2-氯苯胺)、2,2’,5,5’-四氯-4,4’-二胺 基聯苯、2,2’-二氯-4,4’-二胺基-5,5’-二甲氧基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、4,4’-(對亞苯基二異亞丙基)二 苯胺、4,4’-(間亞苯基二異亞丙基)二苯胺、2,2’-雙[4-(4-胺基-2-三氟甲基苯氧基)苯基]六氟丙烷、4,4’-二胺基-2,2’-雙(三氟甲基)聯苯、4,4’-雙[(4-胺基-2-三氟甲基)苯氧基]-φ 八氟聯苯、二(4-胺基苯基)聯苯胺、下述式(D- 1)〜(D— 5) 各自表示的化合物等,Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4,-diaminodiphenylethane, and 4,4. Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl maple, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4,-diamino Benzoquinone aniline, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4,-diaminobiphenyl, 5-amino group 1-(4'-aminophenyl)-l,3,3-trimethylindan, 6-amino-b (4'-aminophenyl)-1,3,3-trimethyl Indane, 3,4,-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4,-diaminobenzophenone, 4,4'-diaminodiphenyl Ketone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2, 2-bis(4-aminophenyl)hexafluoropropane, 2,2·bis[4-(4-aminophenoxy)phenyl] maple, U4_bis(4-aminophenoxy)benzene , 1,3- -17- 201005006 bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl) -10-hydroquinone, 2,7-diamino hydrazine, 9 ,9-bis(4-aminophenyl)anthracene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4'-di Aminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-di Aminobiphenyl, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 2,2'-double [ 4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4 , 4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-φ octafluorobiphenyl, bis(4-aminophenyl)benzidine, the following formula (D-1) ~(D-5) each represented by a compound, etc.

-18- 201005006 ❹ ΪΗ3 /CH3-18- 201005006 ❹ ΪΗ3 /CH3

(D, h2n- s-(D, h2n- s-

NH2 (D-5) (式(D— 4)中的y爲2〜12的整數,式(D-5)中的z爲 5的整數); -19- 201005006 作爲上述脂肪族二胺,可以列舉例如1,1 -間苯二甲 胺、1,3-丙二胺、丁二胺、戊二胺、己二胺、庚二胺、辛 二胺、壬二胺等; 作爲上述脂環式二胺,可以列舉例如1,4-二胺基環己 烷、異佛爾酮二胺、四氫二環戊二烯二胺、三環[6.2.1. 02’7] 十一亞烷基二甲基二胺、4,4’-亞甲基雙(環己胺)、1,3-雙(胺 基甲基)環己烷等; 作爲上述分子內具有2個一級胺基以及該一級胺基以 Φ 外的氮原子的二胺,可以列舉例如2,3-二胺基吡啶、2,6-二胺基吡啶、3,4-二胺基吡啶、2,4-二胺基嘧啶、5,6-二胺 基-2,3-二氰基吡畊、5,6-二胺基·2,4-二羥基嘧啶、2,4-二胺 基-6-二甲胺基-1,3,5-三哄、1,4-雙(3·胺基丙基)哌阱、2,4-—胺基-6-異丙氧基-1,3,5-二哄、2,4-二胺基-6-甲氧基 -1,3,5-三畊、2,4-二胺基-6-苯基-1,3,5-三畊、2,4-二胺基-6-甲基-s-三畊、2,4-二胺基-1,3,5-三哄、4,6-二胺基-2-乙烯 基-s-三阱、2,4-二胺基-5-苯基噻唑、2,6-二胺基嘌呤、5,6-® 二胺基-1,3-二甲基尿嘧啶、3,5-二胺基-1,2,4-三唑、6,9-二胺基-2-乙氧基吖啶乳酸酯、3,8-二胺基-6-苯基菲啶、1,4-二胺基哌畊、3,6-二胺基吖啶、雙(4-胺基苯基)苯基胺、 1-(3,5 -二胺基苯基)_3_癸基琥珀醯胺、二胺基苯 基)-3-十八烷基琥珀醯胺、下述式(D—z)表示的化合物,NH2 (D-5) (y in the formula (D-4) is an integer of 2 to 12, and z in the formula (D-5) is an integer of 5); -19- 201005006 As the above aliphatic diamine, For example, 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, etc.; The diamine may, for example, be 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclo[6.2.1. 02'7] eleven alkylene Dimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, etc.; as the above molecule, having two primary amine groups and the first stage The diamine having an amine group as a nitrogen atom other than Φ may, for example, be 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine or 2,4-diaminopyrimidine. , 5,6-diamino-2,3-dicyanopyridine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino- 1,3,5-triazole, 1,4-bis(3.aminopropyl) pipe trap, 2,4-amino-6-isopropoxy-1,3,5-diindole, 2 ,4-diamino-6-methoxy-1,3,5-three tillage, 2,4-di -6-phenyl-1,3,5-three tillage, 2,4-diamino-6-methyl-s-three tillage, 2,4-diamino-1,3,5-triazine , 4,6-diamino-2-vinyl-s-tripper, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-® diamine -1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridinate lactate, 3,8 -diamino-6-phenylphenanthridine, 1,4-diaminopiperidine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 1-(3, 5-diaminophenyl)_3_mercaptosuccinimide, diaminophenyl)-3-octadecyl succinylamine, a compound represented by the following formula (D-z),

(式(D— I)中,R5爲具有選自吡啶、嘧啶、三阱、哌啶 -20- 201005006 以及ή底阱構成的群組的含氮原子環狀結構的1價有機基 團,X1爲2價的有機基團,R6爲碳原子數爲1〜4的烷基, al爲0〜3的整數)、下述式(D - II)表示的化合物等,(In the formula (D-I), R5 is a monovalent organic group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, triple well, piperidine-20-201005006, and a bottom-bottom well, X1 a divalent organic group, R 6 is an alkyl group having 1 to 4 carbon atoms, and al is an integer of 0 to 3), a compound represented by the following formula (D - II), and the like.

(式(D_ II)中,R7爲具有選自吡啶、嘧啶、三哄、哌 啶以及哌畊構成的群組的含氮原子環狀結構的2價有機基 ® 團,X2各自爲2價的有機基團,存在的多個X2可以相同, 也可以不同,R8各自爲碳原子數爲1〜4的烷基,a2各自 爲0〜3的整數); 作爲上述單取代苯二胺,可以列舉例如下述式(D - III) 表示的化合物等 (R11)a3 h2n(In the formula (D_II), R7 is a divalent organic group having a nitrogen atom-containing cyclic structure selected from the group consisting of pyridine, pyrimidine, triterpene, piperidine, and piperene, and each of X2 is divalent. The organic group may have the same or different X2 groups, each of which is an alkyl group having 1 to 4 carbon atoms, and each of a2 is an integer of 0 to 3); as the monosubstituted phenylenediamine, For example, a compound represented by the following formula (D - III), etc. (R11) a3 h2n

OR9—R10 (ηπ) I nh9 ❹ (式(D - III)中,R9 爲·〇-、-COO-*、-OCO-*、-NHCO-*、 -CONH-*(其中,在以上當中,帶有的連接鍵與R1G 連接)或-CO-,R1G爲具有選自甾體骨架、三氟甲基苯基、 三氟甲氧基苯基和氟代苯基中的骨架或基團的1價有機基 團,或者碳原子數爲6〜30的烷基,R11爲碳原子數爲1〜OR9—R10 (ηπ) I nh9 ❹ (In the formula (D - III), R9 is ·〇-, -COO-*, -OCO-*, -NHCO-*, -CONH-* (wherein the above, With a linkage to R1G) or -CO-, R1G is a backbone or group having a skeleton selected from the group consisting of a steroid skeleton, a trifluoromethylphenyl group, a trifluoromethoxyphenyl group, and a fluorophenyl group. a valence organic group, or an alkyl group having 6 to 30 carbon atoms, and R11 is a carbon atom of 1~

4的烷基,a3爲0〜3的整數); 作爲上述二胺基有機矽氧烷,可以列舉例如下述式(D —IV)表示的化合物等, -21 -The alkyl group of 4, a3 is an integer of 0 to 3), and the compound represented by the following formula (D-IV), etc., as the above-mentioned diaminoorganooxane, -21 -

201005006 r12 H2N-f-CH2 tfH。-ft^H2々NH2 R12 R12 (D-IV) (式(D-IV)中,R12各自爲碳原子數爲i〜12 存在的多個R1 2各自可以相同,也可以不同,p各 3的整數’q爲1〜20的整數)。這些二胺可以單 以上組合使用。 上述芳香族二胺的苯環,任選可被一個或兩 ❹ 碳原子數爲1〜4的烷基(較佳甲基)取代。上述式 (D — II)和(D-III)中的r6、r8和R11各自較佳爲θ a2和a3各自較佳爲〇或1,更佳爲〇。 上述式(D — III)的R1C中的甾體骨架,是指由 全氫菲核構成的結構或其碳-碳鍵中的一個或兩 爲雙鍵的骨架。作爲具有這種甾體骨架的Ri〇的 基團,較佳碳原子數爲17〜51的基團,更佳碳 17〜29的基團。 作爲具有這種甾體骨架的Ri〇的具體例子, 例如膽甾烷-3-基、膽甾-5-烯-3-基、膽甾-24-烯-甾-5,24-二烯-3-基、羊毛甾烷-3-基等。 作爲上述式(D - I)表示的化合物的具體例子 舉例如下述式(D- 6)表示的化合物等; (D-6) 的烴基, 自爲1〜 獨或兩種 個以上的 (D- I)、 3 基,a 1、 環戊院— 個以上改 1價有機 原子數爲 可以列舉 3-基、膽 ,可以列 -22- 201005006 作爲上述式(D_ Π)表示的化合物的具體例子,可以列 舉例如下述式(D- 7)表示的化合物等; qn-^)^NH2 (1>7) 作爲上述式(D - III)表示的化合物的具體例子,可以列 舉例如下述式(D — 8)〜(D- 16)各自表示的化合物等。 ❹201005006 r12 H2N-f-CH2 tfH. - ft^H2々NH2 R12 R12 (D-IV) (In the formula (D-IV), R12 is each a plurality of R1 2 having a carbon number of i~12, and may be the same or different, each of p 3 The integer 'q is an integer from 1 to 20). These diamines may be used alone or in combination. The benzene ring of the above aromatic diamine may be optionally substituted by one or two alkyl groups (preferably methyl groups) having 1 to 4 carbon atoms. Preferably, each of r6, r8 and R11 in the above formulae (D - II) and (D-III) is such that θ a2 and a3 are each preferably 〇 or 1, more preferably 〇. The steroid skeleton in R1C of the above formula (D-III) means a structure composed of a perhydrophenanthrene nucleus or a skeleton in which one or both of carbon-carbon bonds are double bonds. As the group of Ri 具有 having such a steroid skeleton, a group having 17 to 51 carbon atoms is preferable, and a group having 17 to 29 carbon atoms is more preferable. Specific examples of Ri(R) having such a steroid skeleton, such as cholest-3-yl, cholest-5-en-3-yl, cholest-24-ene-indole-5,24-diene- 3-yl, lanostan-3-yl and the like. Specific examples of the compound represented by the above formula (D - I) include, for example, a compound represented by the following formula (D-6); and the hydrocarbon group of (D-6) is independently 1 or more or two or more (D- I), 3 bases, a 1 , Cyclopentanol - The number of organic atoms of one or more valences is exemplified by 3-base, cholesteryl, and -22-201005006 can be listed as a specific example of the compound represented by the above formula (D_ Π). For example, a compound represented by the following formula (D-7); qn-^)^NH2 (1>7) Specific examples of the compound represented by the above formula (D-III) include, for example, the following formula (D). — 8)~(D-16) each represented by a compound or the like. ❹

-23- 201005006-23- 201005006

〇CO OCF coo—( h2n NH: (D-15)〇CO OCF coo—( h2n NH: (D-15)

Λ 中的較佳的聚醯胺酸 對苯二胺、4,4’-二胺 1,5-二胺基萘、2,7--雙[4-(4-胺基苯氧基) 2,2-雙[4-(4-胺基苯氧 作爲用於合成本發明液晶配向劑 的其他二胺,上述當中較佳使用選自 基二苯甲烷、4,4’-二胺基二苯硫醚 二胺基芴、4,4’-二胺基二苯基醚、2,2 苯基]丙烷、9,9-雙(4-胺基苯基)芴、 基)苯基]六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、4,4’-(對 -24- 201005006 亞苯基二異亞丙基)二苯胺、4,4’-(間亞苯基二異亞丙基)二 苯胺、1,4-環己烷二胺、4,4,-亞甲基二(環己胺)、1,4-二(4-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、上述式(D-1)〜(D-5)各自表示的化合物、2,6-二胺基吡啶、3,4-二胺 基吡啶、2,4-二胺基嘧啶、3,6_二胺基吖啶、上述式(D— 6) 表示的化合物、上述式(D — 7)表示的化合物、上述式(D-III)表示的化合物和1,3-雙(3-二胺基丙基)_四甲基二矽氧 烷構成的群組中的至少一種。 〇 作爲上述式(D— III)表示的化合物,較佳上述式(D- III)中R9爲-0-或-COO-*(其中帶有的連接鍵與R1G連 接)、R1()爲具有甾體骨架的1價有機基團的化合物,特佳 爲上述式(D — 8)〜(D — 13)各自表示的化合物。 作爲其他二胺,較佳爲含有選自對苯二胺、4,4’-二胺 基二苯基甲烷、4,4’-二胺基二苯基醚、雙[4-(4·胺基苯氧基) 苯基]颯和上述式(D - III)轰示的化合物構成的群組中的至 少一種的二胺,特佳含有選自對苯二胺、4,4’·二胺基二苯 β 基甲烷、4,4’-二胺基二苯基醚和雙[4-(4-胺基苯氧基)苯基] 颯構成的群組中的至少一種以及上述式(D_ III)表示的化 合物的二胺。 用於合成本發明液晶配向劑中的較佳的聚醯胺酸的二 胺’較佳相對於全部二胺含有1莫耳%以上,更佳含有5 〜90莫耳% ’進一步較佳含有1〇〜80莫耳%,特佳含有15 〜30莫耳%化合物(a)。 用於合成本發明液晶配向劑中的較佳的聚醯胺酸的二 -25- 201005006 胺,較佳相對於全部二胺含有1〜50莫耳%,更佳含有5 〜30莫耳%上述式(d _ III)表示的化合物。 用於合成本發明液晶配向劑中的較佳的聚醯胺酸的二 胺,較佳相對於全部二胺含有30〜90莫耳%,更較佳爲含 有40〜80莫耳%選自對苯二胺、4,4,-二胺基二苯基甲烷、 4,4’·二胺基二苯基醚和二[4-(4-胺基苯氧基)苯基]碾構成 的群組中的至少一種。 <聚醯胺酸的合成> © 本發明液晶配向劑中的較佳的聚醯胺酸,可以通過使 如上所述的四羧酸二酐與含化合物(A)的二胺反應而製得。 供給聚醯胺酸合成反應的四羧酸二酐與二胺的使用比 率,較佳相對於二胺中的1當量胺基,使四羧酸二酐的酸 酐基爲0.2〜2當量的比率,更較佳使其爲〇.7〜1.2當量的 比率。 聚醯胺酸的合成反應,較佳在有機溶劑中,較佳於-20 〜150°C、更佳於0〜l〇〇°C的溫度條件下,較佳進行1〜72 β 小時,更佳進行3〜48小時。這裏’作爲有機溶劑,只要 是能夠溶解生成的聚醯胺酸的溶劑,則對其沒有特別的限 制,可以例示例如1-甲基-2-吡咯烷酮、Ν,Ν-二甲基乙醯 胺、Ν,Ν·二甲基甲醯胺、3-丁氧基-Ν,Ν·二甲基丙醯胺、3-甲氧基-Ν,Ν -二甲基丙酸胺、3 -己氧基-Ν,Ν·二甲基丙酿胺 等醯胺化合物、二甲基亞碾I、r-丁內酯、四甲基脲、六甲 基磷醯三胺等非質子性化合物;間甲基酚、二甲苯酿、苯 酚、鹵代苯酚等酚性化合物等。有機溶劑的用量(α),通常, -26- 201005006 較佳爲使四羧酸二酐和二胺的總量(β)相對於反應溶液的 總量(α+ β)爲0.1〜30重量%的量。另外,當有機溶劑與下 述的不良溶劑聯用時,上述有機溶劑的用量(〇〇應當理解爲 有機溶劑與不良溶劑的合計用量的含義。 上述有機溶劑中,在不使生成的聚醯胺酸析出的範圍 內,還可以聯用通常認爲是聚醯胺酸的不良溶劑的醇類、 酮類、酯類、醚類、鹵代烴類、烴類等。作爲這種不良溶 劑的具體例子,可以列舉例如甲醇、乙醇、異丙醇、環己 © 醇、4-羥基-4-甲基-2-戊酮、乙二醇、丙二醇、1,4-丁二醇、 三甘醇、乙二醇單甲醚、乳酸乙酯、乳酸丁酯、丙酮、甲 基乙基酮、甲基異丁基酮、環己酮、醋酸甲酯、醋酸乙酯、 醋酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、草酸二乙 酯、丙二酸二乙酯、乙醚、乙二醇甲醚、乙二醇乙醚、乙 二醇正丙醚、乙二醇異丙醚、乙二醇正丁醚、乙二醇二甲 基醚、乙二醇乙醚乙酸酯、二甘醇二甲醚、二甘醇二乙醚、 二甘醇單甲醚、二甘醇單乙醚、二甘醇單甲醚乙酸酯、二 ® 甘醇單乙醚乙酸酯、四氫呋喃、二氯甲烷、1,2-二氯乙烷、 1,4-二氯丁烷、三氯乙烷、氯苯、鄰二氯苯、己烷、庚烷、 辛烷、苯、甲苯、二甲苯、二異丁基酮、丙酸異戊酯、異 丁酸異戊酯、二異戊醚等。 當將有機溶劑與如上所述的不良溶劑聯用時,不良溶 劑的使用比率,可以在不使生成的聚醯胺酸析出的範圍內 適當地設定,相對於有機溶劑與不良溶劑的合計量,較佳 爲30重量%以下,更佳爲20重量%以下。 -27- 201005006 如上所述,得到溶解了聚醯胺酸的反應溶液。 該反應溶液,可以將其直接供給液晶配向劑進行調 製,也可以將反應溶液中所含的聚醯胺酸分離出來後供給 液晶配向劑進行調製,或者也可以將分離出的聚醯胺酸精 製後再供給液晶配向劑進行調製。 當將聚醯胺酸脫水閉環製成聚醯亞胺時,可以將上述 反應溶液直接供給脫水閉環反應,也可以將反應溶液中所 含的聚醯胺酸分離出來後供給脫水閉環反應,或者也可以 Φ 將分離出的聚醯胺酸精製後再供給脫水閉環反應。 聚醯胺酸的分離,可以通過將上述反應溶液投入到大 量的不良溶劑中,得到析出物,再在減壓下乾燥該析出物 的方法,或者將反應溶液中的有機溶劑用蒸發器減壓餾出 的方法而進行。另外,通過使該聚醯胺酸再次溶解於有機 溶劑中,然後用不良溶劑使其析出的方法,或者進行一次 或幾次用蒸發器減壓餾出的步驟的方法,可以精製聚醯胺 酸。 ® <聚醯亞胺> 本發明液晶配向劑中的較佳的聚醯亞胺,可以通過將 如上所述的聚醯胺酸脫水閉環而製得。 本發明液晶配向劑中的聚醯亞胺,可以是其前體聚醯 胺酸所具有的醯胺酸結構全部脫水閉環的完全醯亞胺化 物,也可以是僅醯胺酸結構的一部分脫水閉環的、醯胺酸 結構與醯亞胺環結構並存的部分醯亞胺化物。 本發明液晶配向劑中所含的聚醯亞胺,其醯亞胺化率 -28- 201005006 較佳爲4〇莫耳%以上,更佳爲80莫耳%以上。通過使用醯 亞胺化率爲40莫耳%以上的聚醯亞胺,可以獲得能夠形成 荷電洩漏性更佳的液晶配向膜的液晶配向劑。 上述醯亞胺化率,是相對於聚醯亞胺的醯胺酸結構數 與醯亞胺環結構數的合計數量,醯亞胺環結構數所占的比 率用百分率表示的値。此時,醯亞胺環的一部分還可以是 異醯亞胺環。醯亞胺化率可以通過將聚醯亞胺溶於適當的 氘代溶劑(例如氘代二甲基亞颯)中,以四甲基矽烷爲基準 © 物質’在室溫(例如25°C )下測定 W-NMR,由測定結果按 照下述公式(1)求出。 醯亞胺化率(%) = (1 - A”A2x a )xl 00 (1) (公式(1)中,A1爲化學位移10 ppm附近出現的源於 NH基質子的峰面積,A2爲源於其他質子的峰面積,α爲 相對於聚醯亞胺的前體(聚醯胺酸)中的1個ΝΗ基的質子, 其他質子的個數比率)。 聚醯胺酸的脫水閉環,較佳(i)通過加熱聚醯胺酸的方 ® 法,或者(ii)通過將聚醯胺酸溶於有機溶劑中,向該溶液中 加入脫水劑和脫水閉環催化劑並根據需要加熱的方法進 行。 上述(i)的加熱聚醯胺酸的方法中的反應溫度’較佳爲 50〜200 °C,更佳爲60〜170 °C。反應時間較佳爲1〜8小 時,更佳爲3〜5小時。當反應溫度不足5 0 °C時’則脫水 閉環反應不能進行充分,若反應溫度超過200 °C ’則會出 現所得聚醯亞胺的分子量下降的情況。 -29- 201005006 另一方面,在上述(ii)的在聚醯胺酸溶液中添加脫水劑 和脫水閉環催化劑的方法中,作爲脫水劑,可以使用例如 醋酸酐、丙酸酐、三氟乙酸酐等酸酐。脫水劑的用量,根 據所需的醯亞胺化率而定,較佳相對於聚醯胺酸的1莫耳 醯胺酸結構爲0.01〜20莫耳。另外,作爲脫水閉環催化劑, 可以使用例如吡啶、三甲吡啶、二甲吡啶、三乙胺等叔胺。 但是’並不局限於這些。脫水閉環催化劑的用量,較佳相 對於1莫耳所用脫水劑爲0·01〜10莫耳。上述脫水劑、脫 © 水閉環劑的用量越多,可使醯亞胺化率越高。作爲脫水閉 環反應中所用的有機溶劑,可以列舉作爲聚醯胺酸的合成 中所用的有機溶劑而例示的有機溶劑。脫水閉環反應的反 應溫度’較佳爲0〜180°C,更佳爲10〜150°c。反應時間 較佳爲1〜8小時,更佳爲3〜5小時。 上述方法(i)中製得的聚醯亞胺,可以將其直接供給液 晶配向劑進行調製,或者也可以將製得的聚醯亞胺精製後 再供給液晶配向劑進行調製。另外,在上述方法(ii)中,得 ® 到含聚醯亞胺的反應溶液。該反應溶液,可以將其直接供 給液晶配向劑進行調製,也可以從反應溶液中除去脫水劑 和脫水閉環催化劑之後供給液晶配向劑進行調製,還可以 將聚醯亞胺分離出來後供給液晶配向劑進行調製,或者也 可以將分離的聚醯亞胺精製後再供給液晶配向劑進行調 製》從反應溶液中除去脫水劑和脫水閉環催化劑,可以採 用例如溶劑置換等方法。聚醯亞胺的分離、精製,可以採 取與以上作爲聚醯胺酸的分離、精製方法所描述的同樣的 -30- 201005006 操作而進行。 -末端修飾型的聚合物- 本發明液晶配向劑中所含的聚醯胺酸和聚醯亞胺,各 自還可以是進行了分子量調節的末端修飾型聚合物。通過 使用末端修飾型的聚合物,可以在不損害本發明效果的前 提下進一步改善液晶配向劑的塗布性能等。這種末端修飾 型聚合物可以通過在聚醯胺酸的合成時,向聚合反應體系 中加入分子量調節劑而進行。作爲分子量調節劑,可以列 Φ 舉單酐、單胺化合物、單異氰酸酯化合物等。 作爲上述單酐,可以列舉例如馬來酸酐、鄰苯二甲酸 酐、衣康酸酐、正癸基琥珀酸酐、正十二烷基琥珀酸酐、 正十四烷基琥珀酸酐、正十六烷基琥珀酸酐等。作爲上述 單胺化合物,可以列舉例如苯胺,環己胺、正丁胺、正戊 胺、正己胺、正庚胺、正辛胺、正壬胺、正癸胺、正十一 烷胺、正十二烷胺、正十三烷胺、正十四烷胺、正十五烷 胺、正十六烷胺、正十七烷胺、正十八烷胺、正二十烷胺 ® 等。作爲上述單異氰酸酯化合物,可以列舉例如異氰酸苯 酯、異氰酸萘基酯等。 分子量調節劑的使用比率,相對於100重量份聚醯胺 酸合成時所使用的四羧酸二酐和二胺的合計量,較佳爲20 重量份以下,更佳爲10重量份以下。 -溶液黏度- 如上製得的聚醯胺酸和聚醯亞胺,各自較佳當配成濃 度爲10重量%的溶液時,具有20〜800 mP a. S的溶液黏度, -31- 201005006 更佳具有30〜500 mPas的溶液黏度。 上述聚合物的溶液黏度(mPa’s),是對採用該聚合物的 良溶劑調製的濃度爲10重量%的聚合物溶液,用E型旋轉 黏度計在2 5 °C下測定的値。 <其他添加劑> 本發明的液晶配向劑,含有如上所述的特定聚合物作 爲必需成分,根據需要還可以含有其他成分。作爲這種其 他成分,可以列舉例如其他聚合物、黏合性增強劑等。 φ 上述其他聚合物可以爲了改善溶液性能和電學性能而 使用。這種其他聚合物,是特定聚合物以外的聚合物,可 以列舉例如使四羧酸二酐與不含化合物(A)的二胺反應而 製得的聚醯胺酸(以下稱爲“其他聚醯胺酸”)、將該聚醯 胺酸脫水閉環而製得的聚醯亞胺(以下稱爲“其他聚醯亞 胺”)、聚醯胺酸酯、聚酯、聚醯胺、聚矽氧烷、纖維素衍 生物、聚縮醛、聚苯乙烯衍.生物、聚(苯乙烯-苯基馬來醯 亞胺)衍生物、聚(甲基)丙烯酸酯等。其中,較佳爲其他聚 © 醯胺酸或其他聚醯亞胺。 其他聚合物的使用比率,相對於聚合物的合計量(是指 特定聚合物以及其他聚合物的合計量。下同),較佳爲90 重量%以下,更佳爲85重量%以下。 上述黏合性增強劑,可以爲了提高所形成的液晶配向 膜對基板表面的黏合性的目的而使用。作爲這種黏合劑增 強劑,可以列舉例如分子內具有至少一個環氧基的化合物 (以下稱爲“環氧基化合物”)、官能性矽烷化合物等》 -32- 201005006 作爲上述環氧基化合物,可以列舉例如乙二醇二縮水 甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、 三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二 醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油二縮水 甘油醚、2,2-二溴新戊二醇二縮水甘油醚、Ν,Ν,Ν’,Ν’-四縮 水甘油基-間苯二甲胺、1,3-雙(N,N-二縮水甘油基胺基甲基) 環己烷、^:^’,:^’-四縮水甘油基-4,4’-二胺基二苯基甲 烷、3-(N-烯丙基-N-縮水甘油基)胺基丙基三甲氧基矽烷、 © 3-(Ν,Ν·二縮水甘油基)胺基丙基三甲氧基矽烷等。 如上所述的環氧基化合物的使用比率,相對於100重 量份聚合物的合計量,較佳爲40重量份以下,更佳爲0.1 〜30重量份。 作爲上述官能性矽烷化合物,可以列舉例如3-胺基丙 基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基 三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、Ν-(2-胺基乙 基)-3-胺基丙基三甲氧基矽烷、Ν-(2-胺基乙基)-3-胺基丙基 ® 甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3·脲基丙 基三乙氧基矽烷、N-乙氧羰基-3-胺基丙基三甲氧基矽烷、 N-乙氧羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽烷基 丙基三亞乙基三胺、N-三甲氧基矽烷基丙基三亞乙基三 胺、10-三甲氧基矽烷·1,4,7-三氮雜癸烷、10-三乙氧基矽 烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬 基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、Ν-苄基-3-胺基丙基三甲氧基矽烷、Ν_苄基_3_胺基丙基三乙氧 -33- 201005006 基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基 丙基三乙氧基矽烷、N-雙(氧乙烯基)-3-胺基丙基三甲氧基 矽烷、N-二(氧乙烯基)-3_胺基丙基三乙氧基矽烷等。 如上所述的官能性矽烷化合物的使用比率,相對於100 重量份聚合物總量,較佳爲2重量份以下,更佳爲0.01〜 〇 . 2重量份。 本發明的液晶配向劑是將如上所述特定聚合物以及根 據需要任選配合的其他添加劑較佳溶解含於有機溶劑中而 〇 構成的。 作爲本發明液晶配向劑中可以使用的有機溶劑,可以 列舉例如N-甲基-2-吡咯烷酮、r-丁內酯、r· 丁內醯胺、 N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、4-羥基-4-甲基-2-戊酮、乙二醇單甲醚、乳酸丁酯、乙酸丁酯、甲氧基丙酸 甲酯、乙氧基丙酸乙酯、乙二醇甲醚、乙二醇乙醚、乙二 醇正丙醚、乙二醇異丙醚、乙二醇正丁醚(丁基溶纖劑)、 乙二醇二甲基醚、乙二醇乙醚乙酸酯、二甘醇二甲醚、二 ® 甘醇二乙醚、二甘醇單甲醚、二甘醇單乙醚、二甘醇單甲 醚乙酸酯、二甘醇單乙醚乙酸酯、3-丁氧基-Ν,Ν·二甲基丙 醯胺、3-甲氧基-Ν,Ν-二甲基丙醯胺、3-己氧基-Ν,Ν-二甲基 丙醯胺等。 本發明液晶配向劑中的固體含量濃度(液晶配向劑中 溶劑以外的成分的合計重量占液晶配向劑總重量的比率) 考慮黏性、揮發性等而適當地選擇,較佳爲1〜1〇重量% 的範圍。也就是說,本發明的液晶配向劑,如下所述塗布 -34- 201005006 於基板表面,較佳通過加熱形成作爲液晶配向膜的塗膜, 當固體含量濃度不足1重量%時’將導致該塗膜的厚度過 小而不能獲得良好的液晶配向膜;另一方面,當固體含量 濃度超過10重量%時,將導致塗膜厚度過厚而不能獲得良 好的液晶配向膜,並且,液晶配向劑的黏性增大,導致塗 布性能變差。 特佳的固體含量濃度範圍,根據將液晶配向劑塗布於 基板時所採用的方法而不同。例如,當採用旋塗法時,特 〇 佳固體含量濃度爲1.5〜4.5重量%的範圍。當採用印刷法 時,特佳使固體含量濃度爲3〜9重量%的範圍,這樣,可 以使溶液黏度落在12〜50 mPai的範圍。當採用噴墨法 時,特佳使固體含量濃度爲1〜5重量%的範圍,這樣,可 以使溶液黏度落在3〜15 mPa‘s的範圍。 調製本發明液晶配向劑時的溫度,較佳爲〇°C〜200 °C,更佳爲2 0 °C〜6 0 °C。 本發明的液晶顯示元件具有由如上所述的本發明液晶 〇 配向劑形成的液晶配向膜。 作爲本發明液晶顯示元件的較佳工作模式,可以列舉 TN型、VA型和IPS型。 本發明的液晶顯示元件可以通過例如以下(1)〜(3)的 步驟製造。對於步驟(1),所使用的基板根據所需的工作模 式而不同。步驟(2)和(3)是各種工作模式中通用的》 (1)首先,通過在基板上塗布本發明的液晶配向劑,接 著加熱塗布面,而在基板上形成塗膜。 -35- 201005006 (1 ~丨)當製造TN型或VA型液晶顯示元件時,以兩塊 設有形成圖案的透明導電膜的基板作爲一對,較佳採用膠 版印刷法、輥塗法、旋塗法或噴墨印刷法,在其各個形成 透明導電膜的面上分別塗布本發明的液晶配向劑,形成塗 膜。這裏,作爲基板,可以使用例如浮法玻璃、鈉鈣玻璃 等玻璃;聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、 聚醚碾、聚碳酸酯、聚(脂環式烯烴)等塑膠製透明基板。 作爲基板一面上設置的透明導電膜,可以使用氧化錫(Sn02) © 製的NESA膜(美國PPG公司註冊商標)、氧化銦-氧化錫 (ln203 — Sn02)製的ITO膜等,形成圖案的透明導電膜的獲 得,可採用例如在形成無圖案的透明導電膜後通過光刻而 形成圖案的方法、在透明導電膜形成時採用具有所需圖案 的掩模的方法等。在液晶配向劑的塗布時,爲了進一步改 善基板表面和透明導電膜與塗膜的黏合性,還可以在基板 表面中的要形成塗膜的面上,進行預先塗布官能性矽烷化 合物、官能性鈦化合物等的前處理》 ® 在這種基板上塗布了液晶配向劑後,爲了防止液體下 垂等的目的,較佳進行預加熱(預烘焙)。預烘焙溫度較佳 爲30〜200°C,更佳爲40〜150°C,特佳40〜l〇〇°C。預烘 焙時間較佳爲0.25〜10分鐘,更佳爲0.5〜5分鐘。預烘焙 後,爲了完全除去膜中的溶劑以及當液晶配向劑中所含的 聚合物具有醯胺酸結構時根據需要將其進行熱醯亞胺化的 目的,進行熟化(後烘焙)步驟。後烘焙溫度較佳爲80〜300 °C,更佳爲120〜250 °C。後烘焙時間較佳爲5〜200分鐘, -36- 201005006 更佳爲10〜100分鐘。 如此形成的塗膜的厚度,較佳爲0.001〜Ιμιη,更較佳 爲 0.005 〜0.5μιη。 (1 一 2)另一方面,當製造IPS型液晶顯示元件時,較 佳採用膠版印刷法、輥塗法、旋塗法或噴墨印刷法,在設 有形成梳齒形圖案的透明導電膜的基板的導電膜形成面 上,以及沒有設置導電膜的對向基板的一面上,分別塗布 本發明的液晶配向劑,然後較佳加熱各塗布面(預烘焙和後 〇 烘焙)而形成塗膜。 此時對於所使用的基板和透明導電膜的材料、透明導 電膜圖案的形成方法以及對基板的前處理、塗布後的預烘 焙和後烘焙條件、所形成的塗膜的膜厚,與上述(1 - 1)相 同。 對於上述(1 一 1)和(1 一 2)的任一情形,本發明的液晶配 向劑均通過塗布後除去有機溶劑而形成作爲液晶配向膜的 塗膜,當本發明液晶配向劑所含的聚合物爲聚醯胺酸或同 β 時存在醯亞胺環結構和醯胺酸結構的聚醯亞胺時,還可以 在形成塗膜後通過進一步加熱使其進行脫水閉環反應,以 形成進一步醯亞胺化的塗膜。 (2)如上形成的塗膜,可以將其直接作爲VA型液晶顯 示元件用的液晶配向膜使用,也可以任選地對該塗膜面進 行下述的打磨處理。 當如上形成的塗膜作爲ΤΝ型或IPS型液晶顯示元件用 的液晶配向膜使用時,通過對塗膜面進行打磨處理,使塗 -37- 201005006 膜上產生液晶分子配向能而製成液晶配向膜。 打磨處理可以通過採用纏有例如尼龍、人造纖維、棉 花等纖維制的布的輥對塗膜面以一定方向摩擦而進行》 另外,通過對如上形成的液晶配向膜,進行例如專利 文獻4(日本特開平6— 222366號公報)或專利文獻5(日本特 開平6-281 93 7號公報)中所示的、對液晶配向膜的一部分 照射紫外線而使液晶配向膜一部分區域預傾角改變的處 理,或者進行專利文獻6(日本特開平5 - 107544號公報) 中所示的、在液晶配向膜的部分表面上形成抗蝕膜後,以 與先前打磨處理不同的方向進行打磨處理後除去抗蝕膜的 處理,使液晶配向膜每一區域具有不同的液晶配向能,能 夠改善所得液晶顯示元件的視場性能。 (3)製造一對如上形成了液晶配向膜的基板,將兩塊基 板通過間隙(胞間隙)相對設置,使其液晶配向膜的打磨方 向相互垂直或逆平行。將兩塊基板的周邊部位用密封劑貼 合,向由基板表面和密封劑圍成的胞間隙內注充液晶,封 β 閉注入孔,構成液晶胞。然後,在液晶胞的外表面上貼合 偏光片,使其偏光方向與各基板上形成的液晶配向膜的打 磨方向一致或垂直,即可製得液晶顯示元件。這裏,作爲 密封劑,可以使用例如含作爲固化劑和分隔物的氧化鋁球 的環氧樹脂等。作爲液晶,可以列舉向列型液晶和碟狀型 液晶,其中較佳向列型液晶,可以使用例如希夫氏鹸類液 晶、氧化偶氮基類液晶、聯苯類液晶、苯基環己烷類液晶、 酯類液晶、三聯苯類液晶、聯苯基環己烷類液晶、嘧啶類 -38- 201005006 液晶、二氧六環類液晶、雙環辛烷類液晶、立方烷類液晶 等。此外,這些液晶中還可以添加例如氯化膽甾醇、膽甾 醇壬酸酯、膽甾醇碳酸酯等膽甾型液晶、以商品名 “C-15” 、 “CB-15” (默克公司生產)銷售的手性劑、對癸 氧基苯亞甲基-對胺基-2-甲基丁基肉桂酸酯等鐵電性液晶 等而使用。 作爲液晶胞外表面上貼合的偏光片,可以列舉將聚乙 烯醇延伸配向同時吸收碘所得的稱作爲“ Η膜”的偏光膜 〇 夾在醋酸纖維保護膜中而製成的偏光片,或者Η膜自身製 成的偏光片。 如上製造的本發明液晶顯示元件,與以前已知的液晶 顯示元件相比,具有即使長時間連續驅動,顯示性能也不 會變差的優點,具體地說,例如不會發生被認爲是液晶配 向膜熱劣化導致液晶配向不良的起因的背光漏光等。 【實施例】 以下,通過實施例對本發明進行更具體的說明,但是 〇 本發明並不局限於這些實施例。 另外,合成例中的聚合物的溶液黏度,均爲採用Ε型 黏度計在2 5 °C下測定的値。 <化合物(A)的合成> 合成例1(2,6-二胺基苯并噻唑的合成) 合成原料2-胺基-6-硝基苯并唾唑直接使用東京化成 工業(股)的產品。將97.6g(0.50莫耳)2-胺基-6·硝基苯并噻 唑溶於3000ml乙醇中,加入5重量%的鈀/碳90g,在氮氣 -39- 201005006 環境下於70°C攪拌1小時。然後,加入153ml肼一水合物, 在通氮氣流的條件下於回流狀態下携样6小時進行反應。 反應結束後,採用矽藻土(Celite)過濾除去鈀/碳,並從 濾液中除去溶劑。將所得固體用蒸餾水充分洗滌後,乾燥, 即得目標物2,6-二胺基苯并噻唑44.88(54.0%)。 按照上述合成流程重複進行該合成操作,以確保以下 的聚合物的合成所必需量的2,6 -二胺基苯并唾唑。 <特定聚合物的合成> Φ 合成例2(聚醯亞胺的合成1) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 110g(0.50 莫耳)和 l,3,3a,4,5,9b-六氫-8·甲基- 5-(四氫- 2,5-二側氧-3-呋喃基)·萘[l,2-c]-呋喃-1,3-二酮160g(0.50莫 耳)’作爲二胺的對苯二胺84g(0.78莫耳)、2,6-二胺基苯 并噻唑16.5g(0.1莫耳)、2,2-二(三氟甲基)-4,4-二胺基聯苯 32g(0.10莫耳)和 3,6-二(4-胺基苯甲醯氧基)膽留焼 6.4g(0.010莫耳),以及作爲單胺的苯胺2_8g(0.03莫耳)溶 © 於1200gN-甲基-2-吡咯烷酮(NMP)中,在60°C下進行9小 時反應,得到含聚醯胺酸的溶液。取少量所得聚醯胺酸溶 液,加入NMP,配成聚醯胺酸濃度爲10重量%的溶液,測 定的溶液黏度爲58mPa.s。 然後,向以上製得的聚醯胺酸溶液中追加 24〇Qg NMP,再加入400g吡啶和410g醋酸酐,在110°C下進行4 小時脫水閉環反應。脫水閉環反應後,通過將體系內的_ 劑用新的γ-丁內酯進行溶劑置換(通過該溶劑置換操作,# -40- 201005006 脫水閉環反應中使用的吡啶和醋酸酐除去至體系外。下 同)’然後濃縮,得到約3700g含10重量%醯亞胺化率約爲 95 %的聚醯亞胺(PI - 1)的溶液。該聚醯亞胺溶液的溶液黏 度爲 69 mPa's。 合成例3(聚醯亞胺的合成2) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 110g(0.50 莫耳)和 l,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二側氧-3-呋喃基)-萘[l,2·c]-呋喃-l,3-二酮160g(0.50莫 Φ 耳)’作爲二胺的對苯二胺94g(0.87莫耳)、2,6-二胺基苯 并噻唑16.5g(〇.l莫耳)、1,3-雙(3-胺基丙基)四甲基二矽氧 烷 25g(0.10莫耳)和3,6-雙(4-胺基苯甲醯氧基)膽甾烷 9.6g(0.015莫耳),以及作爲單胺的苯胺2.8g(0.030莫耳) 溶於960g NMP中,在60°C下進行6小時反應,得到含聚 醯胺酸的溶液。取少量所得聚醯胺酸溶液,加入NMP,配 成聚醯胺酸濃度爲10重量%的溶液,測定的溶液黏度爲60 mP a· s ° © 然後,向所得的聚醯胺酸溶液中追加2700g NMP,再 加入400g吡啶和410g醋酸酐,在110°C下進行4小時脫 水閉環反應。脫水閉環反應後,通過將體系內的溶劑用新 的γ-丁內酯進行溶劑置換,然後濃縮,得到約3 8 00g含10 重量%醯亞胺化率約爲88%的聚醢亞胺(PI- 2)的溶液。該 聚醯亞胺溶液的溶液黏度爲55 mP a· s。 合成例4(聚醯亞胺的合成3) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 -41- 201005006 110g(0·50 莫耳)和 l,3,3a,4,5,9b-六氫-8-甲基- 5-(四氫- 2,5-一側氧-3-呋喃基呋喃-〗,3_二酮16〇g(〇5〇莫 耳)’作爲二胺的對苯二胺94g(〇 87莫耳)、2 6_二胺基苯 并嚷哩16.5g(〇.i莫耳雙(3_胺基丙基)四甲基二矽氧 院25g(0.10莫耳)和4_(4,_三氟甲氧基苯甲醯氧基)環己基 -3,5-二胺基苯甲酸酯35g(〇 〇8〇莫耳),以及作爲單胺的苯 胺2.8g(0.030莫耳)溶_於1271g NMP中,在60°C下進行6 小時反應’得到含聚醯胺酸的溶液。取少量所得聚醯胺酸 〇 溶液’加入NMP,配成聚醢胺酸濃度爲1〇重量%的溶液, 測定的溶液黏度爲60 mPa.s。 然後’向所得的聚醯胺酸溶液中追加2500g NMP,再 加入400g吡啶和410g醋酸酐,在11〇。(:下進行4小時脫 水閉環反應。脫水閉環反應後,通過將體系內的溶劑用新 的γ-丁內酯進行溶劑置換,然後濃縮,得到約3800g含10 重量%醯亞胺化率約爲96%的聚醯亞胺(P1-3)的溶液。該 聚醯亞胺溶液的溶液黏度爲55 mPa.s。 ® 合成例5(聚醯亞胺的合成4) 將作爲四羧酸二酐的2,3,5 -三羧基環戊基醋酸二酐 110g(0_50莫耳),作爲二胺的對苯二胺43g(0.40莫耳)、2,6-二胺基苯并噻唑16.5g(0.1莫耳)和3-(3,5-二胺基苯甲醯氧 基)膽甾烷52g(0.10莫耳)溶於830g NMP中,在60。(:下進 行6小時反應,得到含聚醯胺酸的溶液。取少量所得聚醯 胺酸溶液,加入NMP,配成聚醯胺酸濃度爲20重量%的溶 液,測定的溶液黏度爲2200 mPa.s。 -42- 201005006 然後,向所得的聚醯胺酸溶液中追加1 500g NMP,再 加入40g吡啶和51g醋酸酐,在11(TC下進行4小時脫水 閉環反應。脫水閉環反應後,通過將體系內的溶劑用新的 NMP進行溶劑置換,然後濃縮,得到約2700g含7重量% 醯亞胺化率約爲50%的聚醯亞胺(PI- 4)的溶液。該聚醯亞 胺溶液的溶液黏度爲30mPai。 合成例6(聚醯亞胺的合成5) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 © ll〇g(〇.5〇莫耳),作爲二胺的對苯二胺49g(0.45莫耳)、2,6-二胺基苯并噻唑16.5g(0.1莫耳)和3-(3,5-二胺基苯甲醯氧 基)膽甾烷26g(0.05莫耳)溶於750g NMP中,在6(TC下進 行6小時反應,得到含聚醯胺酸的溶液。取少量所得聚醯 胺酸溶液,加入NMP,配成聚醯胺酸濃度爲20重量%的溶 液,測定的溶液黏度爲220 0 mP a· s » 然後,向所得的聚醯胺酸溶液中追加1 800g NMP,再 加入40g吡啶和51g醋酸酐,在lure下進行4小時脫水 β 閉環反應。脫水閉環反應後,通過將體系內的溶劑用新的 ΝΜΡ進行溶劑置換,得到約2 5 00g含7重量%醯亞胺化率 約爲50%的聚醯亞胺(PI- 5)的溶液。該聚醯亞胺溶液的溶 液黏度爲50mPa-s。 合成例7(聚醯亞胺的合成6) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酸酐 110g(0.50莫耳),作爲二胺的對苯二胺38g(035莫耳)、2,6-二胺基苯并噻唑16.5g(0.1莫耳)、4,4,-二胺基二苯基甲烷 •43- 201005006 20g(0_l莫耳)和3-(3,5-二胺基苯甲醯氧基)膽甾烷26g(〇〇5 莫耳)溶於810gNMP中,在60°C下進行6小時反應,得到 含聚醯胺酸的溶液。取少量所得聚醯胺酸溶液,加入NMP, 配成聚醯胺酸濃度爲7重量%的溶液,測定的溶液黏度爲 65 mPa·s 〇 然後,向所得的聚醯胺酸溶液中追加1 900g NMP,再 加入80g吡啶和l〇〇g醋酸酐,在U0°C下進行4小時脫水 閉環反應。脫水閉環反應後,通過將體系內的溶劑用新的 ® NMP進行溶劑置換,得到約1 400g含15重量%醯亞胺化率 約爲80 %的聚醯亞胺(PI — 6)的溶液。取少量該聚酿亞胺溶 液,加入NMP,配成聚醯亞胺濃度爲1〇重量%的溶液,測 定的溶液黏度爲90 mPa*s。 合成例8(聚醯亞胺的合成7) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 110g(0.50莫耳),作爲二胺的對苯二胺43g(0.40莫耳)和 2,6-二胺基苯并噻唑16.5g(0.1莫耳)溶於l800gNMP中, ® 在60°C下進行6小時反應,得到含聚醯胺酸的溶液。取少 量所得聚醯胺酸溶液,加入NMP,配成聚醯胺酸濃度爲10 重量%的榕液,測定的溶液黏度爲70 mPa*S。 然後,向所得的聚醯胺酸溶液中追加1800g NMP,再 加入80g吡啶和100g醋酸酐,在110°C下進行4小時脫水 閉環反應。脫水閉環反應後,通過將體系內的溶劑用新的 γ_ 丁內酯進行溶劑置換,然後濃縮,得到約1200g含15重 量%醯亞胺化率約爲89 %的聚醯亞胺(PI - 7)的溶液。取少 -44 - 201005006 量該聚醯亞胺溶液,加入γ- 丁內酯,配成聚醯亞胺濃度爲 10重量%的溶液,測定的溶液黏度爲15〇111]?&.3。 合成例9(聚醯亞胺的合成8) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 1658(0.75莫耳)和1,3,33,4,5,91)_六氫-8_甲基-5_(四氫-2,5-二側氧-3-呋喃基)_萘呋喃-丨,3_二酮78g(0.25莫 耳),作爲二胺的對苯二胺32g(0.30莫耳)、2,6·二胺基苯 并噻唑16.5g(0.1莫耳)、4,4’-二胺基二苯基醚80g(0.4莫 〇 耳)和二{4-(4-胺基苯氧基)苯基}颯85g(0.20莫耳)溶於 2600g NMP中,在6(TC下進行6小時反應,得到含聚醯胺 酸的溶液。取少量所得聚醯胺酸溶液,加入NMP,配成聚 醯胺酸濃度爲10重量%的溶液,測定的溶液黏度爲4 00 m P a · s ° 然後,向所得的聚醯胺酸溶液中追加1 800g NMP,再 加入395g吡啶和310g醋酸酐,在llOt下進行4小時脫 水閉環反應。脫水閉環反應後,通過將體系內的溶劑用新 β 的γ-丁內酯進行溶劑置換,然後濃縮,得到約1 3 5 0g含15 重量%醯亞胺化率約爲85%的聚醯亞胺(PI - 8)的溶液。取 少量該聚醯亞胺溶液,加入γ-丁內酯,配成聚醯亞胺濃度 爲1 0重量%的溶液,測定的溶液黏度爲90 mPa.s。 合成例10(聚醯亞胺的合成9) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 ll〇g(0.50莫耳),作爲二胺的 2,6-二胺基苯并噻唑 82-5g(0.5莫耳)溶於1800gNMP中,在60°C下進行6小時 -45- 201005006 反應,得到含聚醢胺酸的溶液。取少量所得聚醯胺酸溶液, 加入NMP,配成聚醯胺酸濃度爲10重量%的溶液,測定的 溶液黏度爲65 mPa_s。 然後,向所得的聚醯胺酸溶液中追加1800g NMP,再 加入80g吡啶和100g醋酸酐,在1 10°C下進行4小時脫水 閉環反應。脫水閉環反應後,通過將體系內的溶劑用新的 γ-丁內酯進行溶劑置換,然後濃縮,得到約1100g含15重 量%醯亞胺化率約爲83%的聚醯亞胺(PI - 9)的溶液。取少 〇 量該聚醯亞胺溶液,加入γ-丁內酯,配成聚醯亞胺濃度爲 10重量%的溶液,測定的溶液黏度爲70 mP a· s。 合成例11(聚醯亞胺的合成10) 將作爲四羧酸二酐的2,3,5 -三羧基環戊基醋酸二酐 11(^(0.50莫耳),作爲二胺的對苯二胺328(0.30莫耳)、2,6-二胺基苯并噻唑16.5g(0.1莫耳)、2,2’-雙(三氟甲基)苯 16g(0.05 0莫耳)和4,4’-二胺基二苯基甲烷llg(〇,〇50莫耳) 溶於2000g NMP中,在60°C下進行6小時反應,得到含聚 ® 醯胺酸的溶液。取少量所得聚醯胺酸溶液,加入NMP,配 成聚醯胺酸濃度爲10重量%的溶液,測定的溶液黏度爲480 mPa· s ° 然後,向所得的聚醯胺酸溶液中追加1800g NMP,再 加入126g吡啶和163g醋酸酐,在ll〇°C下進行4小時脫 水閉環反應。脫水閉環反應後,通過將體系內的溶劑用新 的γ-丁內酯進行溶劑置換,然後濃縮,得到約130(^含15 重量%醯亞胺化率約爲88%的聚醯亞胺(ΡΙ - 1〇)的溶液。取 -46- 201005006 少量該聚醯亞胺溶液’加入γ-丁內酯,配成聚醯亞胺濃度 爲10重量%的溶液’測定的溶液黏度爲35 mPa.s。 <其他聚合物的合成> 合成例12(其他聚醯胺酸的合成1) 將作爲四羧酸二酐的均苯四酸二酐ll〇g(〇.50莫耳)和 1,2,3,4·環丁烷四羧酸二酐98g(0.50莫耳),作爲二胺的4,4-二胺基二苯基醚200g(l_0莫耳)溶於由230g NMP和2010g γ -丁內酯組成的混合溶劑中,在401下進行3小時反應 © 後,追加1350g γ -丁內酯,得到約3500g含有1〇重量%聚 醯胺酸(PA — 1)的溶液。該聚醯胺酸溶液的溶液黏度爲2〇〇 mPa's 〇 合成例13 (其他聚醯胺酸的合成2) 將作爲四羧酸二酐的1,2,3,4 -環丁烷四羧酸二酐 98g(0,50莫耳)和均苯四酸二酐11〇g(〇5〇莫耳),作爲二胺 的4’4’-—胺基二苯基甲烷2〇〇g(1〇莫耳)溶於由23〇gNMP 和21 0〇g 丁內酯組成的混合溶劑中,在40 〇C下進行3小Preferred polyplycosyl p-phenylenediamine, 4,4'-diamine 1,5-diaminonaphthalene, 2,7-bis[4-(4-aminophenoxy) 2 , 2-bis[4-(4-aminophenoxy) as the other diamine for synthesizing the liquid crystal alignment agent of the present invention, among which the above-mentioned preferred use is selected from the group consisting of diphenylmethane and 4,4'-diaminodiphenyl. Thioetherdiamine hydrazine, 4,4'-diaminodiphenyl ether, 2,2 phenyl]propane, 9,9-bis(4-aminophenyl)fluorene, phenyl)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p--24- 201005006 phenylene diisopropylidene)diphenylamine, 4,4'- Phenyldiisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4,-methylenebis(cyclohexylamine), 1,4-bis(4-aminophenoxy) Benzene, 4,4'-bis(4-aminophenoxy)biphenyl, a compound represented by the above formula (D-1) to (D-5), 2,6-diaminopyridine, 3,4 - a diaminopyridine, a 2,4-diaminopyrimidine, a 3,6-diamino acridine, a compound represented by the above formula (D-6), a compound represented by the above formula (D-7), and the above formula ( Compound represented by D-III) and 1,3-bis(3-diaminopropyl-propyl) At least one of the group consisting of _tetramethyldioxane. In the above formula (D-III), R9 is -0- or -COO-* (wherein the linkage is bonded to R1G), and R1() has The compound of the monovalent organic group of the steroid skeleton is particularly preferably a compound represented by the above formula (D-8) to (D-13). As the other diamine, it preferably contains a compound selected from the group consisting of p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, and bis[4-(4.amine) a diamine of at least one group consisting of a compound of the above formula (D - III), particularly preferably a p-phenylenediamine, a 4,4'-diamine At least one of the group consisting of stilbene-β-methane, 4,4′-diaminodiphenyl ether and bis[4-(4-aminophenoxy)phenyl]anthracene and the above formula (D_) The diamine of the compound represented by III). The preferred diamine of the polyglycolic acid used in the synthesis of the liquid crystal alignment agent of the present invention preferably contains 1 mol% or more, more preferably 5 to 90 mol% relative to all diamines. Further preferably contains 1 〇 ~ 80 mol %, especially good containing 15 ~ 30 mol% of compound (a). The di-25-201005006 amine for use in synthesizing the preferred polyglycolic acid in the liquid crystal alignment agent of the present invention preferably contains 1 to 50 mol%, more preferably 5 to 30 mol%, based on the entire diamine. A compound represented by the formula (d _ III). The preferred polyamine of the polyglycolic acid used in the synthesis of the liquid crystal alignment agent of the present invention preferably contains 30 to 90 mol%, more preferably 40 to 80 mol%, based on the entire diamine. a group consisting of phenylenediamine, 4,4,-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether and bis[4-(4-aminophenoxy)phenyl] mill At least one of the groups. <Synthesis of Polylysine> © Preferred polyphthalic acid in the liquid crystal alignment agent of the present invention can be produced by reacting a tetracarboxylic dianhydride as described above with a diamine containing the compound (A) Got it. The ratio of use of the tetracarboxylic dianhydride to the diamine supplied to the polyaminic acid synthesis reaction is preferably 0.2 to 2 equivalents based on 1 equivalent of the amine group in the diamine, and the anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. More preferably, it is a ratio of 〇7 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at a temperature of -20 to 150 ° C, more preferably 0 to 10 ° C, preferably 1 to 72 β hours, more preferably Good for 3 to 48 hours. Here, 'the organic solvent is not particularly limited as long as it is a solvent capable of dissolving the produced polyamic acid, and examples thereof include 1-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, and the like. Ν,Ν·Dimethylformamide, 3-butoxy-oxime, Ν·dimethylpropanamide, 3-methoxy-oxime, Ν-dimethylpropionate, 3-hexyloxy - anthraquinone compounds such as hydrazine, hydrazine, dimethyl propylamine, dimethyl sulfonium I, r-butyrolactone, tetramethylurea, hexamethylphosphonium triamine; Phenolic compounds such as phenol, xylene, phenol, and halogenated phenol. The amount of the organic solvent (α), usually, -26-201005006 is preferably such that the total amount (β) of the tetracarboxylic dianhydride and the diamine is 0.1 to 30% by weight based on the total amount of the reaction solution (α + β). The amount. Further, when the organic solvent is used in combination with the poor solvent described below, the amount of the above organic solvent (〇〇 is understood to mean the total amount of the organic solvent and the poor solvent. In the above organic solvent, the produced polyamine is not formed. In the range of acid precipitation, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are generally considered to be poor solvents for poly-proline, may be used in combination as a specific solvent. Examples thereof include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, 1,4-butanediol, and triethylene glycol. Ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methoxy propyl Methyl ester, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, Ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, di-glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, diisobutyl ketone, isoamyl propionate, Isoamyl isobutyrate, diisoamyl ether, etc. When the organic solvent is used in combination with the poor solvent as described above, the use ratio of the poor solvent can be appropriately set within a range in which the produced polyamine acid is not precipitated. The total amount of the organic solvent and the poor solvent is preferably 30% by weight or less, more preferably 20% by weight or less. -27- 201005006 As described above, a reaction solution in which polylysine is dissolved is obtained. The solution may be directly supplied to the liquid crystal alignment agent to be prepared, or the polyamic acid contained in the reaction solution may be separated and supplied to the liquid crystal alignment agent for preparation, or the separated polyamic acid may be purified. Supply liquid crystal alignment agent to prepare. When polylysine is dehydrated When the ring is made into a polyimine, the reaction solution may be directly supplied to the dehydration ring-closure reaction, or the poly-proline contained in the reaction solution may be separated and supplied to the dehydration ring-closure reaction, or the separated polymer may be Φ. The proline acid is purified and then supplied to the dehydration ring-closure reaction. The separation of the polyamic acid can be carried out by adding the above reaction solution to a large amount of a poor solvent to obtain a precipitate, and then drying the precipitate under reduced pressure, or The organic solvent in the reaction solution is subjected to a method of distilling off under reduced pressure in an evaporator. Further, the polylysine is dissolved in an organic solvent and then precipitated with a poor solvent, or once or several times. Polyacetamide can be purified by a method of distilling off under reduced pressure in an evaporator. <Polyimine> The preferred polyimine in the liquid crystal alignment agent of the present invention can be obtained by dehydrating and ring-closing the polylysine as described above. The polyimine in the liquid crystal alignment agent of the present invention may be a complete ruthenium imide of a protonic acid structure in which the precursor polyamic acid has a dehydration ring closure, or a partial dehydration ring closure of only the proline structure. a partial ruthenium imide of a valeric acid structure and a quinone ring structure. The polyimine contained in the liquid crystal alignment agent of the present invention preferably has a ruthenium iodide ratio of -28 to 201005006 of 4 〇 mol% or more, more preferably 80 mol% or more. By using a polyimine having a ruthenium iodide ratio of 40 mol% or more, a liquid crystal alignment agent capable of forming a liquid crystal alignment film having better charge leakage property can be obtained. The above ruthenium amide ratio is a total amount of the guanidine structure and the number of quinone ring structures in the polyimine, and the ratio of the number of quinone ring structures is expressed as a percentage. At this time, a part of the quinone ring may also be an isoindole ring. The ruthenium imidization rate can be obtained by dissolving the polyimine in a suitable deuterated solvent (for example, deuterated dimethyl hydrazine) based on tetramethyl decane. The substance 'at room temperature (for example, 25 ° C) The W-NMR was measured, and the measurement result was obtained by the following formula (1). Ruthenium amination rate (%) = (1 - A"A2x a )xl 00 (1) (In equation (1), A1 is the peak area originating from the NH matrix near the chemical shift of 10 ppm, and A2 is the source In the peak area of other protons, α is the proton of one sulfhydryl group in the precursor of polyimine (poly-proline), the ratio of the number of other protons.) The dehydration ring closure of poly-proline Preferably, (i) is carried out by heating the polyaminic acid method or (ii) by dissolving the polyaminic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. The reaction temperature in the method of heating poly-proline in the above (i) is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. The reaction time is preferably from 1 to 8 hours, more preferably from 3 to 3. 5 hours. When the reaction temperature is less than 50 °C, the dehydration ring-closure reaction cannot be sufficient. If the reaction temperature exceeds 200 °C, the molecular weight of the obtained polyimine will decrease. -29- 201005006 In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the polyaminic acid solution of the above (ii), As the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent is determined according to the desired ruthenium imidation ratio, preferably 1 mol of the polyglycolic acid. The structure of the amine acid is 0.01 to 20 mol. Further, as the dehydration ring-closure catalyst, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. However, it is not limited thereto. Preferably, the dehydrating agent is 0. 01~10 mol with respect to 1 mol. The more the dehydrating agent and the dehydrated ring-closing agent are used, the higher the niobium amination rate can be used. The organic solvent is exemplified as the organic solvent used for the synthesis of the polyamic acid. The reaction temperature of the dehydration ring-closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. Preferably, it is 1 to 8 hours, more preferably 3 to 5 hours. The polyimine prepared in the above method (i) can be directly supplied to a liquid crystal alignment agent for modulation, or the obtained polyfluorene can also be obtained. The imine is refined and then supplied to the liquid crystal. Further, in the above method (ii), a reaction solution containing a polyimine is obtained, and the reaction solution may be directly supplied to a liquid crystal alignment agent for preparation, or may be dehydrated from the reaction solution. After the agent and the dehydration ring-closing catalyst are supplied to the liquid crystal alignment agent for preparation, the polyimine may be separated and supplied to the liquid crystal alignment agent for preparation, or the separated polyimine may be purified and then supplied to the liquid crystal alignment agent for preparation. The dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, and for example, a method such as solvent replacement can be used. The separation and purification of the polyimine can be carried out in the same manner as described above for the separation and purification method of polyglycine. - 201005006 Operation. - Terminal-modified polymer - The poly-proline and the polyimine contained in the liquid crystal alignment agent of the present invention may each be a terminal-modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating performance and the like of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention. Such a terminally modified polymer can be carried out by adding a molecular weight modifier to a polymerization reaction system during the synthesis of polyamic acid. As the molecular weight modifier, a monoanhydride, a monoamine compound, a monoisocyanate compound or the like can be listed. As the above-mentioned monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl amber may be mentioned. Anhydride, etc. Examples of the above monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and positive ten Dialkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecaneamine, n-octadecylamine, n-icosylamine®, and the like. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on the total amount of the tetracarboxylic dianhydride and the diamine used in the synthesis of the polyglycolic acid. - solution viscosity - polylysine and polyimine prepared as above, each preferably having a solution viscosity of 20 to 800 mP a. S when formulated into a solution having a concentration of 10% by weight, -31-201005006 Good with a solution viscosity of 30~500 mPas. The solution viscosity (mPa's) of the above polymer is a polymer solution having a concentration of 10% by weight prepared by using a good solvent of the polymer, and measured by an E-type rotational viscometer at 25 °C. <Other Additives> The liquid crystal alignment agent of the present invention contains the specific polymer as described above as an essential component, and may further contain other components as necessary. As such other components, for example, other polymers, an adhesion enhancer, and the like can be given. φ The above other polymers can be used for improving solution properties and electrical properties. The other polymer is a polymer other than the specific polymer, and for example, a polyglycine prepared by reacting a tetracarboxylic dianhydride with a diamine containing no compound (A) (hereinafter referred to as "other poly" "Proline" "), a polyimine (hereinafter referred to as "other polyimine") obtained by dehydration of the poly-proline, a polyphthalamide, a polyester, a polyamide, a polypeptone Oxylkane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate, and the like. Among them, other poly-proline or other polyimine are preferred. The use ratio of the other polymer is preferably 90% by weight or less, and more preferably 85% by weight or less based on the total amount of the polymer (refer to the total amount of the specific polymer and the other polymer, the same applies hereinafter). The above-mentioned adhesiveness enhancer can be used for the purpose of improving the adhesion of the formed liquid crystal alignment film to the surface of the substrate. As such a binder enhancer, for example, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy compound"), a functional decane compound, or the like - 32-201005006 may be mentioned as the above epoxy group compound. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 ,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl-m-phenylene Methylamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, ^:^',:^'-tetraglycidyl-4,4'-diaminodiphenyl Methane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane, © 3-(anthracene, 二glycidyl)aminopropyltrimethoxydecane, and the like. The use ratio of the epoxy group as described above is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total amount of the polymer. The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane or 2-aminopropyl. Triethoxy decane, Ν-(2-aminoethyl)-3-aminopropyltrimethoxydecane, Ν-(2-aminoethyl)-3-aminopropyl® methyl dimethyl Oxydecane, 3-ureidopropyltrimethoxydecane, 3·ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl- 3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecane 1,4,7-triazanonane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindole Acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, Ν-benzyl-3-aminopropyltrimethoxydecane, Ν-benzyl-3-amine Propyl triethoxy-33- 201005006 decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxyhydrazine Alkyl, N-bis(oxyvinyl)-3-aminopropyltrimethoxydecane, N-bis(oxyvinyl)-3-aminopropyltriethoxydecane, and the like. The use ratio of the functional decane compound as described above is preferably 2 parts by weight or less, more preferably 0.01 to 〇. 2 parts by weight, based on 100 parts by weight of the total amount of the polymer. The liquid crystal alignment agent of the present invention is preferably prepared by dissolving a specific polymer as described above and other additives optionally blended as needed in an organic solvent. Examples of the organic solvent which can be used in the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, r-butyrolactone, r·butylide, N,N-dimethylformamide, and N. , N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxylate Ethyl propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene Alcohol ether acetate, diglyme, di-glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Ester, 3-butoxy-indole, hydrazine-dimethylpropanamide, 3-methoxy-indole, hydrazine-dimethylpropanamide, 3-hexyloxy-indole, hydrazine-dimethyl propyl Amidoxime and the like. The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., preferably 1 to 1 Torr. The range of % by weight. That is, the liquid crystal alignment agent of the present invention is coated on the surface of the substrate as described below, preferably by heating to form a coating film as a liquid crystal alignment film, which will cause the coating when the solid content concentration is less than 1% by weight. The thickness of the film is too small to obtain a good liquid crystal alignment film; on the other hand, when the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick to obtain a good liquid crystal alignment film, and the adhesion of the liquid crystal alignment agent The increase in properties leads to poor coating properties. The particularly preferable solid content concentration range differs depending on the method used to apply the liquid crystal alignment agent to the substrate. For example, when the spin coating method is employed, the specific solid content concentration is in the range of 1.5 to 4.5% by weight. When the printing method is employed, it is particularly preferable that the solid content concentration is in the range of 3 to 9 % by weight, so that the viscosity of the solution falls within the range of 12 to 50 mPai. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5 % by weight, so that the solution viscosity can be made to fall within the range of 3 to 15 mPa 's. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇 ° C to 200 ° C, more preferably 20 ° C to 60 ° C. The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal ruthenium alignment agent of the present invention as described above. Preferred working modes of the liquid crystal display device of the present invention include a TN type, a VA type, and an IPS type. The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). For step (1), the substrate used differs depending on the desired mode of operation. Steps (2) and (3) are common to various operation modes. (1) First, a coating film is formed on a substrate by applying a liquid crystal alignment agent of the present invention on a substrate and then heating the coated surface. -35- 201005006 (1 ~ 丨) When manufacturing a TN type or VA type liquid crystal display element, two substrates each having a patterned transparent conductive film are used as a pair, preferably by offset printing, roll coating, or spin In the coating method or the inkjet printing method, the liquid crystal alignment agent of the present invention is applied to each of the surfaces on which the transparent conductive film is formed to form a coating film. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate, polybutylene terephthalate, polyether mill, polycarbonate, poly (aliphatic ring) can be used. Plastic transparent substrate such as olefin). As the transparent conductive film provided on one side of the substrate, a transparent film made of tin oxide (Sn02), a NESA film (registered trademark of PPG, USA), an indium oxide-tin oxide (ln203-Sn02), or the like can be used to form a transparent pattern. The conductive film can be obtained, for example, a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern when a transparent conductive film is formed, or the like. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane compound or a functional titanium may be preliminarily coated on the surface of the substrate on which the coating film is to be formed. Pretreatment of a compound or the like ® After applying a liquid crystal alignment agent to such a substrate, preheating (prebaking) is preferably performed for the purpose of preventing liquid sagging or the like. The prebaking temperature is preferably from 30 to 200 ° C, more preferably from 40 to 150 ° C, and particularly preferably from 40 to 1 ° C. The prebaking time is preferably from 0.25 to 10 minutes, more preferably from 0.5 to 5 minutes. After prebaking, in order to completely remove the solvent in the film and when the polymer contained in the liquid crystal alignment agent has a proline structure, it is subjected to a retanning (post-baking) step for the purpose of thermally imidating it. The post-baking temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. The post-baking time is preferably 5 to 200 minutes, and -36 to 201005006 is preferably 10 to 100 minutes. The thickness of the coating film thus formed is preferably 0.001 to Ιμηη, more preferably 0.005 to 0.5 μm. (1 - 2) On the other hand, when manufacturing an IPS type liquid crystal display element, it is preferable to use an offset printing method, a roll coating method, a spin coating method or an inkjet printing method, and a transparent conductive film having a comb-tooth pattern is provided. Applying the liquid crystal alignment agent of the present invention to the conductive film forming surface of the substrate and the opposite substrate on which the conductive film is not provided, and then preferably heating each coated surface (prebaking and post-baking) to form a coating film. . At this time, the material of the substrate and the transparent conductive film to be used, the method of forming the transparent conductive film pattern, the pre-treatment of the substrate, the pre-baking and post-baking conditions after coating, the film thickness of the formed coating film, and the above ( 1 - 1) Same. In any of the above (1 to 1) and (1 to 2), the liquid crystal alignment agent of the present invention forms a coating film as a liquid crystal alignment film by removing an organic solvent after coating, when the liquid crystal alignment agent of the present invention contains When the polymer is polylysine or a polyimine having a quinone ring structure and a guanine structure in the same state as β, it may be subjected to a dehydration ring-closure reaction by further heating after forming a coating film to form a further hydrazine. The imidized coating film. (2) The coating film formed as described above may be used as a liquid crystal alignment film for a VA liquid crystal display element as it is, or the coating film surface may be optionally subjected to the following polishing treatment. When the coating film formed as described above is used as a liquid crystal alignment film for a ruthenium type or IPS type liquid crystal display element, liquid crystal alignment is produced by polishing the surface of the coating film to produce alignment energy of liquid crystal molecules on the film of -37-201005006. membrane. The polishing treatment can be carried out by rubbing the surface of the coating film in a predetermined direction with a roll of a cloth made of a fiber such as nylon, rayon, or cotton. In addition, the liquid crystal alignment film formed as described above is, for example, Patent Document 4 (Japan) A process of irradiating a part of a liquid crystal alignment film with ultraviolet rays and changing a pretilt angle of a partial region of the liquid crystal alignment film, as shown in Japanese Laid-Open Patent Publication No. Hei 6-281-93, Or, after forming a resist film on a part of the surface of the liquid crystal alignment film, which is shown in the patent document 6 (JP-A-H05-107544), the resist film is removed in a direction different from the previous polishing process to remove the resist film. The treatment makes the liquid crystal alignment film have different liquid crystal alignment energy in each region, and can improve the field of view performance of the obtained liquid crystal display device. (3) A pair of substrates on which the liquid crystal alignment film was formed as described above was fabricated, and the two substrates were placed oppositely through the gap (cell gap) so that the polishing direction of the liquid crystal alignment film was perpendicular or antiparallel to each other. The peripheral portions of the two substrates are bonded together with a sealant, and a liquid crystal is injected into the interstitial space surrounded by the surface of the substrate and the sealant, and the injection hole is sealed to form a liquid crystal cell. Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell so that the polarizing direction thereof coincides with or perpendicular to the rubbing direction of the liquid crystal alignment film formed on each of the substrates, whereby a liquid crystal display element can be obtained. Here, as the sealant, for example, an epoxy resin containing an alumina ball as a curing agent and a separator can be used. Examples of the liquid crystal include nematic liquid crystal and dish-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff's liquid crystal, an azo-based liquid crystal, a biphenyl liquid crystal, or a phenylcyclohexane can be used. Liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine-38-201005006 Liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal liquid crystal, etc. Further, in these liquid crystals, cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate may be added under the trade names "C-15" and "CB-15" (manufactured by Merck). A chiral agent for sale, a ferroelectric liquid crystal such as a nonyloxybenzylidene-p-amino-2-methylbutyl cinnamate, or the like is used. The polarizer to be bonded to the outer surface of the liquid crystal may be a polarizer formed by stretching a polyvinyl alcohol and absorbing iodine to absorb iodine, and a polarizing film called a "ruthenium film" is sandwiched between the cellulose acetate protective film, or A polarizer made of the enamel itself. The liquid crystal display element of the present invention produced as described above has an advantage that the display performance does not deteriorate even if it is continuously driven for a long period of time as compared with the conventionally known liquid crystal display element, and specifically, for example, liquid crystal is not considered to occur. The backlight film is thermally deteriorated to cause backlight leakage or the like which causes a poor alignment of the liquid crystal. [Examples] Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited to the examples. Further, the solution viscosity of the polymer in the synthesis example was measured by a Ε-type viscometer at 25 °C. <Synthesis of Compound (A)> Synthesis Example 1 (Synthesis of 2,6-diaminobenzothiazole) Synthetic starting material 2-Amino-6-nitrobenzoxazole was directly used in Tokyo Chemical Industry Co., Ltd. The product. 97.6 g (0.50 mol) of 2-amino-6-nitrobenzothiazole was dissolved in 3000 ml of ethanol, and 5 wt% of palladium/carbon 90 g was added, and the mixture was stirred at 70 ° C under a nitrogen-39-201005006 environment. hour. Then, 153 ml of hydrazine monohydrate was added, and the reaction was carried out by carrying the sample under reflux for 6 hours under a nitrogen stream. After completion of the reaction, palladium on carbon was removed by filtration through Celite, and the solvent was removed from the filtrate. The obtained solid was sufficiently washed with distilled water and then dried to give the object 2,6-diaminobenzothiazole 44.88 (54.0%). This synthesis operation was repeated in accordance with the above synthetic scheme to ensure the amount of 2,6-diaminobenzoxazole necessary for the synthesis of the following polymer. <Synthesis of Specific Polymer> Φ Synthesis Example 2 (Synthesis 1 of Polyimine) 1 , 3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol) And l,3,3a,4,5,9b-hexahydro-8.methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2-c]- Furan-1,3-dione 160g (0.50 mole) 'p-phenylenediamine as a diamine 84g (0.78 moles), 2,6-diaminobenzothiazole 16.5g (0.1 moles), 2, 2- bis(trifluoromethyl)-4,4-diaminobiphenyl 32g (0.10 mole) and 3,6-bis(4-aminobenzylideneoxy) bilirubin 6.4g (0.010 Mo The ear) and the aniline 2_8g (0.03 mole) as a monoamine were dissolved in 1200 g of N-methyl-2-pyrrolidone (NMP), and reacted at 60 ° C for 9 hours to obtain a polyglycine-containing solution. A small amount of the obtained polylysine solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 58 mPa·s. Then, 24 〇 Qg of NMP was added to the polylysine solution prepared above, and 400 g of pyridine and 410 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone (by the solvent replacement operation, pyridine and acetic anhydride used in the dehydration ring closure reaction of #-40-201005006 were removed to the outside of the system. The same as below]' was then concentrated to obtain about 3700 g of a solution containing 10% by weight of polyimine (PI-1) having a ruthenium iodide ratio of about 95%. The solution viscosity of the polyimine solution was 69 mPa's. Synthesis Example 3 (Synthesis 2 of Polyimine) 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol) and 1,3,3a,4,5 , 9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene [l,2·c]-furan-l,3-dione 160g ( 0.50 mole Φ ear) 'p-phenylenediamine as diamine 94g (0.87 mole), 2,6-diaminobenzothiazole 16.5g (〇.l mole), 1,3-bis(3-amine Propyl) tetramethyldioxane 25g (0.10 moles) and 3,6-bis(4-aminobenzylideneoxy)cholane 9.6g (0.015 moles), and as a monoamine Aniline 2.8 g (0.030 mol) was dissolved in 960 g of NMP, and reacted at 60 ° C for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyaminic acid solution was added, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 60 mP a·s ° © and then added to the obtained poly-proline solution. 2700 g of NMP was further added with 400 g of pyridine and 410 g of acetic anhydride, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 3 800 g of a polyimine containing 10% by weight of ruthenium iodide (about 88%). A solution of PI-2). The solution viscosity of the polyimine solution was 55 mP a·s. Synthesis Example 4 (Synthesis 3 of Polyimine) 2,3,5-Tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride - 41 - 201005006 110 g (0·50 mol) and 1,3 , 3a, 4, 5, 9b-hexahydro-8-methyl-5-(tetrahydro-2,5-one oxy-3-furanfuran-, 3_dione 16 〇g (〇5〇 Mohr) 'p-phenylenediamine as a diamine 94g (〇87 mole), 2 6-diaminobenzophthalene 16.5g (〇.i mol bis(3_aminopropyl)tetramethyl Dioxane 25g (0.10 mol) and 4_(4,_trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate 35g (〇〇8〇莫耳) And 2.8 g (0.030 mol) of aniline as a monoamine dissolved in 1271 g of NMP, and reacted at 60 ° C for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyglycolate solution was taken. NMP was added to prepare a solution having a polyglycine concentration of 1% by weight, and the measured solution viscosity was 60 mPa·s. Then, 2500 g of NMP was added to the obtained poly-proline solution, and 400 g of pyridine and 410 g of acetic acid were further added. Anhydride, at 11 〇. (: 4 hours dehydration ring closure reaction. After dehydration ring closure reaction, by the solvent in the system The new γ-butyrolactone is subjected to solvent displacement and then concentrated to obtain about 3800 g of a solution containing 10% by weight of a polyimine (P1-3) having a ruthenium iodide ratio of about 96%. The viscosity of the solution was 55 mPa·s. Synthesis Example 5 (Synthesis of Polyimide 4) 110 g (0-50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride. 43 g (0.40 mol) of p-phenylenediamine as diamine, 16.5 g (0.1 mol) of 2,6-diaminobenzothiazole, and 3-(3,5-diaminobenzylideneoxy) cholesta 52 g (0.10 mol) of decane was dissolved in 830 g of NMP, and reacted at 60 ° for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution was added, and NMP was added to form a polypeptone. A solution having an amine acid concentration of 20% by weight, and a measured solution viscosity of 2200 mPa·s. -42 - 201005006 Then, adding 1,500 g of NMP to the obtained polyaminic acid solution, and further adding 40 g of pyridine and 51 g of acetic anhydride, 11 (4 hours of dehydration ring closure reaction under TC. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP solvent, and then concentrated to obtain about 2700 g of 7% by weight. A solution of polyimine (PI-4) having a rate of about 50%. The solution viscosity of the polyimine solution is 30 mPai. Synthesis Example 6 (synthesis of polyimine) 5 will be used as tetracarboxylic dianhydride. 2,3,5-tricarboxycyclopentyl acetic acid dianhydride © ll〇g (〇.5〇莫耳), p-phenylenediamine as diamine 49g (0.45mol), 2,6-diamino Benzothiazole 16.5 g (0.1 mol) and 3-(3,5-diaminobenzylideneoxy)cholestane 26 g (0.05 mol) were dissolved in 750 g of NMP for 6 hours at 6 (TC) The reaction was carried out to obtain a solution containing poly-proline. Take a small amount of the obtained polyaminic acid solution, add NMP, and prepare a solution having a polyglycine concentration of 20% by weight, and measure the viscosity of the solution to 220 0 mP a·s » Then, add to the obtained poly-proline solution 1 800 g of NMP was further added with 40 g of pyridine and 51 g of acetic anhydride, and a dehydration β ring closure reaction was carried out for 4 hours under lure. After the dehydration ring closure reaction, a solvent of the system was replaced with a new hydrazine to obtain a solution of about 2,500 g of a polyimine (PI-5) containing 7 wt% of a ruthenium iodide ratio of about 50%. The solution viscosity of the polyimine solution was 50 mPa-s. Synthesis Example 7 (Synthesis 6 of Polyimine) 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and p-phenylenediamine as a diamine 38 g (035 mol), 2,6-diaminobenzothiazole 16.5 g (0.1 mol), 4,4,-diaminodiphenylmethane•43-201005006 20g (0_l mole) and 3-( 3,5-Diaminobenzimidyloxy)cholestane 26 g (〇〇5 mol) was dissolved in 810 g of NMP, and reacted at 60 ° C for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyaminic acid solution was added, NMP was added to prepare a solution having a polyglycine concentration of 7% by weight, and the measured solution viscosity was 65 mPa·s. Then, 1 900 g of the obtained polyaminic acid solution was added. NMP was further added with 80 g of pyridine and 1 g of acetic anhydride, and a dehydration ring-closure reaction was carried out for 4 hours at U0 °C. After the dehydration ring closure reaction, a solvent of the system was replaced with a new ® NMP to obtain about 1 400 g of a solution containing 15% by weight of polyimine (PI-6) having a ruthenium iodide ratio of about 80%. A small amount of the solution of the brewed imine was added, and NMP was added to prepare a solution having a polyamidene concentration of 1% by weight, and the measured solution viscosity was 90 mPa*s. Synthesis Example 8 (Synthesis of Polyiminide 7) 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, p-phenylenediamine as diamine 43 g (0.40 mol) and 2,6-diaminobenzothiazole 16.5 g (0.1 mol) were dissolved in l800 g of NMP, and the reaction was carried out at 60 ° C for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to prepare a mash having a polyglycine concentration of 10% by weight, and the solution viscosity was determined to be 70 mPa*S. Then, 1800 g of NMP was added to the obtained polyamic acid solution, and 80 g of pyridine and 100 g of acetic anhydride were further added thereto, and a dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 1200 g of a polyimine (15-7) containing 15% by weight of a ruthenium iodide ratio of about 89%. )The solution. Take less -44 - 201005006 The amount of the polyimine solution, add γ-butyrolactone, and prepare a solution with a concentration of 10% by weight of polyimine. The viscosity of the solution is determined to be 15〇111]?&.3. Synthesis Example 9 (Synthesis of Polyimine 8) 2,3,5-Tricarboxycyclopentylacetic acid dianhydride 1658 (0.75 mol) and 1,3,33,4,5 as tetracarboxylic dianhydride , 91) _ hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3-furanyl)-naphthalene-furan, 3-dione 78g (0.25 mol) as diamine P-phenylenediamine 32g (0.30 mol), 2,6-diaminobenzothiazole 16.5 g (0.1 mol), 4,4'-diaminodiphenyl ether 80 g (0.4 mol) and {{4-(4-Aminophenoxy)phenyl}indole 85g (0.20 mol) was dissolved in 2600 g of NMP, and reacted at 6 (TC for 6 hours to obtain a polyglycine-containing solution. The obtained polyaminic acid solution was added with NMP to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 400 m P a · s ° . Then, 1 was added to the obtained poly-proline solution. 800 g of NMP, further adding 395 g of pyridine and 310 g of acetic anhydride, and performing a dehydration ring-closure reaction at llOt for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new β γ-butyrolactone solvent, followed by concentration. About 1 3 50 0g of polyethylenimine containing 15% by weight of hydrazine imidization rate of about 85% (P A solution of I - 8). A small amount of the polyimine solution was added, and γ-butyrolactone was added to prepare a solution having a polyamidene concentration of 10% by weight, and the measured solution viscosity was 90 mPa·s. 10 (Synthesis of Polyimine 9) 2,3,5-Tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride 11 〇g (0.50 mol) as 2,6-di of diamine Aminobenzothiazole 82-5 g (0.5 mol) is dissolved in 1800 g of NMP, and reacted at 60 ° C for 6 hours -45 - 201005006 to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution is obtained. NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the measured solution viscosity was 65 mPa_s. Then, 1800 g of NMP was added to the obtained polyaminic acid solution, and then 80 g of pyridine and 100 g of acetic anhydride were added. 1 4 hours dehydration ring closure reaction at 10 ° C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 1100 g of 15% by weight hydrazine imidization rate. A solution of about 83% polyimine (PI-9). Take a small amount of the polyimine solution and add γ-butyrolactone to form a polypeptone. A solution having an amine concentration of 10% by weight, the measured solution viscosity was 70 mP a·s. Synthesis Example 11 (synthesis of polyiminamide 10) 2,3,5-tricarboxycyclopentane as tetracarboxylic dianhydride Acetate dianhydride 11 (^ (0.50 mol), p-phenylenediamine 328 (0.30 mol) as diamine, 16.5 g (0.1 mol), 2,2' of 2,6-diaminobenzothiazole - bis(trifluoromethyl)benzene 16g (0.05 0 mole) and 4,4'-diaminodiphenylmethane 11g (〇, 〇50 mole) dissolved in 2000g NMP, carried out at 60 ° C The reaction was carried out for 6 hours to obtain a solution containing poly-proline. Take a small amount of the obtained polyaminic acid solution, add NMP, and prepare a solution having a polyglycine concentration of 10% by weight, and measure the viscosity of the solution to 480 mPa·s °. Then, add 1800 g of NMP to the obtained poly-proline solution. Further, 126 g of pyridine and 163 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours at ll °C. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 130% (containing 15% by weight of a polyamidiamine having a ruthenium iodide ratio of about 88%). ΡΙ - 1〇) solution. Take -46- 201005006 a small amount of the polyimine solution 'add γ-butyrolactone, and prepare a solution with a concentration of 10% by weight of polyimine. The solution viscosity is 35 mPa. s. <Synthesis of Other Polymers> Synthesis Example 12 (Synthesis of Other Polylysine 1) Pyromellitic dianhydride as a tetracarboxylic dianhydride 11 〇g (〇.50 mol) and 1,2 , 3,4·cyclobutane tetracarboxylic dianhydride 98 g (0.50 mol), as a diamine 4,4-diaminodiphenyl ether 200 g (l_0 mol) dissolved in 230 g NMP and 2010 g γ - In the mixed solvent of butyrolactone, the reaction was carried out for 3 hours at 401, and then 1,350 g of γ-butyrolactone was added to obtain about 3500 g of a solution containing 1% by weight of polyglycine (PA-1). The solution viscosity of the polyaminic acid solution is 2 〇〇mPa's. Synthesis Example 13 (Synthesis 2 of other polylysine) 1,2,3,4-cyclobutanetetracarboxylic acid as tetracarboxylic dianhydride Dianhydride 98g (0,50 moles) and pyromellitic dianhydride 11〇g (〇5〇莫耳), as a diamine 4'4'-aminodiphenylmethane 2〇〇g (1 〇mol) is dissolved in a mixed solvent consisting of 23〇gNMP and 210 〇g butyrolactone, and 3 hours at 40 〇C

D 時反應後’追加135〇g γ_ 丁內酯,得到約35〇〇g含有1〇重 量%聚酿胺酸(PA— 2)的溶液。該聚醯胺酸溶液的溶液黏度 爲 1 2 5 mP a. s。 合成例14(其他聚醯胺酸的合成3) 將作爲四羧酸二酐的1,2,3,4 -環丁烷四羧酸二酐 200g(1.0莫耳),作爲二胺的22,·二甲基-44,二胺基聯苯 21〇g(1.〇莫耳)溶於由370g NMP和3300g γ·丁內酯組成的 混合溶劑中,在4(TC下進行3小時反應,得到約3 500g含 -47- 201005006 有10重量%聚醯胺酸(PA— 3)的溶液。該聚醯胺酸溶液的溶 液黏度爲160 mPa‘s。 合成例15(其他聚醯胺酸的合成4) 將作爲四羧酸二酐的均苯四酸二酐196g(0.9莫耳)和 1,2,3,4-環丁烷四羧酸二酐19_6g(0_l莫耳),作爲二胺的對 苯二胺21.6g(0.20莫耳)和4,4’-二胺基二苯基醚i80g(0 8 莫耳)溶於24〇〇g NMP中,在60°C下進行4小時反應,得 到約2400g含有10重量%聚醯胺酸(PA 一 4)的溶液。該聚醯 © 胺酸溶液的溶液黏度爲200 mPa.s。 合成例16(其他聚醯亞胺的合成1) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 110g(0.50 莫耳)和 l,3,3a,4,5,9b-六氫-8·甲基- 5- (四氫- 2,5- —側氧-3-呋喃基)-萘[l,2-c] -咲喃- i,3_二酮160g(0.50莫 耳),作爲二胺的對苯二胺95g(0.88莫耳)、2,2-雙(三氟甲 基)-4,4-—胺基聯苯32g(0.10莫耳)和3,6_雙(4_胺基苯甲醯 氧基)膽留烷6.4g(0.010莫耳),以及作爲單胺的苯胺 ® 2.8g(0.03莫耳)溶於1 200g NMP中,在6(rc下進行9小時 反應’得到含聚酿胺酸的溶液。取少量所得聚酸胺酸溶液, 加入NMP,配成聚醯胺酸濃度爲1〇重量%的溶液,測定的 溶液黏度爲58 mPa.s。 然後,向所得聚醢胺酸溶液中追加2400g NMP,再加 入400g吡啶和41〇g醋酸酐,在11〇〇c下進行4小時脫水 閉環反應。脫水閉環反應後,通過將體系內的溶劑用新的 γ -丁內醋進fr溶劑置換’然後濃縮,得到約37〇〇g含有10 -48- 201005006 重量%醯亞胺化率約爲95%的聚醯亞胺(PI— n)的溶液。該 聚醯亞胺溶液的溶液黏度爲69mPa.s。 合成例17(其他聚醯亞胺的合成2) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 110g(0.50 莫耳)和 i,3,3a,4,5,9b-六氫-8-甲基 _5-(四氫- 2,5-一側氧-3 -呋喃基)_萘[i,2-c] -呋喃-l,3 -二酮^(^(0.50莫 耳),作爲二胺的對苯二胺94g(〇_87莫耳)、ι,3 -雙(3 -胺基 丙基)四甲基二矽氧烷25g(0.10莫耳)和3,6_雙(4_胺基苯甲 ® 醯氧基)膽甾烷9.6g(〇.015莫耳),以及作爲單胺的十八烷 基胺8.1g(0.030莫耳)溶於960gNMP中,在60〇C下進行6 小時反應’得到含聚醯胺酸的溶液。取少量所得聚醯胺酸 溶液’加入NMP ’配成聚醯胺酸濃度爲1〇重量%的溶液, 測定的溶液黏度爲60mPa.s。 然後’向所得聚醯胺酸溶液中追加2700g NMP,再加 入400g吡啶和41〇g醋酸酐,在ii〇-C下進行4小時脫水 閉環反應。脫水閉環反應後,通過將體系內的溶劑用新的 β 丁內酯進行溶劑置換,得到約2300g含有15重量%醯亞 胺化率約爲95 %的聚醯亞胺(pi 一 12)的溶液。取少量該聚醯 亞胺溶液,加入γ-丁內酯,配成聚醯亞胺濃度爲10重量% 的溶液’測定的溶液黏度爲70mPa.s。 合成例18(其他聚醯亞胺的合成3) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 110g(0.50 莫耳)和 1,3,3&,4,5 915_六氫-8_甲基_5_(四氫-2,5_ 二側氧-3-呋喃基萘[He].呋喃-丨,3-二酮16〇g(〇5〇莫 -49- 201005006 耳)’作爲二胺的對苯二胺88g(0.82莫耳)、U3-雙(3·胺基 丙基)四甲基二矽氧烷25g(0_10莫耳)和4-(4,-三氟甲氧基 苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯34(0.080莫 耳)’以及作爲單胺的苯胺2.8g(0_030莫耳)溶於1200gNN1P 中’在60 °C下進行6小時反應,得到含聚醯胺酸的溶液。 取少量所得聚醯胺酸溶液,加入NMP,配成聚醛胺酸濃度 爲10重量%的溶液,測定的溶液黏度爲60 mPa.s。 然後’向所得聚醯胺酸溶液中追加2500g NMP,再加 ® 入40〇g吡啶和410g醋酸酐,在ll〇°C下進行4小時脫水 閉環反應。脫水閉環反應後,通過將體系內的溶劑用新的 丁內酯進行溶劑置換,然後濃縮,得到約3600g含有10 重量%醯亞胺化率約爲96%的聚醯亞胺(PI — 13)的溶液。該 聚醯亞胺溶液的溶液黏度爲55mPa.s。 合成例19(其他聚醯亞胺的合成4) 將作爲四羧酸二酐的2,3,5 -三羧基環戊基醋酸二酐 110g(0.50莫耳),作爲二胺的對苯二胺43g(0.40莫耳)和 β 3_(3,5·二胺基苯甲醯氧基)膽留烷52g(0.10莫耳)溶於83 0g NMP中,在60°C下進行6小時反應,得到含聚醯胺酸的溶 液。取少量所得聚醯胺酸溶液,加入NMP,配成聚醯胺酸 濃度爲10重量%的溶液,測定的溶液黏度爲60 mPa*s » 然後,向所得聚醯胺酸溶液中追加1900g NMP,再加 入4〇g毗啶和5ig醋酸酐,在litre下進行4小時脫水閉 環反應。脫水閉環反應後,通過將體系內的溶劑用新的NMP 進行溶劑置換,得到約1100g含有15重量%醯亞胺化率約 -50- 201005006 爲50%的聚醯亞胺(PI - 14)的溶液。取少量該聚醯亞胺溶 液,加入NMP,配成聚醯亞胺濃度爲10重量%的溶液,測 定的溶液黏度爲47 mPai » 合成例20(其他聚醯亞胺的合成5) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 110g(0.50莫耳),作爲二胺的對苯二胺49g(0.45莫耳)和 3-(3,5-二胺基苯甲醯氧基)膽甾烷26g(〇.〇5莫耳)溶於750g NMP中’在60°C下進行6小時反應,得到含聚醯胺酸的溶 ® 液。取少量所得聚醯胺酸溶液,加入NMP,配成聚醯胺酸 濃度爲1〇重量%的溶液,測定的溶液黏度爲58 mPa-s。 然後,向所得聚醯胺酸溶液中追加1800gNMP,再加入 40g吡啶和51g醋酸酐,在U〇°C下進行4小時脫水閉環反 應。脫水閉環反應後,通過將體系內的溶劑用新的NMP進 行溶劑置換’得到約1 000g含有15重量%醯亞胺化率約爲 50 %的聚醯亞胺(PI- 15)的溶液。取少量該聚醣亞胺溶液, 加入NMP,配成聚醯亞胺濃度爲1〇重量%的溶液,測定的 @ 溶液黏度爲85mPai。 合成例21 (其他聚醯亞胺的合成6) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 11(^(0.50莫耳),作爲二胺的對苯二胺388(〇35莫耳)、4,4,-二胺基二苯基甲烷20g(0.1莫耳)和3_(3,5_二胺基苯甲醯氧 基)膽笛院26g(0.05莫耳)溶於800g NMP中,在60。(:下進 行6小時反應’得到含聚醯胺酸的溶液。取少量所得聚醯 胺酸溶液’加入NMP,配成聚醯胺酸漉度爲1〇重量%的溶 -51 - 201005006 液,測定的溶液黏度爲60 mPa_s。 然後,向所得聚醯胺酸溶液中追加1 800gNMP,再加入 80g吡啶和100g醋酸酐,在110°C下進行4小時脫水閉環 反應。脫水閉環反應後,通過將體系內的溶劑用新的NMP 進行溶劑置換,得到約105 Og含有15重量%醯亞胺化率約 爲80%的聚醯亞胺(P1-1 6)的溶液。取少量該聚醯亞胺溶 液,加入NMP,配成聚醯亞胺濃度爲10重量%的溶液,測 定的溶液黏度爲87 mPa*s。 e 合成例22(其他聚醯亞胺的合成7) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 110g(0.50莫耳),作爲二胺的對苯二胺54g(0.50莫耳)溶於 1 800g NMP中,在60°C下進行6小時反應,得到含聚醯胺 酸的溶液。取少量所得聚醯胺酸溶液,加入NMP,配成聚 醯胺酸濃度爲10重量%的溶液,測定的溶液黏度爲75 mPa· s 6 然後,向所得聚醯胺酸溶液中追加1 800gNMP,再加入 ® 8 0g吡啶和100g醋酸酐,在1 1(TC下進行4小時脫水閉環 反應。脫水閉環反應後,通過將體系內的溶劑用新的γ-丁 內酯進行溶劑置換,然後濃縮,得到約14 00g含有15重量 %醯亞胺化率約爲91 %的聚醯亞胺(PI — 17)的溶液。取少量 該聚醯亞胺溶液,加入γ-丁內酯,配成聚醯亞胺濃度爲10 重量%的溶液,測定的溶液黏度爲150 mP a· s。 合成例23 (其他聚醯亞胺的合成8) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酐 -52- 201005006 165g(0.75 莫耳)和 1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二側氧-3·呋喃基)_萘[1,2_c]_呋喃_l,3_二酮78g(0·25莫 耳)’作爲二胺的對苯二胺43g(0.40莫耳)、4,4’-二胺基二 苯基醚 80g(〇.4莫耳)和雙{4-(4-胺基苯氧基)苯基}碾 85g(0.20莫耳)溶於2600g NMP中,在60°C下進行6小時 反應’得到含聚醯胺酸的溶液。取少量所得聚醯胺酸溶液, 加入NMP ’配成聚醯胺酸濃度爲丨〇重量%的溶液,測定的 溶液黏度爲1〇〇 mPa.s。 然後’向所得聚醯胺酸溶液中追加1 800 g NMP,再加 入80g吡啶和i〇〇g醋酸酐,在110°C下進行4小時脫水閉 環反應。脫水閉環反應後,通過將體系內的溶劑用新的γ-丁內酯進行溶劑置換,然後濃縮,得到約2700g含有15重 量%醯亞胺化率約爲81 %的聚醯亞胺(PI - 18)的溶液。取少 量該聚醯亞胺溶液,加入γ-丁內酯,配成聚醯亞胺濃度爲 10重量%的溶液,測定的溶液黏度爲95 mP a· s。 合成例24(其他聚醯亞胺的合成9) 將作爲四羧酸二酐的2,3,5-三羧基環戊基醋酸二酸酐 110g(0.50莫耳),作爲二胺的對苯二胺43g(〇4〇莫耳)、2,2,_ 雙(二氟甲基)苯16g(0.050莫耳)和4,4,-二胺基二苯基甲烷 llg(0.050莫耳)溶於2600gNMP中,在60°C下進行6小時 反應,得到含聚醯胺酸的溶液。取少量所得聚醯胺酸溶液, 加入NMP,配成聚醯胺酸濃度爲1〇重量%的溶液,測定的 溶液黏度爲480 mPa*s。 然後’向所得聚酿胺酸溶液中追加18〇〇gNMP,再加入 -53- 201005006 8〇g吡啶和100g醋酸酐,在ll〇°C下進行4小時脫水閉環 反應。脫水閉環反應後,通過將體系內的溶劑用新的γ-丁 內酯進行溶劑置換,然後濃縮,得到約2500g含有15重量 %醯亞胺化率約爲88 %的聚醯亞胺(PI - 19)的溶液。取少量 該聚醯亞胺溶液,加入γ-丁內酯,配成聚醯亞胺濃度爲10 重量%的溶液,測定的溶液黏度爲90 mPa_s。 實施例1 <液晶配向劑的調製> φ 將換算成聚醯亞胺(PI — 2)相當於20重量份的量的上 述合成例3中製得的含聚醯亞胺(PI - 2)的溶液與換算成聚 醯胺酸(PA— 1)相當於80重量份的量的上述合成例12中製 得的含聚酪胺酸(PA - 1)的溶液進行混合,以γ-丁內酯:Ν-甲基-2-吡咯烷酮:丁基溶纖劑之比爲71 : 17 : 12的重量 比,向其中加入γ-丁內酯、Ν-甲基-2-吡咯烷酮和丁基溶纖 劑,再加入2重量份作爲黏合性增強劑的環氧基化合物 Ν,Ν,Ν’,Ν’-四縮水甘油基-4,4’-二胺基二苯基甲烷,配成固 〇 體含量濃度爲3.5重量%的溶液。將該溶液充分攪拌後,用 孔徑爲Ιμιη的濾器過濾,調製出液晶配向劑。 採用該液晶配向劑如下進行評價。 <液晶顯示元件的製造和評價> [液晶顯示元件的製造] (1)液晶配向劑的塗布和液晶配向膜的形成 採用旋塗機,在旋轉速度爲2000rpm、旋轉時間爲20 秒的條件下,將以上調製的液晶配向劑塗布在厚度爲1mm -54- 201005006 的玻璃基板的一面上設置的ITQ膜制透明導電膜上,在8〇 °C的加熱板上預烘焙1分鐘後,再在2 0 〇 °C下後烘培1小 時,形成膜厚爲0.08 μηι的塗膜。 (2)打磨處理 採用裝有纏繞人造纖維布的輥的打磨機,在輥轉速爲 400 rpm、操作臺移動速度爲3cm/秒,絨毛擠入長度爲 0.4mm的條件下,對上述塗膜進行打磨處理,使塗膜上產 生液晶配向能,製成液晶配向膜。 © (3)塗布了液晶配向膜的基板的洗滌、乾燥 將以上製得的具有液晶配向膜的基板,在超純水中用 超聲波洗滌1分鐘後,在100 °C的潔淨烘箱中乾燥10分鐘。 重複同樣的操作,製作兩塊(一對)具有液晶配向膜的基板。 (4)液晶注入步驟、偏光片的黏合、貼合 然後,在該一對具有液晶配向膜的基板的具有液晶配 向膜的各外緣上,塗布加入了直徑爲5.5μιη的氧化鋁球的 環氧樹脂黏合劑後,使液晶配向膜面相對地重合並壓合, β 使黏合劑固化。接著,由液晶注入口向基板間塡充介電常 數各向異性顯示爲正値的向列型液晶(默克公司生產, MLC-622 1)後,用丙烯酸類光固化黏合劑將液晶注入口封 閉,在基板外側的兩面上貼合偏光片,製造出液晶顯示元 件。 [液晶顯示元件的評價] (1)液晶配向性的評價 採用光學顯微鏡對以上製造的液晶顯示元件進行觀 -55- .201005006 察,此時,沒有漏光的,液晶配向性評價爲“良好”,確 認有漏光的,液晶配向性評價爲“不良”。該液晶顯示元 件的液晶配向性爲“良好”。 (2)耐熱性的評價(耐熱應力實驗) 對以上製造的液晶顯示元件,首先,在167毫秒的時 間跨度下施加5V的電壓,施加時間爲60微秒,然後測定 從電壓解除至167毫秒後的電壓保持率。此時的數値作爲 初期電壓保持率(VHRBF)。測定VHRBF後,將液晶顯示元 ❹ 件置於100 °C的烘箱中,施加1 000小時的熱應力。然後將 液晶顯示元件在室溫下靜置冷卻至室溫後,測定施加熱應 力後的電壓保持率vhraf。求出熱應力施加前後的電壓保 持率的變化率,該變化率不足5%的,耐熱性評價爲“良 好” ,5%以上的,耐熱性評價爲“不良”。該液晶顯示元 件的耐熱性爲“良好”。 實施例2~5 除了聚合物分別使用表1中所示量的表1中所示種類 ® 的聚合物以外,與實施例1同樣地操作,分別調製液晶配 向劑,製造液晶顯示元件,並進行評價。結果列於表2。 實施例6 <液晶配向劑的調製> 取換算成聚醯亞胺(PI-4)相當於100重量份的量的上 述合成例5中製得的含聚醯亞胺(PI - 4)的溶液,向其中以 N-甲基-2-吡咯烷酮:丁基溶纖劑之比爲5 0: 5 0的重量比 加入N-甲基-2-吡咯烷酮和丁基溶纖劑,再加入2重量份作 -56- 201005006 爲黏合性增強劑的環氧基化合物n,n,n’,n’-四縮水甘油基 -4,4’-二胺基二苯基甲烷,配成固體含量濃度爲3.5重量% 的溶液。將該溶液充分攪拌後,用孔徑爲的濾器過濾, 調製出液晶配向劑。 <液晶顯示元件的製造和評價> 作爲液晶,使用介電常數各向異性顯示爲負値的向列 型液晶(默克公司生產’ MLC-2038)’並且’在液晶顯示元 件的製作步驟中,不進行(2)打磨處理,除此以外,與實施 ❹ 例1同樣地操作,製造液晶顯示元件’進行液晶配向性和 耐熱性的評價,結果列於表2。 實施例7和8 除了聚合物分別使用表1中所示量的表1中所示種類 的聚合物以外,與實施例6同樣地操作’分別調製液晶配 向劑,製造液晶顯示元件,並進行評價。結果列於表2。 實施例9 <液晶配向劑的調製> ® 取換算成聚醯亞胺(PI - 7)相當於100重量份的量的合 成例8中製得的含聚醯亞胺(PI - 7)的溶液,向其中加入作 爲黏合性增強劑的1〇重量份環氧基化合物Ν,Ν,Ν’,Ν’-四縮 水甘油基-4,4’-二胺基二苯基甲烷和0.75重量份官能性矽 烷化合物3-[2-(3-三甲氧基矽烷基丙基胺基)乙基胺基]丙 酸甲酯,再以γ-丁內酯:丁基溶纖劑之比爲80:20的重量 比加入γ-丁內酯和丁基溶纖劑,配成固體含量濃度爲3.5 重量%的溶液。將該溶液用孔徑爲Ιμπι的濾器過濾,調製 -57- 201005006 出液晶配向劑。 <液晶顯示元件的製造和評價> 作爲液晶,使用介電常數各向異性顯示爲正値的向列 型液晶(默克公司生產,MLC-2019),除此以外,與實施例 1同樣地操作,製造液晶顯示元件,進行液晶配向性和耐 熱性的評價,結果列於表2。 實施例1 0和1 1 除了聚合物分別使用表1中所示量的表1中所示種類 〇 的聚合物以外,與實施例9同樣地操作,分別調製液晶配 向劑,製造液晶顯示元件,並進行評價。結果列於表2。 實施例1 2 <液晶配向劑的調製> 將換算成聚醯亞胺(P1-10)相當於40重量份的量的上 述合成例11中製得的含聚醯亞胺(PI - 10)的溶液與換算成 聚醯胺酸(PA — 4)相當於60重量份的量的上述合成例15中 製得的含聚醯胺酸(PA- 4)的溶液進行混合’以γ-丁內酯: © Ν-甲基-2-吡咯烷酮:丁基溶纖劑之比爲40 : 40 : 20的重 量比,向其中加入γ-丁內酯、Ν·甲基-2-吡咯烷酮和丁基溶 纖劑,再加入1 〇重量份作爲黏合性增強劑的環氧基化合物 Ν,Ν,Ν,,Ν’-四縮水甘油基- 4,4’-二胺基二苯基甲烷,配成固 體含量濃度爲3.5重量%的溶液。將該溶液充分攪拌後’用 孔徑爲Ιμιη的濾器過濾,調製出液晶配向劑。 採用該液晶配向劑如下進行評價。 <液晶顯示元件的製造和評價> -58- 201005006 作爲液晶,使用介電常數各向異性顯示爲正値的向列 型液晶(默克公司生產,MLC-2019),除此以外,與實施例 1同樣地操作,製造液晶顯示元件,進行液晶配向性和耐 熱性的評價,結果列於表2。 比較例1〜5 除了聚合物使用表1中所示量的表1中所示種類的聚 合物以外,與實施例i同樣地操作,調製液晶配向劑,製 造液晶顯示元件,並進行評價。結果列於表2。 Φ 比較例6〜8 除了聚合物分別使用表1中所示量的表1中所示種類 的聚合物以外,與實施例6同樣地操作,分別調製液晶配 向劑,製造液晶顯示元件,並進行評價。結果列於表2。 比較例9和1 0 除了聚合物分別使用表1中所示量的表1中所示種類 的聚合物以外’與實施例9同樣地操作,分別調製液晶配 向劑,製造液晶顯示元件,並進行評價。結果列於表2。 ® 比較例1 1 除了聚合物分別使用表1中所示量的表1中所示種類 的聚合物以外,與實施例1 2同樣地操作,分別調製液晶配 向劑’製造液晶顯示元件,並進行評價。結果列於表2。 -59- 201005006 ❹ο £ 匿 mg 匿 (軍最%) CS rj cs CN ΓΊ Μ 2 i (窜暈%) r-· 卜 r- Ο Ο 〇 ο r- r- ι> !- 〇 Ο 〇 j PQ (窜最%) ι«·Η i-H Ο Ο Ο f-H f-H 〇 〇 〇 S !〇 SM 给 m g im $ __ Μ o Ο o o o ο ο ο 0.75 0.75 0.75 ο Ο o o Ο Ο 〇 〇 〇 0.75 0.75 Ο 1 1 1 1 幽 I I I MSPP MSPP MSPP I 1 1 1 I 1 1 1 1 MSPP MSPP I 鬆 4n § __ thtrtl 啊 <N CN CS <S o Ο Ο Ο ο ο ο Ο (S CN CS <S Ο 〇 〇 〇 〇 ο Ο m 祕 酹 m m GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM <jn 趦 狴 m m s __ tlmll full Ο ο ο ο Ο ο § 〇 〇 〇 Ο ο m tltnll w PA-l PA-2 PA-3 PA-3 PA-3 I 義 I I I 1 PA-4 PA-l PA-2 PA-3 PA-3 PA-3 1 1 1 I I PA-4 Nu K ϋ s ΦΜ 〇mi pit Ο ο Ο Ο Ο Ο ο — o 〇 〇 〇 Ο Ο ο κη 種類 PI-2 PI-2 PI-1 PI-2 PI-3 ΡΙ-4 ΡΙ-5 ΡΙ-6 ΡΙ-7 PI-8 PI-9 PI-10 PI-12 PI-12 PI-11 PI-12 PI-13 PI-14 PI-15 PI-16 PI-17 PI-18 PI-19 I實施例l |實施例2 I實施例3 |實施例4 |實施例5 1實施例ό 丨實施例7 丨實施例8 丨實施例9 1實施例10 1實施例li 實施伊m 丨比較例1 比較例2 丨比較例3 |比較例4 比較例5 丨比較例6 比較例7 比較例8 比較例9 比較例10 比較例11 -09- 201005006 參 ❹ 表2 液晶顯示元件 液晶 液晶配 向性 耐熱性 液晶名稱 介電常數 各向異性 實施例1 6221 正 良好 良好 實施例2 6221 正 良好 良好 實施例3 6221 正 良好 良好 實施例4 6221 正 良好 良好 實施例5 6221 正 良好 良好 實施例6 2038 負 良好 良好 實施例7 2038 負 良好 良好 實施例8 2038 負 良好 良好 實施例9 2019 正 良好 良好 實施例10 2019 正 良好 良好 實施例11 2019 正 良好 良好 實施例12 2019 正 良好 良好 比較例1 6221 正 良好 不良 比較例2 6221 正 良好 不良 比較例3 6221 正 良好 不良 比較例4 6221 正 良好 不良 比較例5 6221 正 良好 不良 比較例6 2038 負 良好 不良 比較例7 2038 負 良好 不良 比較例8 2038 負 良好 不良 比較例9 2019 正 良好 不良 比較例10 2019 正 良好 不良 比較例11 2019 正 良好 不良 另外 成中的簡 ,表1中的黏合性增強劑的“種類”欄和溶劑組 稱,分別爲以下含義。 -61 - 201005006 <黏合性增強劑> 環氧基化合物 GAPM: 1^,:^,:^’,:^’-四縮水甘油基-4,4’-二胺基二苯基 甲苯 官能性矽烷化合物 MSPP : 3-[2-(3-三甲氧基矽烷基丙基胺基)乙基胺基] 丙酸甲酯 <溶劑組成> β BL : γ-丁內酯 NMP : Ν-甲基-2-吡咯烷酮 BC : 丁基溶纖劑 另外,表2中的“液晶名稱”欄中記載的內容分別爲 以下含義。 6221 : MLC-6221(商品名,默克公司生產) 2 03 8: MLC-203 8(商品名,默克公司生產) 2019: MLC-2019(商品名,默克公司生產) θ 【目賴單綱】 4rrt 無0 【主要元件符號說明】 姐》 j\w -62-When D was reacted, 135 〇g γ-butyrolactone was added to obtain about 35 〇〇g of a solution containing 1 〇 by weight of poly-tantoic acid (PA-2). The solution viscosity of the polyamic acid solution was 1 2 5 mP a.s. Synthesis Example 14 (Synthesis 3 of Other Polylysine) 200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 22 as a diamine Dimethyl-44, diaminobiphenyl 21 〇g (1. oxime) was dissolved in a mixed solvent consisting of 370 g of NMP and 3300 g of γ·butyrolactone, and reacted at 4 (TC for 3 hours). A solution of about 3 500 g containing -47-201005006 with 10% by weight polyglycine (PA-3) was obtained. The solution viscosity of the polyaminic acid solution was 160 mPa's. Synthesis Example 15 (Other polylysines Synthesis 4) 196 g (0.9 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 19_6 g (0-1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as diamine 21.6 g (0.20 mol) of p-phenylenediamine and 80 g (0 8 mol) of 4,4'-diaminodiphenyl ether were dissolved in 24 g of NMP and reacted at 60 ° C for 4 hours. A solution containing about 10% by weight of polyglycine (PA-4) was obtained. The solution viscosity of the poly(A) acid solution was 200 mPa.s. Synthesis Example 16 (Synthesis of Other Polyimine) 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 110g (0.50 mole) And l,3,3a,4,5,9b-hexahydro-8.methyl-5-(tetrahydro-2,5-sideoxy-3-furanyl)-naphthalene [l,2-c]- Iridium-i,3-dione 160g (0.50 mole), p-phenylenediamine as a diamine 95g (0.88 moles), 2,2-bis(trifluoromethyl)-4,4-amino group Biphenyl 32g (0.10 mol) and 3,6-bis(4-aminobenzyl methoxy) choline 6.4 g (0.010 mol), and aniline as a monoamine 2.8 g (0.03 mol) Dissolved in 1 200g of NMP, and reacted at 6 (rc for 9 hours) to obtain a solution containing poly-araminic acid. Take a small amount of the obtained polyamic acid solution, add NMP, and prepare a polyglycine concentration of 1% by weight. The solution has a measured solution viscosity of 58 mPa·s. Then, 2400 g of NMP is added to the obtained polyamic acid solution, 400 g of pyridine and 41 g of acetic anhydride are further added, and a dehydration ring-closing reaction is carried out for 4 hours at 11 〇〇c. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butane vinegar into the fr solvent and then concentrated to obtain about 37 〇〇g containing 10 -48-201005006% by weight 醯 imidization rate is about 95 a solution of % polyimine (PI-n). The solution of the polyimine solution is sticky The degree is 69 mPa·s. Synthesis Example 17 (Synthesis 2 of Other Polyimine) 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol) and i, 3,3a,4,5,9b-hexahydro-8-methyl_5-(tetrahydro-2,5-one oxy-3-furanyl)-naphthalene [i,2-c]-furan-l , 3 -dione ^ (^ (0.50 mol), p-phenylenediamine as a diamine 94 g (〇_87 mol), iota, 3 -bis(3-aminopropyl)tetramethyldioxine 25g (0.10 moles) of alkane and 9.6g (〇.015 moles) of 3,6-bis(4-aminobenzylidene® methoxy)cholane, and octadecylamine 8.1g as monoamine (0.030 mol) was dissolved in 960 g of NMP and reacted at 60 ° C for 6 hours to give a solution containing poly-proline. A small amount of the obtained polyaminic acid solution 'supplemented with NMP' was added to a solution having a polyglycine concentration of 1% by weight, and the measured solution viscosity was 60 mPa·s. Then, 2700 g of NMP was added to the obtained polyaminic acid solution, and 400 g of pyridine and 41 g of acetic anhydride were further added, and a dehydration ring-closure reaction was carried out for 4 hours under ii〇-C. After the dehydration ring closure reaction, a solvent of the system is replaced with a new β-butyrolactone to obtain about 2300 g of a solution containing 15% by weight of a polyamidimide (pi-12) having a ruthenium iodide ratio of about 95%. . A small amount of the polyimine solution was added, and γ-butyrolactone was added to prepare a solution having a concentration of 10% by weight of polyimine. The solution viscosity was 70 mPa·s. Synthesis Example 18 (Synthesis 3 of Other Polyimine) 2,3,5-Tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol) and 1,3,3&,4 , 5 915_hexahydro-8-methyl_5_(tetrahydro-2,5-di-oxo-3-furanylnaphthalene [He].furan-indole, 3-diketone 16〇g (〇5〇莫- 49- 201005006 Ear) 'p-phenylenediamine as a diamine 88g (0.82 mol), U3-bis(3·aminopropyl)tetramethyldioxane 25g (0_10 mol) and 4-(4 , -Trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate 34 (0.080 mol)' and aniline as a monoamine 2.8 g (0-030 mol) dissolved in 1200 g NN1P The solution was carried out at 60 ° C for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution was added, and NMP was added to prepare a solution having a polyalginic acid concentration of 10% by weight. The viscosity is 60 mPa·s. Then, 2500 g of NMP is added to the obtained polyamic acid solution, and 40 g of pyridine and 410 g of acetic anhydride are added thereto, and the dehydration ring-closure reaction is carried out for 4 hours at ll ° C. After replacing the solvent in the system with a new butyrolactone solvent Then, it was concentrated to obtain about 3600 g of a solution containing 10% by weight of polyimine (PI-13) having a ruthenium iodide ratio of about 96%. The solution viscosity of the solution of the polyimide solution was 55 mPa·s. Synthesis of other polyimines 4) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride 110 g (0.50 mol), p-phenylenediamine as diamine 43 g (0.40 Mo The ear) and β 3_(3,5·diaminobenzylideneoxy)cholane 52g (0.10 mol) were dissolved in 83 0 g of NMP, and reacted at 60 ° C for 6 hours to obtain polydecylamine. A solution of acid. Take a small amount of the obtained polyaminic acid solution, add NMP, and prepare a solution with a polyglycine concentration of 10% by weight, and measure the viscosity of the solution to 60 mPa*s. Then, to the obtained poly-proline solution 1900g of NMP was added, 4 〇g of pyridinium and 5ig acetic anhydride were added, and the dehydration ring-closure reaction was carried out for 4 hours under litre. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP to obtain about 1100 g of 15 The weight % 醯 imidization rate is about -50 - 201005006 is a 50% solution of polyimine (PI - 14). Take a small amount of the polyimine solution, add NMP, formulated as a solution having a polyamidene concentration of 10% by weight, has a solution viscosity of 47 mPai. » Synthesis Example 20 (Synthesis of Other Polyimine 5) 2, 3, 5 as Tetracarboxylic Acid dianhydride - Tricarboxycyclopentyl acetic acid dianhydride 110 g (0.50 mol), p-phenylenediamine as a diamine 49 g (0.45 mol) and 3-(3,5-diaminobenzylideneoxy)cholestane 26 g (〇.〇5 mol) was dissolved in 750 g of NMP to carry out a reaction at 60 ° C for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to prepare a solution having a polyglycine concentration of 1% by weight, and the viscosity of the solution was determined to be 58 mPa-s. Then, 1800 g of NMP was added to the obtained polyamic acid solution, and 40 g of pyridine and 51 g of acetic anhydride were further added, and a dehydration ring-closing reaction was carried out for 4 hours at U °C. After the dehydration ring closure reaction, a solution of about 1 000 g of a polyimine (PI-15) having a ruthenium iodide ratio of about 15% was obtained by solvent-replacement of the solvent in the system with new NMP. A small amount of the solution of the glycine imine was added, and NMP was added to prepare a solution having a polyamidene concentration of 1% by weight, and the viscosity of the solution was determined to be 85 mPai. Synthesis Example 21 (Synthesis 6 of other polyimine) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 11 (^ (0.50 mol)) as a tetracarboxylic dianhydride, as a diamine of benzene Diamine 388 (〇35 mol), 4,4,-diaminodiphenylmethane 20 g (0.1 mol) and 3-(3,5-diaminobenzylideneoxy) gallone 26 g (0.05 Mol) was dissolved in 800 g of NMP, and the reaction was carried out at 60 ° for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyamic acid solution was added to NMP to form a polyglycolic acid. 1 〇% by weight of solution -51 - 201005006, the measured solution viscosity is 60 mPa_s. Then, 1 800 g of NMP is added to the obtained polyaminic acid solution, and then 80 g of pyridine and 100 g of acetic anhydride are added, and the reaction is carried out at 110 ° C. After the dehydration ring closure reaction, the solvent in the system is replaced with a new NMP solvent to obtain about 105 Og of polyfluorene (15%) containing 15% by weight of ruthenium iodide. 6) Solution: A small amount of the polyimine solution was added, NMP was added, and a solution having a concentration of 10% by weight of polyimine was prepared, and the viscosity of the solution was determined to be 87 mPa*s. 2 (Synthesis of other polyimines 7) 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 54 g of p-phenylenediamine as a diamine ( 0.50 mol) dissolved in 1 800 g of NMP, and reacted at 60 ° C for 6 hours to obtain a solution containing poly-proline. A small amount of the obtained polyaminic acid solution was added, and NMP was added to prepare a polyglycine concentration. 10% by weight of the solution, the measured solution viscosity is 75 mPa·s 6 Then, 1 800 g of NMP is added to the obtained polyaminic acid solution, and then 80 g of pyridine and 100 g of acetic anhydride are added, and the mixture is subjected to 1 1 (TC for 4 hours). Dehydration ring closure reaction. After the dehydration ring closure reaction, the solvent in the system is replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 140 g of polyfluorene containing 15% by weight of ruthenium iodide ratio of about 91%. A solution of imine (PI-17). Take a small amount of the polyimine solution, add γ-butyrolactone, and prepare a solution with a polyamidene concentration of 10% by weight. The measured solution viscosity is 150 mP a·s. Synthesis Example 23 (Synthesis of Other Polyimine 8) 2,3,5-Tricarboxycyclopentyl Acetate dianhydride as a tetracarboxylic dianhydride - 52 - 20 1005006 165g (0.75 mole) and 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3·furanyl)-naphthalene 1,2_c]_furan-1,3-dione 78g (0·25 mol) 'p-phenylenediamine as diamine 43g (0.40 mol), 4,4'-diaminodiphenyl ether 80g (〇.4mol) and bis{4-(4-aminophenoxy)phenyl}milled 85g (0.20 mole) dissolved in 2600g of NMP and reacted at 60 ° C for 6 hours to give polycondensation A solution of proline. A small amount of the obtained polyaminic acid solution was taken, and NMP' was added to prepare a solution having a polyglycine concentration of 丨〇% by weight, and the measured solution viscosity was 1 〇〇 mPa.s. Then, 1 800 g of NMP was added to the obtained polyamic acid solution, and 80 g of pyridine and i〇〇g acetic anhydride were further added thereto, and a dehydration ring-closing reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 2700 g of a polyimine (PI-containing 15% by weight of a ruthenium iodide ratio of about 81%). 18) solution. A small amount of the polyimine solution was added, and γ-butyrolactone was added to prepare a solution having a polyamidene concentration of 10% by weight, and the solution viscosity was determined to be 95 mP a·s. Synthesis Example 24 (Synthesis of Other Polyimine 9) 110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as a tetracarboxylic dianhydride, p-phenylenediamine as a diamine 43g (〇4〇莫耳), 2,2,_bis(difluoromethyl)benzene 16g (0.050 mol) and 4,4,-diaminodiphenylmethane 11g (0.050 mol) dissolved in 2600g NMP The reaction was carried out at 60 ° C for 6 hours to obtain a polyglycine-containing solution. A small amount of the obtained polyaminic acid solution was taken, and NMP was added to prepare a solution having a polyglycine concentration of 1% by weight, and the viscosity of the solution was determined to be 480 mPa*s. Then, 18 〇〇g of NMP was added to the obtained polyacrylic acid solution, and then -53-201005006 8 〇g of pyridine and 100 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out for 4 hours at 11 °C. After the dehydration ring closure reaction, the solvent in the system was replaced with a new γ-butyrolactone solvent, and then concentrated to obtain about 2500 g of a polyamidene containing 15% by weight of a ruthenium iodide ratio of about 88% (PI - 19) solution. A small amount of the polyimine solution was added, and γ-butyrolactone was added to prepare a solution having a polyamidene concentration of 10% by weight, and the solution viscosity was determined to be 90 mPa_s. Example 1 <Preparation of Liquid Crystal Aligning Agent> φ The polyimine-containing amine (PI-2) obtained in the above Synthesis Example 3 in an amount equivalent to 20 parts by weight in terms of polyimine (PI-2) The solution is mixed with a polytyramine (PA-1)-containing solution prepared in the above Synthesis Example 12 in an amount equivalent to 80 parts by weight in terms of polyglycine (PA-1), to γ-butyl Lactone: Ν-methyl-2-pyrrolidone: butyl cellosolve ratio of 71: 17: 12 by weight, to which γ-butyrolactone, Ν-methyl-2-pyrrolidone and butyl cellosolve were added, and Adding 2 parts by weight of an epoxy compound Ν, Ν, Ν', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane as an adhesion enhancer to a solid content of 3.5% by weight solution. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of Ιμηη to prepare a liquid crystal alignment agent. The liquid crystal alignment agent was used for evaluation as follows. <Manufacturing and Evaluation of Liquid Crystal Display Element> [Production of Liquid Crystal Display Element] (1) Application of Liquid Crystal Aligning Agent and Formation of Liquid Crystal Alignment Film Using a spin coater at a rotation speed of 2000 rpm and a rotation time of 20 seconds Next, the above-prepared liquid crystal alignment agent is applied onto a transparent conductive film of ITQ film provided on one surface of a glass substrate having a thickness of 1 mm -54 to 201005006, and prebaked on a hot plate at 8 ° C for 1 minute, and then After baking at 20 ° C for 1 hour, a coating film having a film thickness of 0.08 μη was formed. (2) Grinding treatment The above coating film was carried out under the conditions of a roller rotation speed of 400 rpm, a table moving speed of 3 cm/sec, and a pile extrusion length of 0.4 mm, using a grinding machine equipped with a roller wound with a rayon cloth. The polishing treatment is performed to produce a liquid crystal alignment energy on the coating film to form a liquid crystal alignment film. © (3) Washing and drying of the substrate coated with the liquid crystal alignment film The substrate having the liquid crystal alignment film prepared above was ultrasonically washed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes. . The same operation was repeated to produce two (a pair of) substrates having a liquid crystal alignment film. (4) Liquid crystal injection step, bonding and bonding of the polarizer, and then a ring of alumina balls having a diameter of 5.5 μm is applied to each of the outer edges of the pair of liquid crystal alignment films having the liquid crystal alignment film. After the oxy-resin adhesive, the liquid crystal alignment film surface is relatively heavily combined and pressed, and β is used to cure the adhesive. Next, a liquid crystal injection port is used to fill a liquid crystal injection port with a dielectric-curable anisotropic liquid crystal (manufactured by Merck, MLC-622 1). The film was sealed, and a polarizing plate was bonded to both surfaces of the substrate to produce a liquid crystal display element. [Evaluation of Liquid Crystal Display Element] (1) Evaluation of liquid crystal alignment property The liquid crystal display element manufactured above was observed with an optical microscope. In this case, when there is no light leakage, the liquid crystal alignment property is evaluated as "good". When it was confirmed that there was light leakage, the liquid crystal alignment property was evaluated as "poor". The liquid crystal alignment property of the liquid crystal display element was "good". (2) Evaluation of heat resistance (heat stress test) For the liquid crystal display element manufactured above, first, a voltage of 5 V was applied for a time span of 167 msec, the application time was 60 μsec, and then the voltage was released until after 167 msec. Voltage retention rate. The number at this time is taken as the initial voltage holding ratio (VHRBF). After the VHRBF was measured, the liquid crystal display element was placed in an oven at 100 ° C, and a thermal stress of 1 000 hours was applied. Then, the liquid crystal display element was allowed to stand at room temperature and cooled to room temperature, and then the voltage holding ratio vhraf after the application of the thermal stress was measured. The rate of change of the voltage holding ratio before and after the application of the thermal stress was determined. When the rate of change was less than 5%, the heat resistance was evaluated as "good", and the heat resistance was evaluated as "poor". The heat resistance of the liquid crystal display element was "good". (Examples 2 to 5) In the same manner as in Example 1, except that the polymer of the type ® shown in Table 1 shown in Table 1 was used, the liquid crystal alignment agent was prepared, and a liquid crystal display element was produced. Evaluation. The results are shown in Table 2. Example 6 <Preparation of Liquid Crystal Aligning Agent> The polyimidazole (PI - 4 ) prepared in the above Synthesis Example 5 in an amount equivalent to 100 parts by weight in terms of polyimine (PI-4) was used. a solution in which N-methyl-2-pyrrolidone and butyl cellosolve are added in a weight ratio of N-methyl-2-pyrrolidone:butyl cellosolve of 50:50, and 2 parts by weight are added thereto - 56- 201005006 The epoxy compound n, n, n', n'-tetraglycidyl-4,4'-diaminodiphenylmethane, which is a binder enhancer, is formulated to have a solid content concentration of 3.5% by weight. The solution. After the solution was thoroughly stirred, it was filtered through a filter having a pore size to prepare a liquid crystal alignment agent. <Production and Evaluation of Liquid Crystal Display Element> As a liquid crystal, a nematic liquid crystal (manufactured by Merck & Co. 'MLC-2038)' which exhibits a negative dielectric anisotropy is used and a manufacturing step of a liquid crystal display element In the same manner as in the first example, the liquid crystal display element was produced and evaluated for liquid crystal alignment and heat resistance. The results are shown in Table 2, except that the polishing treatment was carried out in the same manner as in Example 1. Examples 7 and 8 In the same manner as in Example 6, except that the polymer of the type shown in Table 1 shown in Table 1 was used, the liquid crystal alignment agent was separately prepared, and a liquid crystal display element was produced and evaluated. . The results are shown in Table 2. Example 9 <Preparation of Liquid Crystal Aligning Agent> ® Polyimine-containing amine (PI-7) obtained in Synthesis Example 8 in an amount equivalent to 100 parts by weight in terms of polyimine (PI-7) a solution to which 1 part by weight of an epoxy compound Ν, Ν, Ν', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane and 0.75 by weight as a binder enhancer are added. a functional decane compound 3-[2-(3-trimethoxydecylpropylamino)ethylamino]propyl propionate, then a ratio of γ-butyrolactone:butyl cellosolve of 80:20 The weight ratio was added to γ-butyrolactone and butyl cellosolve to prepare a solution having a solid content concentration of 3.5% by weight. The solution was filtered through a filter having a pore size of Ιμπι to prepare a liquid crystal alignment agent of -57 to 201005006. <Production and Evaluation of Liquid Crystal Display Device> The liquid crystal display device is a nematic liquid crystal (manufactured by Merck & Co., MLC-2019) having a positive dielectric anisotropy, and is the same as in the first embodiment. The liquid crystal display element was produced and evaluated for liquid crystal alignment and heat resistance. The results are shown in Table 2. Example 1 0 and 1 1 In the same manner as in Example 9, except that the polymer of the type 〇 shown in Table 1 shown in Table 1 was used, respectively, a liquid crystal alignment agent was prepared to produce a liquid crystal display element. And evaluate. The results are shown in Table 2. Example 1 2 <Preparation of Liquid Crystal Aligning Agent> The polyimine-containing amine (PI - 10 ) prepared in the above Synthesis Example 11 in an amount equivalent to 40 parts by weight in terms of polyimine (P1-10) The solution is mixed with a polyglycine (PA-4)-containing solution prepared in the above Synthesis Example 15 in an amount equivalent to 60 parts by weight in terms of poly-proline (PA-4). Lactone: Ν-methyl-2-pyrrolidone: butyl cellosolve ratio of 40:40:20 by weight, to which γ-butyrolactone, Ν·methyl-2-pyrrolidone and butyl cellosolve are added. An additional 1 part by weight of an epoxy compound Ν, Ν, Ν, Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane as a binder enhancer is added to a solid content concentration of 3.5% by weight solution. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of Ιμηη to prepare a liquid crystal alignment agent. The liquid crystal alignment agent was used for evaluation as follows. <Production and Evaluation of Liquid Crystal Display Element> -58-201005006 As a liquid crystal, a nematic liquid crystal (manufactured by Merck, MLC-2019) which exhibits positive dielectric anisotropy is used as a liquid crystal, and In the same manner as in Example 1, a liquid crystal display device was produced, and liquid crystal alignment properties and heat resistance were evaluated. The results are shown in Table 2. Comparative Examples 1 to 5 A liquid crystal display element was prepared and evaluated in the same manner as in Example i except that the polymer of the type shown in Table 1 shown in Table 1 was used. The results are shown in Table 2. Φ Comparative Examples 6 to 8 In the same manner as in Example 6, except that the polymer of the type shown in Table 1 shown in Table 1 was used, a liquid crystal alignment agent was prepared, and a liquid crystal display element was produced. Evaluation. The results are shown in Table 2. Comparative Examples 9 and 10 In the same manner as in Example 9, except that the polymer of the type shown in Table 1 shown in Table 1 was used, respectively, a liquid crystal alignment agent was prepared, and a liquid crystal display element was produced and carried out. Evaluation. The results are shown in Table 2. ® Comparative Example 1 1 A liquid crystal display element was produced by preparing a liquid crystal alignment agent in the same manner as in Example 12 except that the polymer of the type shown in Table 1 shown in Table 1 was used. Evaluation. The results are shown in Table 2. -59- 201005006 ❹ο £ 隐mg 隐(军最%) CS rj cs CN ΓΊ Μ 2 i (窜晕%) r-· 卜r- Ο Ο 〇ο r- r- ι> !- 〇Ο 〇j PQ (窜%%) ι«·Η iH Ο Ο Ο fH fH 〇〇〇S !〇SM to mg im $ __ Μ o Ο ooo ο ο ο 0.75 0.75 0.75 ο Ο oo Ο Ο 〇〇〇 0.75 0.75 Ο 1 1 1 1 幽 III MSPP MSPP MSPP I 1 1 1 I 1 1 1 1 MSPP MSPP I 松 4n § __ thtrtl 啊<N CN CS <S o Ο Ο Ο ο ο ο Ο (S CN CS <S Ο 〇 〇〇〇ο Ο m tips mm GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM GAPM <jn 趦狴mms __ tlmll full Ο ο ο ο Ο ο § 〇〇 ο ο m tltnll w PA-l PA-2 PA-3 PA-3 PA-3 I Yi III 1 PA-4 PA-l PA-2 PA-3 PA-3 PA-3 1 1 1 II PA-4 Nu K ϋ s ΦΜ 〇mi pit Ο ο Ο Ο Ο ο ο — o 〇〇〇Ο Ο ο κη Type PI-2 PI-2 PI-1 PI-2 PI-3 ΡΙ-4 ΡΙ-5 ΡΙ-6 ΡΙ -7 PI-8 PI-9 PI-10 PI-12 PI-12 PI-11 PI-12 PI-13 PI-14 PI-15 PI-16 PI-17 PI-18 PI-19 I Example 1 | Example 2 I Example 3 | Example 4 | Example 5 1 Example丨 丨 Example 7 丨 Example 8 丨 Example 9 1 Example 10 1 Example li Example I m 丨 Comparative Example 1 Comparative Example 2 丨 Comparative Example 3 | Comparative Example 4 Comparative Example 5 丨 Comparative Example 6 Comparative Example 7 Comparison Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 -09- 201005006 Reference Table 2 Liquid Crystal Display Element Liquid Crystal Liquid Crystal Alignment Heat Resistance Liquid Crystal Name Dielectric Anisotropy Example 1 6221 Positive Good Example 2 6221 Good and good Example 3 6221 just good good example 4 6221 positive good good example 5 6221 positive good good example 6 2038 negative good good example 7 2038 negative good good example 8 2038 negative good good example 9 2019 positive good implementation Example 10 2019 Positive good Example 11 2019 Positive good Example 12 2019 Positive good Good Comparative Example 1 6221 Positive good bad Comparative Example 2 6221 Positive good bad Comparative Example 3 6221 Positive good bad ratio Example 4 6221 Positive Good Defects Comparative Example 5 6221 Positive Good Defects Comparative Example 6 2038 Negative Good Defects Comparative Example 7 2038 Negative Good Defects Comparative Example 8 2038 Negative Good Defects Comparative Example 9 2019 Positive Good Defects Comparative Example 10 2019 Positive Good Defects Comparative Example 11 2019 It is good and bad. In addition, the "type" column and the solvent group of the adhesion enhancer in Table 1 are respectively referred to as the following meanings. -61 - 201005006 <Adhesion enhancer> Epoxy compound GAPM: 1^,:^,:^',:^'-tetraglycidyl-4,4'-diaminodiphenyltoluene function The decane compound MSPP: 3-[2-(3-trimethoxydecylpropylamino)ethylamino]methyl propionate <solvent composition> β BL : γ-butyrolactone NMP : Ν- Methyl-2-pyrrolidone BC : butyl cellosolve In addition, the contents described in the column of "liquid crystal name" in Table 2 have the following meanings. 6221 : MLC-6221 (trade name, manufactured by Merck) 2 03 8: MLC-203 8 (trade name, produced by Merck) 2019: MLC-2019 (trade name, produced by Merck) θ [Target] 4rrt No 0 [Main component symbol description] Sister" j\w -62-

Claims (1)

201005006 七、申請專利範圍: 1. 一種液晶配向劑,其特徵在於含有選自聚醯胺酸和聚醯 亞胺構成的群組中的至少一種聚合物,其中上述聚合物 的分子中的至少一部分具有下述式(A)201005006 VII. Patent application scope: 1. A liquid crystal alignment agent characterized by containing at least one polymer selected from the group consisting of polyamic acid and polyimine, wherein at least a part of the molecules of the above polymer Has the following formula (A) 表示的結構。 2.如申請專利範圍第1項之液晶配向劑,其中上述式(A)表 示的結構爲選自下述式(A— 1)〜(A— 3)各自表示的結構 構成的群組中的至少一種結構, (R")nThe structure represented. 2. The liquid crystal alignment agent of claim 1, wherein the structure represented by the above formula (A) is selected from the group consisting of structures represented by the following formulas (A-1) to (A-3). At least one structure, (R")n 式(A—1)中的Ra爲鹵素原子、氰基、異氰基、-OCN、 -NCO、-SCN、-NCS或疊氮基,η爲0〜3的整數, 各自表示爲連接鍵; 式(Α-2)和(Α— 3)中的1^和Re各自獨立地爲氫原 -63- 201005006 子、鹵素原子、氨基、異氰基、-〇CN、-NC0、_SCN、-NCS 或叠氮基,各自表示爲連接鍵。 3. 如申請專利範圍第1或2項之液晶配向劑’其中上述聚合 * 物爲選自下述構成的群組中的至少一種聚合物’該群組由 使四羧酸二酐與含有具有上述式(A)表示的結構和2個胺 基的化合物的二胺反應而製得的聚醯胺酸以及將該聚醯 胺酸脫水閉環而得到的聚醯亞胺構成。 4. 如申請專利範圍第3項之液晶配向劑,其中具有上述式(A) ❹ 表示的結構和2個胺基的化合物爲選自下述式(A-1- 1)、(A-2— 1)和(A—3 — 1)各自表示的化合物構成的群輯 中的至少一種,Ra in the formula (A-1) is a halogen atom, a cyano group, an isocyano group, -OCN, -NCO, -SCN, -NCS or an azide group, and η is an integer of 0 to 3, each represented by a linkage; 1^ and Re in the formulas (Α-2) and (Α-3) are each independently hydrogen-63-201005006, halogen atom, amino group, isocyano group, -〇CN, -NC0, _SCN, -NCS Or an azide group, each represented as a linkage. 3. The liquid crystal alignment agent of claim 1 or 2 wherein the above polymerization product is at least one polymer selected from the group consisting of: the group consists of tetracarboxylic dianhydride and The polyamine acid obtained by reacting the diamine of the compound of the above formula (A) with the diamine of the compound of the two amine groups, and the polyimine obtained by dehydrating and ring-closing the polyamine. 4. The liquid crystal alignment agent of claim 3, wherein the compound having the structure represented by the above formula (A) 和 and the two amine groups is selected from the following formula (A-1- 1), (A-2) - 1) and at least one of the group consisting of the compounds represented by (A - 3 - 1), 式(A— 1 一 1)中的《^和η分別與上述式(A — 1)中的定 義相同,Ya爲單鍵或碳原子數爲6〜1〇的伸芳基; -64 - 201005006 式(A — 2 — 1)和(A — 3 — 1)中的Rb和Rc分別與上述式 (A — 2)或(A— 3)中的定義相同,Yb和γ。各自獨立地爲單 鍵或碳原子數爲6〜1〇的伸芳基。 5.如申請專利範圍第3或4項之液晶配向劑,其中上述二胺 進一步含有下述式(D - in)表示的化合物, h2nIn the formula (A-1 to 1), "^ and η are respectively the same as defined in the above formula (A-1), and Ya is a single bond or an extended aryl group having 6 to 1 carbon atoms; -64 - 201005006 Rb and Rc in the formulae (A - 2 - 1) and (A - 3 - 1) are the same as defined in the above formula (A-2) or (A-3), respectively, Yb and γ. Each is independently a single bond or an extended aryl group having 6 to 1 carbon atoms. 5. The liquid crystal alignment agent according to claim 3, wherein the diamine further contains a compound represented by the following formula (D - in), h2n (D-III) ❹ 式(D—III)中 ’R9 爲- 0-、-COO-*'-OCO-*、-NHCO-*、 -CONH·*或-CO-,其中,在以上當中,帶有“ 的連接 鍵與RlG連接,R1(>爲具有選自甾體骨架、三氟甲基苯基、 三氣甲氧基苯基和氟代苯基中的骨架或基團的1價有機 基團’或者碳原子數爲6〜3〇的烷基,Rii爲碳原子數爲 1〜4的垸基,a3爲〇〜3的整數。 6. 如申請專利範圍第5項之液晶配向劑,其中上述式(D-III)中的R9爲-〇·或- COO-*,其中帶有“*,,的連接鍵與 ® R10連接,R1g爲具有甾體骨架的1價有機基團》 7. 如申請專利範圍第3至6項中任一項之液晶配向劑,其 中二胺進一步含有選自對苯二胺、4,4,_二胺基二苯基甲 院、4,4’·二胺基二苯基醚和二[4_(4_胺基苯氧基)苯基]碾 構成的群組中的至少一種。 8. 如申請專利範圍第3至7項中任一項之的液晶配向劑, 其中四竣酸二肝含有選自12,34_環丁烷四羧酸二酐、 2,3,5-二羧基環戊基醋酸二酐、13,3&,45,9卜六氫_8_甲基 -5-(四氫-2,5-二側氧-3-呋喃基)_萘[nc]-呋喃_i,3-二酮 -65- 201005006 、 和均苯四酸二酐構成的群組中的至少一種。 9. 一種液晶顯示元件,其特徵在於具有由如申請專利範圍 第1至8項中任一項之液晶配向劑形成的液晶配向膜。(D-III) ' In the formula (D-III), 'R9 is -0-, -COO-*'-OCO-*, -NHCO-*, -CONH·* or -CO-, of which, in the above, A linkage having "a linkage to RlG, R1 (> is a monovalent having a skeleton or group selected from the group consisting of a steroid skeleton, a trifluoromethylphenyl group, a trimethylmethoxyphenyl group, and a fluorophenyl group) The organic group 'or an alkyl group having 6 to 3 carbon atoms, Rii is a fluorenyl group having 1 to 4 carbon atoms, and a3 is an integer of 〇 to 3. 6. Liquid crystal alignment according to item 5 of the patent application And R9 in the above formula (D-III) is -〇· or -COO-*, wherein a linkage bond with "*," is linked to ® R10, and R1g is a monovalent organic group having a steroid skeleton 7. The liquid crystal alignment agent according to any one of claims 3 to 6, wherein the diamine further contains a selected from the group consisting of p-phenylenediamine, 4,4,-diaminodiphenyl-based, 4, 4 At least one of the group consisting of 'diaminodiphenyl ether and bis[4-(4-aminophenoxy)phenyl] mill. 8. As claimed in any of claims 3 to 7. Liquid crystal alignment agent, wherein the tetracethopic acid dihepatic contains a tetracarboxylic acid selected from the group consisting of 12,34-cyclobutane tetracarboxylate Dihydride, 2,3,5-dicarboxycyclopentyl acetic acid dianhydride, 13,3&,45,9 hexahydro-8-methyl-5-(tetrahydro-2,5-di-oxo-3 -furanyl)-naphthalene [nc]-furan-i,3-dione-65-201005006, and at least one of the group consisting of pyromellitic dianhydride. 9. A liquid crystal display element characterized by having A liquid crystal alignment film formed of a liquid crystal alignment agent according to any one of claims 1 to 8. -66- 201005006 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0 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式:-66- 201005006 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 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
TW098120197A 2008-06-17 2009-06-17 Liquid crystal alignment agent and liquid crystal display element TWI460210B (en)

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