TW201113328A

TW201113328A - Liquid crystal aligning agent

Info

Publication number: TW201113328A
Application number: TW99131365A
Authority: TW
Inventors: Shouichi Nakata; Eiji Hayashi; Michinori Nishikawa
Original assignee: Jsr Corp
Priority date: 2009-09-16
Filing date: 2010-09-16
Publication date: 2011-04-16
Also published as: KR101628787B1; CN102020994B; JP2011084724A; JP5699469B2; CN102020994A; TWI602878B; KR20110030310A

Abstract

The present invention provides a liquid crystal aligning agent, and said liquid crystal aligning agent can give liquid crystal aligning film good property of pre-tilt angle, and not causing poor display property even if the liquid crystal panel driven for a long time. The above-mentioned liquid crystal aligning agent comprises at least one polymer selected from the group consisting of polyamic acid obtained from reacting tetracarboxylic acid dianhydride and diamine, and polyimide formed from dehydrating said polyamic acid and allowing it closing-ring; wherein tetracarboxylic acid dianhydride comprises at least one selected from the group consisting of 3, 5, 6-tricarboxy-2-carboxymethylnorbornan-2: 3, 5: 6-dianhydride and 2, 4, 6, 8-tetracarboxy-bicyclo[3.3.0]octan-2: 4, 6: 8-dianhydride, and diamine comprises the diamine having photo-reactive structure.

Description

201113328 六、發明說明：【發明所屬之技術領域】本發明係關於液晶配向劑。更詳細而言，係關於即使通過光照射少的光配向法，也可以提供適合性能的液晶配向膜的液晶配向劑。【先前技術】目前，作爲液晶顯示元件的運行模式，已知的有使用具有正的介電各向異性的液晶分子的Τ N (扭曲向列）型、 STN(超扭曲向列）型等以及使用具有負的介電各向異性的液晶分子的VA(垂直配向）型等液晶顯示元件，爲了將各種液晶分子進行配向控制，主要使用由有機膜形成的液晶配向膜（專利文獻1〜4)。上述TN型、STN型中的液晶配向膜爲了使液晶分子高速回應’上述VA型等中的液晶配向膜爲了使液晶運行時的傾斜方向固定，必須分別具有預傾角性質。作爲提供該預傾角性質的方法’對前者來說一般是摩擦法，對後者來說一般是摩擦法、在基板表面設置突起物的方法等。其中，摩擦法有可能會由於工程中產生的灰塵或靜電產生顯示不佳或電路破壞的問題；另一方面，在基板表面設置突起物的方法可能會損害所得的液晶顯示元件的亮度，所以都具有問題。因此，作爲對它們賦予變化的預傾角的方法，提出了所謂的光配向法，該方法是從相對膜法線傾斜的方向，對 201113328 感光性薄膜照射紫外線的方法（專利文獻5和非專利文獻 1)。近年來，液晶顯示元件特別是在電視用途快速發展，與目前的液晶顯示元件相比，可以實現特別長時間的視聽。然而，已知的是目前已知的液晶顯示元件如果長時間連續運行，則顯示品質變差。其原因之一可以認爲是由於長時間運行，液晶配向膜長時間曝露在光中，可能變差。因此，在液晶配向膜的領域中，正在硏究即使長時間連續運行時，顯示性能也不會變差的材料。例如，專利文獻6中提出了使用具有交聯結構的配向膜材料。然而，即使是同一文獻的技術，在長時間連續運行時，顯示品質變差的抑制程度也不足。 [先前技術文獻] [專利文獻] [專利文獻1] 日本特開昭56-9 1 277號公報 [專利文獻2] 日本特開平1 - 1 205 2 8號公報 [專利文獻3] 日本特開平11-258605號公報 [專利文獻4] 日本特開2002-250924號公報 [專利文獻5]日本特開2004-83810號公報 [專利文獻6]日本特開2008-216985號公報 [專利文獻7]曰本特開2010-97188號公報 [非專利文獻] [非專利文獻 1] J· of the SID 1 1 /3, 2003, p579 201113328 [非專利文獻 2] T. J. Scheffer et. al., J. Appl. Phys. vol. 48, pl783 (1977) [非專利文獻 3] F. Nakano et. al., JPN. J. Appl. Phys. vol. 19, p2013 (1980) 【發明內容】發明欲解決之課題本發明的目的在於提供一種液晶配向劑，該液晶配向劑可以通過光配向法得到良好的預傾角性質，而且可以提供在長時間連續運行時，不會導致顯示性質變差的液晶配向膜。用以解決課題之手段根據本發明，本發明之上述目的和優點通過一種液晶配向劑實現，其特徵在於：包含由四羧酸二酐和二胺反應得到的聚醯胺酸以及該聚醯胺酸脫水閉環形成的聚醯亞胺構成的群組中選出的至少一種聚合物，其中四羧酸二酐包含由3,5,6-三羧基-2-羧甲基降冰片烷-2:3,5:6-二酐和 2,4,6,8-四羧基二環[3.3.0]辛烷- 2:4,6:8-二酐構成的群組中選出的至少一種，二胺包含具有光反應性結構的二胺。發明效果本發明的液晶配向劑與作爲能夠適用光配向法的液晶配向劑之現有公知的液晶配向劑相比，可以形成即使長時間連續運行時，顯示性質也不會變差的液晶配向膜。 -6- 201113328 因此’在將本發明的液晶配向膜用於液晶顯示元件時’所得的液晶顯示元件的顯示性質、可靠性等各種性質優異。因此’該液晶顯示元件可以有效地適用於各種裝置，例如桌上用計算機、手錶、座鐘、計數顯示板 '文字處理器、個人電腦、液晶電視等裝置。【實施方式】用以實施發明之形態本發明的液晶配向劑，如上所述，包含由四羧酸二酐和二胺反應得到的聚醯胺酸以及該聚醯胺酸脫水閉環形成的聚醯亞胺構成的群組中選出的至少一種聚合物（以下，有時也稱作“特定聚合物”），其中四羧酸二酐包含由3,5,6-三羧基-2-羧甲基降冰片烷- 2:3,5:6-二酐和2,4,6,8 -四羧基二環[3.3.0]辛烷- 2:4,6:8-二酐構成的群組中選出的至少一種，二胺包含具有光反應性結構的二胺。 <四羧酸二酐> 作爲用於合成本發明中的聚醯胺酸的四羧酸二酐，是包含由3,5,6-三羧基-2-羧甲基降冰片烷-2:3,5:6-二酐和 2,4,6,8-四羧基二環[3.3.0]辛烷- 2:4,6:8-二酐構成的群組中選出的至少一種的四羧酸二酐。作爲用於合成前述聚醯胺酸的四羧酸二酐，相對於全部四羧酸二酐，較佳含有80莫耳％以上、更佳含有90莫耳 %以上的由3，5,6-三羧基-2-羧甲基降冰片烷- 2:3,5:6-二酐和 2,4,6,8 -四羧基二環[3.3.0]辛烷- 2:4,6:8 -二酐構成的群組中選出的至少一種。 .201113328 作爲用於合成前述聚醯胺酸的四羧酸二酐，可以將上述兩種以外的四羧酸二酐一起使用，可以列舉出例如上述兩種以外的脂肪族四羧酸二酐、脂環式四羧酸二酐、芳香族四羧酸二酐等。作爲它們的具體的例子，其中作爲脂肪族四羧酸二酐，可以列舉出例如丁烷四羧酸二酐等；作爲脂環式四羧酸二酐，可以列舉出例如1，2，3，4 -環丁烷四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、 1，3,33,4,5,91?-六氫-5-(四氫-2,5-二氧代-3-呋喃基）-萘并 [l，2-c]呋喃-〗，3·二酮、1，3,3&，4,5,91)-六氫-8-甲基-5-(四氫 -2,5 -二氧代· 3 ·呋喃基）-萘并[1，2 - c ]呋喃-1，3 -二酮、3 -氧雜二環[3.2.1]辛-2,4 -二酮-6-螺-3’ -(四氫呋喃-2，，5’-二酮）、 5-(2,5-二氧代四氫-3-呋喃基）-3 -甲基-3-環己烯-1,2-二甲酸酐、4,9-二氧雜三環[5.3.1.02·6]十一烷-3,5,8，10-四酮等；作爲芳香族四羧酸二酐，可以列舉出例如均苯四羧酸二酐等；以及使用專利文獻7(日本特開20 1 0-97 1 8 8號公報）中記載的四羧酸二酐。 <二胺〉用於合成本發明中的聚醯胺酸的二胺是包含具有光反應性結構的二胺的二胺。作爲上述光反應性結構，較佳具有能夠進行選自通過光照射異構化和二聚化的至少一種反應的功能的結構，可以列舉出例如下式（Α-2)所示的結構。 -8 - 201113328201113328 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a liquid crystal alignment agent. More specifically, it is a liquid crystal alignment agent which can provide a liquid crystal alignment film suitable for performance even when the light alignment method is small by light irradiation. [Prior Art] At present, as an operation mode of a liquid crystal display element, a Τ N (twisted nematic) type, an STN (super twisted nematic) type, etc. using liquid crystal molecules having positive dielectric anisotropy, and the like are known. A liquid crystal display element such as a VA (vertical alignment) type using a liquid crystal molecule having a negative dielectric anisotropy, and a liquid crystal alignment film formed of an organic film is mainly used for the alignment control of various liquid crystal molecules (Patent Documents 1 to 4) . The liquid crystal alignment film in the TN type and the STN type has a pretilt property in order to fix the liquid crystal molecules at a high speed. The liquid crystal alignment film in the VA type or the like is required to have a pretilt angle in order to fix the tilt direction during liquid crystal operation. As a method of providing the pretilt property, the former is generally a rubbing method, and the latter is generally a rubbing method, a method of providing a projection on a surface of a substrate, and the like. Among them, the rubbing method may cause poor display or circuit damage due to dust or static electricity generated in the project; on the other hand, the method of providing protrusions on the surface of the substrate may damage the brightness of the obtained liquid crystal display element, so both Have problems. Therefore, as a method of imparting a change in the pretilt angle to them, a so-called photo-alignment method is proposed, which is a method of irradiating ultraviolet rays to a 201113328 photosensitive film from a direction inclined with respect to a film normal (Patent Document 5 and Non-Patent Literature) 1). In recent years, liquid crystal display elements have been rapidly developed, particularly in television applications, and can be viewed for a particularly long time as compared with current liquid crystal display elements. However, it is known that currently known liquid crystal display elements deteriorate in display quality if they are continuously operated for a long period of time. One of the reasons for this is considered to be that the liquid crystal alignment film is exposed to light for a long period of time due to long-term operation, and may be deteriorated. Therefore, in the field of liquid crystal alignment films, materials which do not deteriorate in display performance even when continuously operated for a long period of time are being studied. For example, Patent Document 6 proposes to use an alignment film material having a crosslinked structure. However, even in the technique of the same document, when the continuous operation is continued for a long period of time, the degree of suppression of display quality deterioration is insufficient. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. JP-A-2002-83810 (Patent Document No.) JP-A-2010-97188 [Non-Patent Document] [Non-Patent Document 1] J. of the SID 1 1 / 3, 2003, p579 201113328 [Non-Patent Document 2] TJ Scheffer et. al., J. Appl. Phys Vol. 48, pl783 (1977) [Non-Patent Document 3] F. Nakano et. al., JPN. J. Appl. Phys. vol. 19, p2013 (1980) SUMMARY OF THE INVENTION Problems to be Solved by the Invention The object of the present invention is to provide a liquid crystal alignment agent which can obtain good pretilt property by photo-alignment method and which can provide a liquid crystal alignment film which does not cause deterioration in display properties when continuously operated for a long period of time. Means for Solving the Problems According to the present invention, the above objects and advantages of the present invention are achieved by a liquid crystal alignment agent comprising a polylysine obtained by reacting a tetracarboxylic dianhydride with a diamine and the polyamine At least one polymer selected from the group consisting of polyfluorene rings formed by acid dehydration ring closure, wherein the tetracarboxylic dianhydride comprises 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3 At least one selected from the group consisting of 5:6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, diamine A diamine having a photoreactive structure is included. EFFECTS OF THE INVENTION The liquid crystal alignment agent of the present invention can form a liquid crystal alignment film which does not deteriorate in display properties even when it is continuously operated for a long period of time, as compared with a conventionally known liquid crystal alignment agent which is capable of applying a liquid crystal alignment agent to a photo-alignment method. -6-201113328 Therefore, the liquid crystal display element obtained when the liquid crystal alignment film of the present invention is used for a liquid crystal display element is excellent in various properties such as display properties and reliability. Therefore, the liquid crystal display element can be effectively applied to various devices such as a desktop computer, a watch, a desk clock, a counter display panel, a word processor, a personal computer, a liquid crystal television, and the like. [Embodiment] The liquid crystal alignment agent of the present invention contains a polylysine obtained by reacting tetracarboxylic dianhydride with a diamine and a polyfluorene formed by dehydration of the polyglycolic acid as described above. At least one polymer selected from the group consisting of imines (hereinafter sometimes referred to as "specific polymers"), wherein the tetracarboxylic dianhydride comprises 3,5,6-tricarboxy-2-carboxymethyl a group consisting of norbornane-2:3,5:6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride At least one selected, the diamine comprises a diamine having a photoreactive structure. <tetracarboxylic dianhydride> As a tetracarboxylic dianhydride for synthesizing the polyamic acid in the present invention, it is composed of 3,5,6-tricarboxy-2-carboxymethylnorbornane-2 : at least one selected from the group consisting of 3,5:6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride Tetracarboxylic dianhydride. The tetracarboxylic dianhydride for synthesizing the polyamic acid preferably contains 80 mol% or more, more preferably 90 mol% or more of 3,5,6-, based on the total tetracarboxylic dianhydride. Tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8 At least one selected from the group consisting of dianhydrides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . An alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride or the like. Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, butane tetracarboxylic dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include 1, 2, and 3, 4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,33,4,5,91?-hexahydro-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphtho[l,2-c]furan-,3·dione, 1,3,3&,4,5,91)-hexahydro-8- 5-(4-hydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1 Octyl-2,4-dione-6-spiro-3'-(tetrahydrofuran-2,5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3 -methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4,9-dioxatricyclo[5.3.1.02·6]undecane-3,5,8,10-tetraone, etc.; Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like; and tetracarboxylic dianhydride described in Patent Document 7 . <Diamine> The diamine used for the synthesis of the poly-proline in the present invention is a diamine containing a diamine having a photoreactive structure. The photoreactive structure preferably has a structure capable of performing at least one reaction selected from the group consisting of isomerization and dimerization by light irradiation, and examples thereof include a structure represented by the following formula (Α-2). -8 - 201113328

(式（A-2)中，d是0或1，A1和A2分別是碳原子數爲 1~6的烷基、碳原子數爲卜6的烷氧基、鹵原子或氰基’ e 和f分別是0〜4的整數，“ 分別表示連接鍵）。作爲上式（A-2)中的A1和A2分別以碳原子數爲1~6的烷氧基爲較佳。e和f分別較佳爲〇。具有光反應性結構的二胺進一步包含具有使液晶分子配向的功能的部位者爲較佳’作爲還具有該部位的光反應性結構，例如可以列舉出選自由下式（A-2-1)和（A-2-2)分別表示的結構中的至少一種結構。(In the formula (A-2), d is 0 or 1, and A1 and A2 are each an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 6 carbon atoms, a halogen atom or a cyano group 'e and f is an integer of 0 to 4, respectively, and "connecting bonds respectively". A1 and A2 in the above formula (A-2) are preferably alkoxy groups having 1 to 6 carbon atoms, respectively. Preferably, the diamine having a photoreactive structure further includes a moiety having a function of aligning liquid crystal molecules, and is preferably a photoreactive structure having the site, and is, for example, selected from the following formula (A) At least one of the structures represented by -2-1) and (A-2-2), respectively.

(A-2-1)(A-2-1)

式（A-2-1)和（A-2-2)中，A1 ' A2、d、e和f分別和上式 (A-2-2) (A-2)中的定義相同， 201113328 R1和R11分別是碳原子數爲1~20的院基 1〜8的氟代烷基或具有脂環結構的碳原子數基， X11和 Χιη分別是-0.、_CO_' -CO-0-、-C -NR-CO- ' -CO-NR- > -NR-C0-0- ' -O-CO-NR-或-0-C〇-0-(其中，R是氫原子或碳原子數爲 R111分別是亞甲基、伸芳基、2價的脂環3 -CH = CH-或-C三C-，其中Rni所具有的氫原子以上可以被氰基、鹵原子或碳原子數爲1 ~4 ί h是1~6的整數， i是0〜2的整數，存在多個上述XM和Rin時，它們可以彼以不同， j是0或1，而且“ +”分別表示連接鍵）作爲上式（A-2-1)和（A-2-2)中的R1和Rn 1 ~ 20的烷基，可以列舉出例如甲基、正丁基己基、正庚基、正十八烷基等。作爲R1和ϊ 爲1〜20的烷基，從能夠顯示出良好的液晶配發，分別以碳原子數爲1〜12的直鏈烷基爲較原子數爲3〜12的直鏈烷基，特佳爲碳原子婁鏈院基。、碳原子數爲爲 4〜30的烴 • -CO- ' -NR-、 ' -NR-CO-NR-1〜4的烷基）， …-Si(CH〇2-、的一個或兩個 β烷基取代，此相同，也可〇的碳原子數爲、正戊基、正 (11的碳原子數向性的觀點出佳，更佳爲碳 $[爲4〜1 2的直 -10- 201113328 作爲R1和Rn的碳原子數爲1〜8的氟代烷基，從能夠顯示出良好的液晶配向性的觀點出發，分別較佳爲碳原子數爲3~6的直鏈氟代烷基，可以列舉出例如3,3,3·三氟代正丙基、4,4,4-三氟代正丁基、4,4,5,5,5-五氟代正戊基、 4,4,5,5,6,6,6-七氟代己基等。作爲R1和Rn的具有脂環結構的碳原子數爲4~30的烴基的具體例子，可以列舉出環己基甲基、膽甾烷基、膽甾嫌基、羊毛留院基等。 Χπ和Χ1Π分別較佳爲-0-。具有光反應性結構的二胺可以在一個分子中具有一個或兩個以上的該光配向性結構，較佳具有一個或兩個該結構。作爲具有該結構的具有光反應性結構的二胺的具體例子，分別是作爲具有上式（A - 2 -1)所示的結構的二胺，可以列舉出例如下式（Α-2·1-1)~(Α-2-1-13)分別表示的化合物等； -11 - 201113328In the formulae (A-2-1) and (A-2-2), A1 'A2, d, e, and f are the same as defined in the above formula (A-2-2) (A-2), respectively, 201113328 R1 And R11 are a fluoroalkyl group having 1 to 20 carbon atoms or a carbon atom group having an alicyclic structure, and X11 and Χιη are -0., _CO_' -CO-0-, respectively. -C -NR-CO- ' -CO-NR- > -NR-C0-0- ' -O-CO-NR- or -0-C〇-0- (where R is a hydrogen atom or a carbon atom R111 is a methylene group, an aryl group, a divalent alicyclic ring, 3-CH=CH- or -C-C-, wherein Rni has a hydrogen atom or more of a cyano group, a halogen atom or a carbon atom. 1 ~ 4 ί h is an integer from 1 to 6, and i is an integer from 0 to 2. When there are a plurality of the above XM and Rin, they may be different from each other, j is 0 or 1, and "+" indicates a connection key) Examples of the alkyl group of R1 and Rn 1 to 20 in the above formulas (A-2-1) and (A-2-2) include methyl, n-butylhexyl, n-heptyl and n-octadecane. Base. The alkyl group having R1 and ϊ of from 1 to 20 is a linear alkyl group having a carbon number of from 1 to 12 and a linear alkyl group having an atomic number of from 3 to 12, respectively, in order to exhibit good liquid crystal distribution. It is especially good for carbon atoms. , one or two hydrocarbons having a carbon number of 4 to 30, -CO- '-NR-, '-NR-CO-NR-1~4 alkyl group, ...-Si(CH〇2-, The β-alkyl group is substituted, and the same, or the number of carbon atoms, n-pentyl group, and positive (11 carbon atom number directionality is preferred, and more preferably carbon $ [4 to 1 2 straight-10 -201113328 The fluoroalkyl group having 1 to 8 carbon atoms as R1 and Rn is preferably a linear fluoroalkane having 3 to 6 carbon atoms from the viewpoint of exhibiting good liquid crystal alignment. The base may, for example, be 3,3,3·trifluoro-n-propyl, 4,4,4-trifluoro-n-butyl, 4,4,5,5,5-pentafluoro-n-pentyl, 4 4,5,5,6,6,6-heptafluorohexyl, etc. Specific examples of the hydrocarbon group having 4 to 30 carbon atoms having an alicyclic structure of R1 and Rn include a cyclohexylmethyl group. A cholesteryl group, a cholestyramine group, a wool leaver base, etc. Χπ and Χ1Π are preferably -0-, respectively. A diamine having a photoreactive structure may have one or two or more optical alignments in one molecule. a structure, preferably having one or two of the structures. As having the structure Specific examples of the diamine of the photoreactive structure are diamines having a structure represented by the above formula (A - 2 -1), and examples thereof include the following formula (Α-2·1-1)~(Α -2-1-13) respectively indicated compounds; -11 - 201113328

OC4H9OC4H9

h2nH2n

(A-2-1-2)(A-2-1-2)

(A-2-1-3)(A-2-1-3)

OO

12- 20111332812-201113328

(A-2-1-9) 13- 201113328(A-2-1-9) 13-201113328

(A-2-1-11)(A-2-1-11)

作爲具有上式（A-2-2)所示的結構的二胺，可以列舉出例如下式（A-2-2-1)表示的化合物等。 -14- 201113328The diamine having a structure represented by the above formula (A-2-2) may, for example, be a compound represented by the following formula (A-2-2-1). -14- 201113328

COO——(CH2)6—〇COO——(CH2)6—〇

H 上述二胺較佳進一步含有由下式（A_0)和（A_3)構成的群組中選出的至少一種，H The above diamine preferably further contains at least one selected from the group consisting of the following formulas (A_0) and (A_3).

(式（A-0)中’ X1表示單鍵' 亞甲基、碳原子數爲2或3 的伸院基、*-0-、*-C00-、*-〇C〇-、或 *-X’-Ri-X’-(其中 ’ X’ 分別表示 +.〇.、+_c〇〇_S+-〇c〇.(其中“+”表不帶有其的連接鍵朝向式（A-0)的左方向）， R1分別是碳原子數爲2或3的伸烷基，帶“ ”的連接鍵和二胺基苯基連接），(In the formula (A-0), 'X1 represents a single bond', a methylene group, a carbon number of 2 or 3, a group of *0-, *-C00-, *-〇C〇-, or *- X'-Ri-X'- (where 'X' denotes +.〇., +_c〇〇_S+-〇c〇. respectively (where the "+" table does not have its connection key orientation (A-0) In the left direction), R1 is an alkylene group having 2 or 3 carbon atoms, a linking bond with "" and a diaminophenyl group),

Ring1和Ring2各自獨立地是伸環己基或伸苯基， X’·是單鍵'+-0-、+-C00 -或者、OC〇-(其中“+”表示帶有其的連接鍵朝向式（A-0)的左方向）， a是0或l，b是0〜3的整數， b爲2以上時，多個存在的X "和R i n g2分別相互相同’ 也可以不同，a爲0時，位於式（A-Ο)的最左邊的X"是單鍵’ c是0~20的整數，α和冷分別是0〜2c + l的整數’其中 a+)5=2c+l，而且 a + b = 0 時，c 不是 0); -15- 201113328Ring1 and Ring2 are each independently a cyclohexyl group or a phenyl group, and X'· is a single bond '+-0-, +-C00 - or OC〇- (where "+" means a bond-oriented type with a bond (A-0) in the left direction), a is 0 or l, b is an integer of 0 to 3, and when b is 2 or more, a plurality of X " and R in g2 are respectively identical to each other 'may be different, a When 0, the leftmost X" located in the formula (A-Ο) is a single key 'c is an integer from 0 to 20, and α and cold are integers of 0~2c + l respectively, where a+)5=2c+l , and when a + b = 0, c is not 0); -15- 201113328

(式（A-3)中，R,M各自獨立地是氫原子或碳原子數爲 1〜12的烷基，尺”和Rv各自獨立地是氫原子或甲棊）° 作爲上式（A-0)所币的化合物的較佳結構，可以列舉出例如下式所示的化合物(In the formula (A-3), R and M are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and the ruthenium and Rv are each independently a hydrogen atom or a formazan.) As the above formula (A) -0) A preferred structure of the compound of the coin, which may, for example, be a compound represented by the following formula

CcH2c+1 (A-1) h2n. h2n (式（A-l)中，X1 是 *-〇-、'COO-或 *-oco·(其中’帶 “ 的連接鍵和二胺基苯基連接）’3是0或1’b是0~2的整數’ C是1~20的整數）。作爲上式（A-1)中的X1較佳爲· -◦-或*-coo-(其中，帶 “ 的連接鍵和二胺基苯基連接）°作爲基團已H2…-的具體例子，可以列舉出例如甲基、乙基、正丙基、正丁基、正戊基、正己基 '正庚基、正辛基、正壬基、正癸基 '正十二垸基、正十三院基、正十四烷基、正十五院基、正十六烷基、正十七烷基、正十八院基、正十九院基、正二十院基等。二胺基苯基的兩個胺基，相對於其他基團較佳爲 2,4-位或3,5-位。 -16- 201113328 作爲上式（A -1)所示的化合物的具體例子· ’可以例如下式（A-卜1)~(Α·卜4)分別表示的化合物等。CcH2c+1 (A-1) h2n. h2n (In the formula (Al), X1 is *-〇-, 'COO- or *-oco· (where 'the linkage of 'band' and diaminophenyl linkage)' 3 is 0 or 1'b is an integer of 0 to 2 'C is an integer of 1 to 20.) X1 in the above formula (A-1) is preferably -◦- or *-coo- (wherein "The linking bond and the diaminophenyl group are bonded." Specific examples of the group H2...- may, for example, be methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl Heptyl, n-octyl, n-decyl, n-decyl'-n-decyl, n-triene, n-tetradecyl, n-xyl, n-hexadecyl, n-heptadecyl , the 18th courtyard base, the 19th courtyard base, the 20th courtyard base, etc. The two amine groups of the diaminophenyl group are preferably the 2,4-position or the 3,5-position relative to the other groups. -16-201113328 A specific example of the compound represented by the above formula (A-1) can be, for example, a compound represented by the following formula (A-Bu 1)-(Α·卜4).

nh2 列舉出 (A-1-1) (A-1-2) H2N—^~~0—(CH2)17CH3 (A-1-4) NH2 上式（A-l)中’ a和b較佳不同時爲0。上式（A-3)中，Rni、1^和Rv分別較佳爲氫原号連接到上式（A-3)的苯環的兩個胺基’相對於氮佳爲2,4-位。作爲上式（A-3)所示的化合物，最佳爲N，N-二 -2,4-二胺基苯胺》作爲用於合成前述聚醯胺酸的二胺，可以將上光反應性結構的二胺、上式（A-Ο)和（A-3)所示的二胺二胺一起使用，可以列舉出例如上述以外的脂肪族脂環式二胺、芳香族二胺、二胺基有機矽氧烷等。原子較烯丙基述具有以外的二胺、作爲它 -17- 201113328 們的具體例子，分別是作爲脂肪族二胺’可以列舉出例如 1，1 -間二甲苯二胺、1，3 -丙二胺、1，4 - 丁二胺、1，5 ·戊二胺、 1,6-己二胺等；作爲脂環式二胺，可以列舉出例如1,4-二胺基環己烷、4,4’-亞甲基二（環己基胺）、1，3-二（胺基甲基）環己烷等；作爲芳香族二胺，可以列舉出例如對伸苯基二胺、4，4 ’ -二胺基二苯基甲烷、4,4’-二胺基二苯基硫醚、1，5-二胺基萘、2,2’-二甲基-4,4’-二胺基聯苯、4,4’-二胺基-2,2’-二（三氟甲基）聯苯、2,7-二胺基弗、4,4’-二胺基二苯基醚、2,2-二[4-(4-胺基苯氧基）苯基]丙烷、9,9-二（4-胺基苯基）莽、2,2-二[4-(4-胺基苯氧基）苯基]六氟丙烷、2,2-二（4·胺基苯基）六氟丙烷、4,4’-(對伸苯基二亞異丙基）二（苯胺）、4,4’-(間伸苯基二亞異丙基）二（苯胺）、1，4-二（4-胺基苯氧基）苯、 4,4’-二（4-胺基苯氧基）聯苯、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、3,6-二胺基咔唑、 N-甲基-3,6-二胺基咔唑、N-乙基-3,6-二胺基咔唑、N-苯基 -3,6-二胺基咔唑、1!^’-二（4-胺基苯基）-聯苯胺、1化-二（4-胺基苯基）-Ν,Ν’ -二甲基聯苯胺、膽甾烷氧基-3,5 -二胺基苯、膽甾烯氧基-3 ,5 -二胺基苯、3,5 -二胺基苯甲酸膽甾烷基酯、3,5-二胺基苯甲酸膽甾烯基酯' 3,5_二胺基苯甲酸羊毛甾烷基酯等；作爲一胺基有機砂氧垸’可以列舉出例如1，3 _二（3 _胺基丙基）-四甲基二矽氧烷等， -18- 201113328 以及使用專利文獻7(日本特開2010-97188號：記載的二胺。 [二胺的組成] 用於合成本發明中的聚醯胺酸的二胺，是包含述的具有光反應性結構的二胺的二胺，可以進一步含由上述式（A-0)和（A-3)構成的群組中選出的至少胺以及其他二胺。作爲合成本發明中的聚醯胺酸使用的二胺，相部二胺，較佳含有50~99莫耳％，更佳含有70〜95赛述具有光反應性結構的二胺；相對於全部二胺，較佳含有1~50莫耳％，更佳含莫耳％選自由上述式（A-0)和（A-3)構成的群組的至少胺；相對於全部二胺，可以含有20莫耳％以下的範一步可以含有1 0莫耳％以下的範圍的其他二胺；用於合成本發明中的聚醯胺酸的二胺較佳只由有光反應性結構的二胺和選自由上述式（A-0)和（A 的群組的至少一種二胺構成。 [分子量調節劑] 在合成前述聚醯胺酸時’可以使用適當的分子劑，和如上所示的四羧酸二胺和二胺一起’合成末型聚合物。通過形成該末端修飾型聚合物’可以不發明的效果地改善液晶配向劑的塗布性（印刷性）。士報）中如上所任意包一種二對於全 ί耳％上有2〜20 一種二圍，進上述具 -3)構成量調節端修飾損害本 -19- 201113328 作爲前述分子量調節劑，可以列舉出例如酸單酐、單胺化合物、單異氰酸酯化合物等。作爲它們的具體例子，分別是作爲酸單酐，可以列舉出例如馬來酸酐、鄰苯二甲酸酐、衣康酸酐、正癸基水楊酸酐、正十二烷基水楊酸酐、正十四烷基水楊酸酐、正十六烷基水楊酸酐等；作爲單胺化合物，可以列舉出例如苯胺、環己基胺、正丁胺、正戊胺、正己胺、正庚胺、正辛基胺等；作爲單異氰酸酯化合物，可以列舉出例如異氰酸苯基酯、異氰酸萘基酯等。分子量調節劑的使用比例，相對於使用的四羧酸二酐和二胺的總計1 00重量份，較佳爲20重量份以下，更佳爲 1 〇 k量份以下。 <聚醯胺酸的合成> 作爲聚醯胺酸的合成反應中使用的四羧酸二酐和二胺的使用比例，相對於1當量二胺的胺基，四羧酸二酐的酸酐基較佳爲0.2〜2當量的比例，更佳爲0.3~ 1.2當量的比例。聚醯胺酸的合成反應較佳在有機溶劑中進行，較佳在 -20°C〜150°C，更佳在Ot ~100°C下，較佳進行0.1〜120小時，更佳進行0.5〜4 8小時。其中，作爲有機溶劑，可以列舉出例如N -甲基-2 -吡咯烷酮' N，N-二甲基乙醯胺、Ν,Ν-二甲基甲醯胺、二甲基亞楓、r -丁內酯、四甲基脲、六甲基磷醯三胺等非質子性極性溶劑； -20- 201113328 間甲酚、二甲苯酚、苯酚、鹵代苯酚等酚性溶劑。有機溶劑的用量（a)較佳爲四羧酸二酐和二胺的總量（b)相對於反應溶液的全部量（a + b)是1~50重量％的量。如上’可以得到溶解聚醯胺酸形成的反應溶液。該反應溶液可以直接用於製備液晶配向劑，也可以在分離反應溶液中含有的聚醯胺酸後，用於製備液晶配向劑’或者將分離的聚醯胺酸精製後，用於製備液晶配向劑。將聚醯胺酸脫水閉環形成聚醯亞胺時，可以將上述反應溶液直接用於脫水閉環反應；也可以分離反應溶液中含有的聚醯胺酸分離後’用於脫水閉環反應；或者將分離的聚醯胺酸精製後’用於脫水閉環反應。聚醯胺酸的分離和精製可以通過公知的方法進行。 <聚醯亞胺的合成> 前述聚醯亞胺可以通過將如上合成的聚醯胺酸脫水閉環醯亞胺化得到。本發明中的聚醯亞胺可以是作爲其前體的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；也可以只是醯胺酸結構的一部分脫水閉環，醯胺酸結構和醯亞胺環結構並存的部分醯亞胺化物。本發明中的聚醯亞胺的醯亞胺化率較佳爲30 %以上，更佳爲40〜90%。該醯亞胺化率是以百分率表示醯亞胺環結構的數量佔據聚醯亞胺的醯胺酸結構的數量和醯亞胺環結構的數量的總量的比例。聚醯胺酸的脫水閉環較佳以通過加熱聚醯胺酸的方 -21 - 201113328 法，或者將聚醯胺酸溶解在有機溶劑中，在該溶液中添加脫水劑和脫水閉環催化劑，根據需要加熱的方法進行。其中，以由後者之方法進行者較佳。在上述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，可以列舉出例如乙酸酐、丙酸酐、三氟乙酸酐等酸酐。作爲脫水劑的用量，相對於1莫耳聚醯胺酸的醯胺酸結構，較佳爲0.01〜20莫耳。作爲脫水閉環催化劑，可以列舉出例如吡啶、三甲基吡啶、二甲基吡啶、三乙胺等3級胺。作爲脫水閉環催化劑的用量，相對於1莫耳使用的脫水劑，較佳爲0.01〜10莫耳。作爲脫水閉環反應中使用的有機溶劑，可以列舉出作爲合成聚醯胺酸使用的溶劑例示的有機溶劑。作爲脫水閉環反應的反應溫度較佳爲0~180°C，更佳爲10〜150°C。作爲反應時間較佳爲1.0〜120小時，更佳爲2.0〜30小時。這樣可以得到含有聚醯亞胺的反應溶液。該反應溶液可以將其直接用於製備液晶配向劑，也可以從反應溶液除去脫水劑和脫水閉環催化劑後，用於製備液晶配向劑；還可以分離聚醯亞胺後，用於製備液晶配向劑；或者將分離的聚醯亞胺精製後，用於製備液晶配向劑。這些精製操fp 可以根據公知的方法進行。 <其他成分> 本發明的液晶配向膜含有如上的特定聚合物作爲必胃成分，根據需要也可以含有其他成分。作爲該其他成分， -22- 201113328 可以列舉出例如上述特定聚合物以外的聚合物（以下，稱作其他聚合物）、在分子內具有至少一個環氧基的化合物 (以下’稱作“環氧化合物”）、官能性矽烷化合物等。 [其他聚合物] 上述其他聚合物可以用於改善溶液性質和電性質。作爲該其他聚合物，是如上特定聚合物以外的聚合物，可以列舉出例如四羧酸二酐和不含上述具有光反應性結構的二胺的二胺反應得到的聚醯胺酸（以下，稱作“其他聚醯胺酸”）、將該聚醯胺酸脫水閉環形成的聚醯亞胺（以下，稱作“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。它們之中，較佳爲其他聚醯胺酸和其他聚醯亞胺，更佳爲其他聚醯胺酸。作爲用於合成上述其他聚醯胺酸或其他聚醯亞胺的四羧酸二酐’可以列舉出和作爲用於合成特定聚合物的四羧酸二酐的上述同樣的四羧酸二酐，較佳使用選自由1,2,3,4-環丁烷四羧酸二酐和均苯四羧酸二酐構成的群組的至少一種。作爲用於合成其他聚醯胺酸或其他聚醯亞胺的二胺，可以列舉出用於合成特定聚合物的二胺中，上述具有光反應性結構的二胺以外的二胺，相對於使用的全部二胺，較佳含有50莫耳％以上，更佳含有80莫耳％以上的選自由對 -23- 201113328 伸苯基二胺、4,4·二胺基二苯基甲烷和4,4_二胺基二苯基醚構成的群組的至少一種。作爲其他聚合物使用比例，相對於聚合物的總量（是指上述特定聚合物和其他聚合物的總量，以下相同），較佳爲 90重量％以下’更佳爲50〜80重量％。 [環氧化合物] 作爲上述環氧化合物’可以列舉出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 -二溴代新戊二醇二縮水甘油醚、1，3,5,6 -四縮水甘油基-2,4-己二醇' Ν,Ν,Ν’，Ν’ -四縮水甘油基-間二甲苯二胺、1,3-二（Ν,Ν-二縮水甘油基胺基甲基）環己烷、Ν,Ν,Ν’，Ν’-四縮水甘油基- 4,4’-二胺基二苯基甲烷、Ν,Ν -二縮水甘油基 -苄基胺、Ν,Ν-二縮水甘油基-胺基甲基環己烷等。相對於聚合物總計100重量份，這些含有環氧基的化合物的混合比例較佳爲40重量份以下，更佳爲0.1〜30重量份。 [官能性砂院化合物] 作爲上述官能性矽烷化合物，可以列舉出例如3 -胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、安基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基）-3·胺基丙基三甲氧基矽烷、N-(2-胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、3-醯脲丙基三甲氧基矽烷、3-醯脲丙 -24- 201113328 基三乙氧基砂院' N -乙氧基羯基-3-胺基丙基三甲氧基砂烷、N·乙氧基羰基-3-胺基丙基三乙氧基矽烷、^三乙氧基甲矽烷基丙基三伸乙基三胺、N-三甲氧基甲矽烷基丙基三伸乙基三胺、10 -三甲氧基甲矽烷基_1，4,7 -三氮雜癸烷、1〇· 三乙氧基甲矽烷基-1，4,7-三氮雜癸烷、9-三甲氧基甲矽烷基 •3,6-二氮雜壬基乙酸酯、9-三乙氧基甲矽烷基-3,6·二氮雜壬基乙酸酯、N -苄基-3-胺基丙基三甲氧基矽院、N -节基- 3-胺基丙基三乙氧基砂院、N -苯基·3·胺基丙基三甲氧基砂烷、Ν·苯基-3-胺基丙基三乙氧基矽烷、Ν_二（氧化伸乙基）-3 -胺基丙基三甲氧基砂院、Ν -二（氧化亞乙基）_3_胺基丙基三乙氧基矽烷等。相對於聚合物總計1 0 0重量份，這些官能性矽烷化合物的混合比例較佳爲2重量份以下，更佳爲〇 . 〇 2 ~ 0.2重量份。 <液晶配向劑> 本發明的液晶配向劑將如上特定聚合物和根據需要任意混合的其他添加劑較佳在有機溶劑中溶解含有而構成。作爲可以在本發明的液晶配向劑中使用的有機溶劑，可以列舉出作爲聚醯胺酸的合成反應中使用的溶劑例示的溶劑。另外’還可以適當選擇目前作爲聚醯胺酸和聚醯亞胺的貧溶劑而被確認的有機溶劑一起使用。作爲該有機溶劑較佳的例子，可以列舉出例如Ν-甲基-2-吡咯烷酮、r -丁內酯、r -丁內醯胺' N，N-二甲基甲醯胺、Ν,Ν-二甲基乙 -25- 201113328 醯胺、4-經基-4-甲基-2·戊酮、乙二醇單甲基醚、乳酸丁酯、乙酸丁醋 '甲基甲氧基丙酸酯、乙基乙氧基丙酸酯、乙二醇甲基醚、乙二醇乙基醚、乙二醇正丙基醚、乙二醇異丙基醚、乙二醇正丁基醚（丁基溶纖劑）、乙二醇二甲基醚、乙二醇乙基醚乙酸酯、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二異丁基酮、丙酸異戊基酯、異丁酸異戊基酯、二異戊基醚等。它們可以單獨使用’或者也可以混合兩種以上使用。本發明的液晶配向劑的固體成分濃度（液晶配向劑中’除去有機溶劑以外的成分的總重量佔據液晶配向劑的總重量的比例），考慮黏性、揮發性等適當選擇，較佳爲1 ~ 1 〇重量％的範圍。也就是，本發明的液晶配向劑可以通過將其塗布到基板表面，除去有機溶劑，形成液晶配向膜的塗膜，但是在固體成分濃度小於1重量％時，該塗膜的膜厚過小，可能難以得到良好的液晶配向膜；另一方面，在固體成分濃度超過10重量％時，塗膜的膜厚過大，同樣可能難以得到良好的液晶配向膜，而且液晶配向劑的黏性增大，塗布性質可能不足。特佳的固體成分濃度的範圍根據在基板上塗布液晶配向劑時採用的方法而異。例如，在使用旋塗法進行時，固體成分濃度特佳爲1.5 ~4.5重量％的範圍。在使用印刷法進行時，固體成分濃度爲3〜9重量％的範圍’由此’溶液黏度 -26- 201113328 特佳爲12〜50mPa .s的範圍。在使用噴墨法進行時，固體成分濃度爲1〜5重量％的軺圍，由此，溶液黏度特佳爲 3~ 1 5mPa · s 的範圍。 <液晶配向膜的形成方法> 本發明的液晶配向劑適合用於通過光配向法形成液晶配向膜。作爲形成液晶配向膜的方法，可以列舉出例如將液晶配向劑塗布到基板上，形成塗膜，從相對塗膜面傾斜的方向在該塗膜上照射偏光或者非偏光的紫外線，或者從相對塗膜面垂直的方向在該塗膜上照射偏光紫外線，對塗膜賦予液晶配向能的方法。首先’通過例如輕塗法、旋塗法、印刷法、噴墨法等適當的塗布方法’在設置圖案狀透明導電膜的基板的透明導電膜側，塗布本發明的液晶配向劑。塗布後，通過將該塗布面預加熱（預烘焙），然後燒製（後烘焙）形成塗膜。預烘焙條件例如是在40~120°C下進行〇.卜5分鐘，後烘培條件較佳在120〜300°C、更佳爲150〜250°C下，較佳進行5〜200 分鐘’更佳進行10~100分鐘。後烘焙後的塗膜的膜厚較佳爲 0.0 0 1 〜1// m ’ 更佳爲〇. 〇〇 5 ~ 0.5 " m。作爲前述基板’可以使用例如由像浮法玻璃、鈉玻璃這樣的玻璃；像聚對苯二甲酸乙二酯、聚對苯二甲酸丁二醋、聚醚颯、聚碳酸醋這樣的塑膠等形成的透明基板等。 -27- 201113328 作爲前述透明導電膜可以使用由Sn〇2形成的NESA 膜、由ImCh-SnO2形成的ITO膜等。爲了形成這些透明導電膜的圖案’可以使用光蝕刻法或者形成透明導電膜時使用掩膜的方法等。塗布液晶配向劑時，爲了使基板或透明導電膜與塗膜的黏結性更好，可以在基板和透明導電膜上，預先塗布官能性矽烷化合物、鈦酸鹽化合物等。接著，通過照射偏光或者非偏光的紫外線，對該塗膜賦予液晶配向能，前述塗膜成爲液晶配向膜。這裏，作爲放射線，可以使用包含150~800nm的波長的光的紫外線和可見光線，較佳包含300〜400n m的波長的光的紫外線。使用的放射線爲偏光（直線偏光或部分偏光）時，可以從相對塗膜面垂直的方向照射，也可以爲了賦予預傾角而從傾斜的方向照射。另一方面，在照射非偏光時，照射必須從相對塗膜面傾斜的方向進行。作爲照射放射線的光源，可以使用例如低壓水銀燈、高壓水銀燈、重氫燈、金屬鹵化物燈、氬共振燈、氙燈、準分子鐳射等。前述較佳波長區域的紫外線可以通過將前述光源和例如濾光片 '衍射光柵等一起使用的手段等得到。放射線的照射量較佳爲U/m2以上、不足1 0,000J/m2，更佳爲10〜3,000〗/m2。另外，通過光配向法在由目前已知液晶配向劑形成的塗膜上賦予液晶配向能時’必須要 10,000J/m2以上的放射線照射量。但是，如果使用本發明的 -28- 201113328 液晶配向劑，光配向法時的放射線照射量即使爲3,000〗/m2 以下，進而爲l,000J/m2以下，進一步爲300J/m2以下，也可以賦予良好的液晶配向能，有助於削減液晶顯示元件的製造成本。 <液晶顯示元件的製造方法> 本發明的液晶顯示元件具有由本發明的液晶配向劑形成的液晶配向膜。本發明的液晶顯示元件例如可以如下製造。準備兩塊如上形成液晶配向膜的基板，通過在這兩塊基板間配置液晶，製造液晶胞。在製造液晶胞時，可以列舉出例如下述兩種方法。第一種方法是目前已知的方法。首先，爲了使各液晶配向膜對向設置，通過間隙（盒間隙），將兩塊基板對向配置，使用密封劑，將兩塊基板的周邊部位貼合，在由基板表面和密封劑分割的胞間隙內注入塡充液晶後，密封注入孔，可以製造液晶胞。第二種方法是稱作ODF(One Drop Fill，滴注）方式的方法。在形成液晶配向膜的兩塊基板中的一個基板上的規定位置，塗布例如紫外光固化性的密封劑，然後在液晶配向膜面上滴加液晶後’貼合另一個基板以使液晶配向膜對向，然後’在基板的整面照射紫外光，使密封劑固化，由此可以製造液晶胞。 -29- 201113328 在任一種方法的情況下’希望接著將液晶胞加熱到使用的液晶各向同性的溫度後，緩慢冷卻到室溫，除去液晶注入時的流動配向》然後’通過在液晶胞的外側表面貼合偏振片，可以得到本發明的液晶顯示元件。這裏，液晶配向膜爲水平配向性時，通過調整形成液晶配向膜的兩塊基板中，照射直線偏光放射線的偏光方向形成的角度和各基板與偏振片的角度，可以得到具有TN型或STN型液晶胞的液晶顯示元件。另一方面，在液晶配向膜爲垂直配向性時，使形成液晶配向膜的兩塊基板中的容易配向的軸的方向平行地構成液晶胞，在其中貼合偏振片，並使其偏光方向和容易配向的軸形成45°的角度，可以形成具有垂直配向型液晶胞的液晶顯示元件。作爲前述密封劑，可以使用例如含有作爲隔片的氧化鋁球和固化劑的環氧樹脂等。作爲前述液晶，較佳使用例如向列型液晶 '碟型液晶等。在爲TN型液晶胞或STN型液晶胞時，較佳具有正的介電各向異性的向列型液晶，可以使用例如聯苯類液晶、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、嘧啶類液晶、二噚烷類液晶、雙環辛院類液晶、立方烷類液晶等。另外’前述液晶中’可以進一步添加使用例如氯化二氫膽固醇（choksty1 chloride)、膽固醇壬 201113328 酸酯、膽固醇碳酸酯等膽固醇液晶；以商品名“ C-15” 、 “CB-15” （Merck公司製造）銷售的手性試劑；對癸氧基亞苄基-對胺基-2·甲基丁基肉桂酸酯等鐵電性液晶等。另一方面，在爲垂直配向型液晶胞時，較佳具有負的介電各向異性的向列型液晶，可以使用例如二氰基苯類液晶、嗒阱類液晶、西夫鹼類液晶、氧化偶氮基類液晶、聯苯類液晶、苯基環己烷類液晶等。作爲液晶胞的外側使用的偏振片，可以列舉出一邊將聚乙烯醇延展配向，一邊用醋酸纖維素保護膜夾住吸收碘稱作“H膜”的偏光膜形成的偏振片或由Η膜本身形成的偏振片。這樣製造的本發明的液晶顯示元件，顯示性能優異，即使長時間使用，顯示性能也不會變差。 [實施例] 以下，通過實施例，對本發明進行更具體地說明，但是本發明並不受到這些實施例的限定。以下的合成例中的聚合物的溶液黏度、聚醯亞胺的醯亞胺化率分別通過下述方法評價。 [聚合物的溶液黏度] 聚合物的溶液黏度（mPa . s)是對各聚合物溶液，使用Ε 型旋轉黏度計，在2 5 °C下測定。 -31 - 201113328 <聚醯亞胺的醯亞胺化率> 少量分取各合成例得到的含有聚醯亞胺的溶液，投入到純水中，過濾得到的沉澱，從而分離出聚醯亞胺。將該聚醯亞胺在室溫下充分減壓乾燥後，溶解到重氫化二甲基亞颯中，以四甲基矽烷作爲基準物質，從室溫下測定的 j-NMR，通過下述數學式（1)求得。醯亞胺化率（％ )= (l-A'/A、a )xl00 (1) (數學式（1)中，A1是來自化學位移l〇ppm附近顯現出的NH基的質子的峰面積，A2是來自其他質子的峰面積， α 是其他質子的個數相對於一個聚醯亞胺的前體（聚醯胺酸）中的ΝΗ基的質子的比例）。 <特定聚合物的合成例和比較合成例> [聚醯胺酸的合成例] 合成例1 ~ 4 2和比較合成例1 ~ 6 將表1所示的種類和量的二胺和四羧酸二酐混合，以該順序加入到135g的Ν-甲基-2-吡咯烷酮中溶解，並形成二胺和四羧酸二酐的總重量相對於反應溶液的全部重量爲 1 0重量％的溶液，將其在60 °C下反應6小時，分別得到各 150g的含有10重量％聚醯胺酸（A-1)〜（A-42)和（R-1)〜（R-6) 的溶液。這裏得到的各溶液的黏度合倂到表1中表示。 [聚醯亞胺的合成] 合成例43~65和比較合成例7~12 -32- 201113328 將表2所示的種類和量的二胺和四羧酸二酐混合’以該順序加入到1 3 5 g的N ·甲基-2 -吡咯烷酮中溶解’並形成二胺和四羧酸二酐的總重量相對於反應溶液的全部重量爲 1 0重量％的溶液，將其在6 0 °C下反應6小時’分別得到各 150g的含有10重量％聚醯胺酸的溶液。這裏得到的各溶液的黏度合倂到表2中表示。接著，將這些含有各聚醯胺酸的溶液中，分別添加表 2所示的量的吡啶和乙酸酐，在1 1 0°C下，進行4小時脫水閉環反應。脫水閉環反應後，體系內的溶劑用新的N -甲基 -2 -吡咯烷酮進行溶劑置換（通過本操作，將脫水閉環反應中使用的吡啶和乙酸酐除去到體系外），從而分別得到含有1 5 重量％聚醯亞胺（B-45)〜（B-67)和（S-7)~(S-12)的溶液。各溶液的產量、分別取出少量各溶液加入N -甲基-2 -吡咯烷酮稀釋到10重量％測定的溶液黏度和各聚醯亞胺的醯亞胺化率分別合倂到表2中表示。 -33- 201113328 [表1] 二胺四羧酸二酐聚醯胺酸種類用量用量溶液黏度 (g) 漠耳）種類 (g) (莫耳）名稱 (mPa.s) 合成例1 d-1 9.7 0.021 t-1 5.3 0.021 A-l 25 合成例2 d-2 9.9 0.020 t-1 5.1 0.020 A-2 16 合成例3 d-3 10.0 0.020 t-1 5.0 0.020 A-3 16 合成例4 d-4 10.2 0.019 t-1 4.8 0.019 A-4 19 合成例5 d-5 9.6 0.022 M 5.4 0.022 A-5 23 合成例6 d-6 10.4 0.018 t-1 4.6 0.018 A-6 20 合成例7 d-6 10.4 0.018 t-2 4.6 0.018 A-7 22 合成例8 d-7 10.1 0.020 t-1 4.9 0.020 A-8 21 合成例9 d-7 10.1 0.020 t-2 4.9 0.020 A-9 15 合成例10 d-8 12.1 0.012 t-1 2.9 0.012 A-10 22 合成例11 d-8 12.1 0.012 t-2 2.9 0.012 A-ll 16 合成例12 d-9 10.2 0.019 t-1 4.8 0.019 A-12 21 合成例13 d-9 10.2 0.019 t-2 4.8 0.019 A-13 20 合成例14 d-10 10.5 0.018 t-1 4.5 0.018 A-14 19 合成例15 d-10 10.5 0.018 t-2 4.5 0.018 A-15 15 合成例16 d-11 12.2 0.011 t-1 2.8 0.011 A-16 19 合成例17 d-12 12.0 0.012 t-1 3.0 0.012 A-17 20 合成例18 d-13 12.1 0.012 t-1 2.9 0.012 A-18 25 合成例19 d-14 10.7 0.017 t-1 4.3 0.017 A-19 20 合成例20 d-14 10.7 0.017 t-2 4.3 0.017 A-20 25 合成例21 d-14 10.3 0.016 t-1 4.3 0.017 A-21 19 -34- 201113328 d-15 0.4 0.001 合成例22 d-6 9.9 0.018 t-1 4.6 0.019 A-22 15 d-16 0.4 0.001 合成例23 d-7 9.6 0.019 t-1 4.9 0.020 A-23 24 d-16 0.4 0.001 合成例24 d-8 11.8 0.011 t-1 3.0 0.012 A-24 21 d-16 0.3 0.001 合成例25 d-9 9.7 0.018 t-1 4.9 0.019 A-25 16 d-16 0.4 0.001 合成例26 d-10 10.0 0.017 t-1 4.6 0.018 A-26 24 d-16 0.4 0.001 合成例27 d-14 10.3 0.016 t-1 4.3 0.017 A-27 21 d-16 0.4 0.001 合成例28 d-14 10.3 0.016 t-2 4.3 0.017 A-28 18 d-16 0.4 0.001 合成例29 d-6 10.0 0.018 t-1 4.7 0.019 A-29 20 d-17 0.4 0.001 合成例30 d-7 9.7 0.019 t-1 5.0 0.020 A-30 22 d-17 0.4 0.001 -35- 201113328 [表1 ]續表二胺四羧酸二酐聚醯胺酸用量用量溶液黏度種類 (g) (莫耳）種類 (g) (莫耳）名稱 (mPa.s) d-8 11.8 0.011 A-31 合成例31 d-17 0.2 0.001 t-1 3.0 0.012 21 d-9 9.8 0.018 A-32 合成例32 d-17 0.4 0.001 t-1 4.9 0.019 24 d-10 10.1 0.017 A-33 合成例33 d-17 0.3 0.001 t-1 4.6 0.018 21 d-14 10.3 0.016 A-34 合成例34 d-17 0.3 0.001 t-1 4.3 0.017 24 d-14 10.3 0.016 A-35 合成例35 d-17 0.3 0.001 t-2 4.3 0.017 25 d-6 10.3 0.018 A-36 合成例36 d-19 0.2 0.001 t-1 4.8 0.019 16 d-7 10.0 0.019 A-37 合成例37 d-19 0.2 0.001 t-1 5.1 0.020 23 d-8 12.3 0.012 A-38 合成例38 d-19 0.1 0.001 t-1 3.1 0.012 20 d-9 10.1 0.019 A-39 合成例39 d-19 0.2 0.001 t-1 5.0 0.020 20 合成例40 d-10 10.4 0.018 t-1 4.7 0.019 A-40 24 -36- 201113328 d-19 0.2 0.001 合成例41 d-14 10.7 0.017 t-1 4.5 0.018 A-41 21 d-19 0.2 0.001 合成例42 d-14 10.7 0.017 t-2 4.5 0.018 A-42 23 d-19 0.2 0.001 比較合成例1 d-6 10.7 0.019 t-3 4.3 0.019 R-l 19 比較合成例2 d-7 10.4 0.020 t-3 4.6 0.020 R-2 19 比較合成例3 d-8 12.3 0.012 t-3 2.7 0.012 R-3 18 比較合成例4 d-9 10.5 0.020 t-3 4.5 0.020 R-4 20 比較合成例5 d-10 10.8 0.019 t-3 4.2 0.019 R-5 22 比較合成例6 d-11 12.5 0.011 t-3 2.5 0.011 R-6 21 5 -37- 201113328 -¥ 醯亞胺化聚合物溶液黏度 (mPa*s) OO ON cn 03 CN CN 醯亞胺化率 (%) ίο CN cn to cn On ίο 溶液產量 (g) ?—Η 2 ON m OO cn T—H I·1 1 Os cn r-^ 03 T—^ 名稱 Β-45 B-46 B-47 B-48 B-49 B-50 B-51 B-52 蘅擊用量(g) 1.88 1.46 OO 〇〇 1-( 1 2.00 2.00 1 -< ON 1 i 1—^ 0.92 Os 0.92 Os r—H 1.52 On 1.52 種類乙酸酐吡啶乙酸酐吡啶乙酸酐吡啶乙酸酐 1 吡啶乙酸酐吡啶乙酸酐毗啶乙酸酐吡啶乙酸酐吡啶聚醯胺酸溶液黏度 (mPa，s) OO OO to 名稱 Α-46 A-47 A-48 A-49 A-50 A-51 A-52 A-53 四羧酸二酐用量 Μ好 0.018 0.018 0.020 0.020 0.012 0.012 0.019 0.019 3 On 〇\ On Os CS oq oq 種類 1—Η csi i—H CN 1 t csi 1 ' < cs 用量 0.018 0.018 0.020 0.020 0.012 1 0.012 0.019 0.019 3 10.39 10.39 10.09 10.09 12.09 12.09 10.18 10.18 種類 v〇 X3 X3 OO ΤΪ3 OO Os crs τΐί 合成例43 合成例44 合成例45 合成例46 合成例47 合成例48 合成例49 合成例50 _8ε_ 201113328 CO CSJ OO r-j On CN cn un m wn On r-1 1 Η r H oo CO . < On cn JO B-53 B-54 Β-55 B-56 B-57 B-58 B-59 B-60 oq 1-^ v〇〇〇 5^ I < cn l_ < T-H VO v〇 CO 〇\ 00 1 1 T*—^ f-H CN CN 1—^ 0.94 乙酸酐吡啶乙酸酐吡啶乙酸酐吡啶乙酸酐吡啶乙酸酐吡啶乙酸酐吡啶乙酸酐吡啶乙酸酐口比陡 oo r- 卜 A-54 A-55 Α-56 A-57 A-58 A-59 i A-60 A-61 0.018 0.018 0.017 0.017 0.017 0.019 1 0.020 0.012 1〇 CO cn cn vq On 1 ) 03 • t CN t—i T-( 1 < τ—^ 0.018 0.018 1 0.017 0.017 0.016 0.001 0.018 0.001 i- 0.019 0.001 0.011 0.001 10.47 10.47 1 10.73 1 1 10.73 10.3 寸〇\ vo cK oq cn d-10 d-10 d-14 d-14 d-14 d-15 X3 d-16 3 d-16 oo d-16 合成例51 合成例52 合成例53 合成例54 合成例55 合成例56 合成例57 合成例58 _6ε — 5 201113328 漱韆【CS1概】醯亞胺化聚合物溶液黏度 (mPa.s) cn CM oo 醯亞胺化率 (%) _ CN CN VO csj OO ON 溶液產量 (§) On m r—Η ， < 1 · 1—^ 等 i 1 r—^ 名稱 B-61 B-62 B-63 B-64 B-65 B-66 爷藏 t m 关m 用量 (g) 1.98 cn f—l. 1.86 1.44 i 1 v〇 cn· 1 i 1.76 \〇 cn 3.52 2.73 r '< 種類乙酸酐吡啶乙酸酐吡啶 1 乙酸酐口比陡乙酸酐吡啶乙酸酐吡啶乙酸酐聚醯胺酸溶液黏度 (mPa.s) VO oo 名稱 A-62 A-63 A-64 i A-65 A-66 A-67 四羧酸二酐用量 Μ好 0.019 0.018 0.017 ! :0.017 0.017 0.017 μ as MD CO CO CO CO 種類 r—i i—H r—H l~( T—< 用量 (莫耳） 0.018 0.001 0.017 0.001 0.016 0.001 0.016 0.001 0.016 0.001 0.016 10.0 寸· CO 产_ H 寸· CO 〇寸· CO cn ! 種類〇\ d-16 d-10 d-16 d-14 d-16 d-14 d-16 d-14 d-16 d-14 合成例59 合成例60 合成例61 合成例62 合成例63 合成例64 0寸· s 201113328 ON σ> OO σ\ CN ί〇 <m cn cn oo m VO 1 < 1" i ο f—Η Ο 1—^ B-67 OO εΛ ο\ <h S-10 S-ll S-12 τ—Η 1 1.77 i 1.37 r—H T—^ 2.07 $ >"·Η 0.94 2.03 oo rnl*'1 1 i 1.16 0.90 吡啶乙酸酐口比陡乙酸酐吡啶乙酸酐吡啶乙酸酐吡啶乙酸酐吡啶乙酸酐吡啶乙酸酐 _定 VO οο as [>· 1 1 A-68 j 1 1 ck OO ώ ώ R-10 R-ll R-12 0.017 0.019 0.020 0.012 0.020 0.019 0.011 CO cn vq v〇 (N ν〇 CN r—( CO ΓΟ CO cn cn 0.001 0.016 0.001 0.019 0.020 0.012 0.020 1 0.019 0.011 m cn o CO 1 10.74 10.45 12.34 10.53 1 10.81 12.45 1 d-17 d-14 d-18 \o X3 ΟΟ τΪ3 〇\ ~a d-10 d-11 合成例65 比較合成例7 比較合成例8 比較合成例9 比較合成例10 比較合成例11 比較合成例12 201113328 另外，表1和表2中的二胺和四羧酸二酐的簡稱分別是以下含義。 [二胺] 具有光反應性結構的二胺 d-Ι :上式（A-2-1-1)所示的化合物 d-2:上式（A-2-1-2)所示的化合物 d - 3 :上式（A - 2 - 1 - 3 )所示的化合物 d-4:上式（A-2-1-4)所示的化合物 d-5:上式（A-2-2-1)所示的化合物 d-6:上式（A-2-1-5)所示的化合物 d-7:上式（A-2-1-6)所示的化合物 d-8:上式（A-2-1-7)所示的化合物 d-9:上式（A-2-1-8)所示的化合物 d-ΙΟ:上式（A-2-1-9)所示的化合物 d-ΙΙ :上式（A-2-1-10)所示的化合物 d-12:上式（A-2-1-11)所示的化合物 d-13:上式（A-2-1-12)所示的化合物 d-14:上式（A-2-1-13)所示的化合物上式（A -1)所示的二胺 d-15:上式（A-1-1)所示的化合物 d-16:上式（A-1-2)所示的化合物 d-17:上式（A-1-3)所示的化合物 d-18:上式（A-1-4)所示的化合物 -42- 201113328 上式（Α·3)所示的二胺 d-19: Ν，Ν -二烯丙基- 2,4 -二胺基苯胺其他二胺 d-20: 3,5 -二胺基苯甲酸膽甾院基酯 [四羧酸二酐] t-Ι : 3，5,6 -三羧基-2-羧甲基降冰片烷-2:3,5:6 -二酐 t-2 : 2,4,6,8-四羧基二環[3·3.0]辛烷·2:4,6:8-二酐 t-3: 2,3,5-三羧基環戊基乙酸二酐 <其他聚合物的合成例> [其他聚醯胺酸的合成] 合成例OPA-1 將作爲四羧酸二酐的98g(〇_50莫耳）1，2,3,4·環丁烷四羧酸二酐和1 10g(0.50莫耳）均苯四羧酸二酐以及作爲二胺的200g(1.0莫耳）4,4，-二胺基苯基甲烷’溶解到由230g的 N -甲基-2-吡咯烷酮和r-丁內酯形成的2l〇〇g混合溶劑中，在4 0 °C下反應3小時後’追加1，3 5 0 g的r - 丁內酯，得到含有ίο重量％聚醯胺酸（OPA-1)的溶液。該聚醯胺酸溶液的溶液黏度爲125mPa_s。合成例OPA-2 將作爲四羧酸二酐的2002(1.0莫耳Η，2,3,4·環丁烷四羧酸二酐和作爲二胺的210g(1.0莫耳）的2,2、二甲基-4,4’-二胺基聯苯，溶解到由370g的N -甲基-2-Π比略·院酮和3300g 的r - 丁內酯形成的混合溶劑中’在4 0 °C下反應3小時’ -43- 201113328 得到含有10重量％聚醯胺酸（OPA-2)的溶液。該聚醯胺酸溶液的溶液黏度爲160mPa-s。實施例1 I. 液晶配向劑的製備將作爲聚合物的上述合成例PA-1得到的含有聚醯胺酸（PA-1)的溶液和上述合成例OPA-1得到的含有聚醯胺酸 (OPA-1)的溶液，以聚醯胺酸（PA-1):聚醯胺酸 (OPA-1 ) = 20:80(重量比）混合，在其中加入τ -丁內酯（BL)、 N -甲基-2-吡咯烷酮（NMP)和丁基溶纖劑（BC)，充分攪拌，形成溶劑組成BL:NMP:BC = 30:20:50(重量比），固體成分濃度爲3重量％的溶液。該溶液使用孔徑1 a m的過濾器過濾，製備液晶配向劑。 II. 液晶胞的製造在帶有由ITO膜的透明電極的玻璃基板的透明電極面上，通過旋塗法，塗布上述製備的液晶配向劑，在8 0。(：的熱板上，加熱1分鐘（預烘焙），除去溶劑後，在箱內氮氣置換的200 °C的烘箱中，加熱40分鐘（後烘焙），形成平均膜厚1，000A的塗膜。接著，在該塗膜的表面，使用Hg-Xe 燈和格蘭-泰勒棱鏡，從基板法線傾斜4 0。的方向，照射含有波長313nm的輝線的偏光紫外線200J/m2，賦予液晶配向性，形成液晶配向膜。重複相同的操作，製造一對（兩塊）具有液晶配向膜的基板。 -44 - 201113328 在上述基板中的一塊的具有液晶配向膜的面的外周，通過絲網印刷塗布加入了直徑5.5 // m的氧化鋁球的環氧樹脂黏合劑後，將一對基板的液晶配向膜面對向配置，壓接以使各基板的紫外線光軸往基板面的投影方向逆平行，在 1 50°C下花費1小時將黏合劑熱固化。接著，從液晶注入口，在基板間的間隙中，塡充負型液晶（Merck公司製造， MLC-6608)後，通過環氧類黏合劑密封液晶注入口》然後，爲了除去液晶注入時的流動配向，將其加熱到1 20°C後，緩慢冷卻到室溫，製造液晶胞。對該液晶胞分別通過以下方法評價液晶配向性、預傾角和電壓保持率。評價結果如表3所示。 III.液晶胞的評價 (1) 液晶配向性的評價對上述製造的液晶胞，通過偏光顯微鏡觀察在2 5 °C下將5V電壓ON’OFF(施加·解除）時，有無異常區域，在沒有異常區域時，評價爲液晶配向性“良好”。 (2) 預傾角的評價根據非專利文獻 2(T. J. Scheffer et. al., J. Appl. Phys. vol. 48, pl783(1977))和非專利文獻 3(F. Nakano, et. al.，JPN. J. Appl· Phys. vol. 19，p2013(1980))中記載的方法，通過使用He-Ne鐳射的結晶旋轉法，測定預傾角。 -45- 201113328 (3) 耐光性的評價對上述製造的液晶胞，在70 °C下，以60微秒的施加時間、167毫秒的間隔施加5V的電壓後，通過（株）東陽 Technica製造的“VHR-Γ測定從解除施加到167毫秒後的電壓保持率（初期電壓保持率（VHIN))。接著，對該液晶胞，使用以碳弧爲光源的耐候儀，進行5,000小時的光照射，對光照射後的液晶胞，通過和上述同樣的方法，再次測定電壓保持率（照射後電壓保持率（VHAF))。此時，在電壓保持率的維持率（（VHAF)/(VHIN))爲90% 以上時，認爲耐光性“良好”，在不足90%時，認爲耐光性“不好”。 (4) 殘留DC電壓的評價對上述製造的液晶胞，在60°C的環境溫度下施加2小時重疊了直流5V的30Hz、3V的矩形波，通過閃光消除法求得切斷直流電壓後殘留在液晶胞內的電壓（殘留DC電壓）。該値爲餘像性質的指標，該値大約爲1 5 0 mV以下時，認爲餘像性質良好，該値大約爲50mV以下時，認爲餘像性質特別優異。實施例2~75和比較例1〜12 除了在上述實施例1中，作爲聚合物使用表3所示的種類和量以外，和實施例1同樣地製備液晶配向劑，製造液晶胞進行評價。評價結果如表3所示。 -46- 201113328 u嗽一評價結果殘留DC 電壓(mV) - CS cn 〇〇 v〇 to Co C5 1〇耐光性維持率 (VHAF/VHINX%) 94.4 94.6 91.5 92.7 93.7 1 94.0 CS Os 93.3 93.0 94.5 95.2 92.3 92.4 92.6 92.7 照射後電壓保持率 VHAF(%) 94.0 90.7 [ 93.2 91.6 92.6 92.3 94.5 91.8 91.7 91,7 92.0 初期電壓保持率 VHIN(%) 99.5 cK ON as On 99.3 99.3 〇\ ON 99.5 99.2 99.2 99.6 cn σ< ο «·〇 σ< Os 99.3 ON 99.2 預傾角 0 5 S5 £ 5 〇〇 £5 £5 S5 oo OO 〇〇〇〇液晶配向性良好良好良好良好良好良好良好良好良好良好良好良好良好良好良好液晶配向劑中使用的聚合物比例 (重量份） § g § g g g s g § 名稱聚醯胺酸(OPA-1) 聚醯胺酸(OPA-l) 聚醯胺酸(OPA-l) 聚醯胺酸(OPA-l) 聚醯胺酸(OPA-l) 聚醯胺酸(OPA-2) 1 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 比例 (重量份). 8 R 名稱聚醯胺酸(A-1) 聚醯胺酸(A-2) 聚醯胺酸(A-3) 聚醯胺酸(A-4) 聚醯胺酸(A-5) 聚醯胺酸(A-6) 聚醯胺酸(A-7) 聚醯胺酸(A-8) 聚醯胺酸(A-9) 聚醯胺酸(A-10) 聚醯胺酸(A-11) 聚醯胺酸(A-12) 聚醯胺酸(A-13) 聚醯胺酸(A-14) 聚醯胺酸(A-15) 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 201113328 5 〇〇〇〇〇〇\ S δ CO ITi s § 93.8 as 93.9 95.2 cn wS σ\ 94.4 92.8 92.3 92.3 [ 94.0 92.4 93.7 93.6 CO ON 93.0 94.3 93.6 , 1 94.3 1 93.8 | 94.4 93.5 92.2 91.9 Γ 91.7 i 93.6 91.8 93.3 93.0 92.6 99.2 99.2 99.6 丨〇\ 〇\ 99.6 99.0 cS ON 99.3 99.6 99.3 99, 99.4 99.6 99.4 99.5 〇〇 £ δ 〇〇〇〇 § S 良好良好良好良好良好良好良好良好良好良好良好 1- 良好良好良好良好 1 1 1 • 8 g § § 1 1 1 • 聚醯胺酸(0PA-1) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(0PA-2) 聚醯胺酸(0PA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) Ο ο 8 〇 Ο 聚醯胺酸(Α-⑹ 聚醯胺酸(A-17) 聚醯胺酸(A-18) 聚醯胺酸(A-19) 聚醯胺酸(A-19) 聚醯胺酸(Α-19) 聚醯胺酸(A-19) 聚醯胺酸(A-19) 聚醯胺酸(A-19) 聚醯胺酸(A-20) < i 狴 m 嵌聚醯胺酸(A-22) 1 1聚醯胺酸(A-23) 聚醯胺酸(A-24) 聚醯胺酸(A-25) 實施例16 實施例17 實施例18 實施例19 實施例20 實施例21 實施例22 實施例23 實施例24 實施例25 實施例26 實施例27 實施例28 實施例29 實施例30 _8寸· 201113328 I概«K嗽】評價結果殘留DC 電壓(mV) VO VD δ s S 耐光性維持率 (VHAF/VHINX%) 95.0 oi Os CO 〇\ 92.8 92.8 93.3 J 93.7 91.5 93.0 Η ON 98.3 99,0 98.6 照射後電壓保持率 VHAF(%) 94.2 91.6 1 92.3 92.0 92.4 92.9 93.0 90.8 92.4 91.3 97.8 to oo ON 98.0 初期電壓保持率 VHIN(%) 99.2 99.5 99.2 as 99.6 99.5 99.3 99.3 99.4 σ< ON 99.4 99.4 99.4 預傾角 0 〇\ CO 〇〇〇\ 〇〇液晶配向性良好良好良好良好良好 1 良好良好良好良好良好良好良好良好 <!□ 嵌 S 旺 m π 比例 (重量份） s g g g g 名稱聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(0ΡΑ-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(0PA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) ΤΓ S K 比例 (重量份） 8 名稱聚醯胺酸(A-26) 聚醯胺酸(A-27) 聚醯胺酸(A-28) 聚醯胺酸(A-29) 聚醯胺酸(A-30) 聚醯胺酸(Α-31) 聚醯胺酸(A-32) 聚醯胺酸(A-33) 聚醯胺酸(A-34) 聚醯胺酸(A-35) 聚醯胺酸(A-36) 聚醯胺酸(A-37) 聚醯胺酸(A-38) 實施例31 實施例32 實施例33 實施例34 實施例35 實施例36 實施例37 實施例38 實施例39 實施例40 實施例41 實施例42 實施例43 201113328 s CN 〇〇 cn vrj m m - 5 97.4 97.2 97.3 97.3 92.5 92.0 92.3 ! 94.3 94.5 93.8 91.4 94.2 92.2 96.6 96.6 96.5 96.9 92.0 90.6 1 91.6 91.9 93.9 93.9 93.4 90.6 94.2 93.5 91.4 CN 〇< ON 99.4 ON ON 99.5 99.4 99.5 99.6 99.6 99.6 99.3 99.5 σί ON 99.0 99.2 σ< ON 〇〇 Ό 〇〇 CO \〇〇〇 \〇〇〇 OO 〇〇良好良好良好良好良好良好良好良好良好良好良好 ! 良好良好良好良好 S § g g 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(0PA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(0PA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(0PA-2) ! 聚醯胺酸(0PA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(A-39) 聚醯胺酸(A-40) 聚醯胺酸(A-41) 聚醯胺酸(A42) 聚醯亞胺(B-45) 聚醯亞胺(B-46) 聚醯亞胺(B-47) 聚醯亞胺(B-48) 聚醯亞胺(B-49) 聚醯亞胺(B-50) 聚醯亞胺(B-51) i- 1 聚醯亞胺(B-52) 聚醯亞胺(B-53) 聚醯亞胺(B-54) 聚醯亞胺(B-55) 實施例44 實施例45 實施例46 實施例47 實施例48 實施例49 實施例50 實施例51 實施例52 實施例53 實施例54 實施例55 實施例56 實施例57 實施例58 s -s- 201113328 評價結果殘留DC 電壓(mV) r〇 5 VO S VO CO m CO 5 耐光性維持率 (VHAF/VHINX%) On 93.0 94.5 92.3 94.5 95.2 92.5 CS 94.3 〇\ 92.9 93.3 92.7 照射後電壓保持率 VHAF(%) 91.7 92.3 93.9 91.7 94,4 92.2 91.5 93.7 92.6 92.0 92.5 92.0 初期電壓保持率 VHIN(%) 99.5 99.3 99.4 99.3 99.5 Γ—Μ σ< ON 99.6 cn cK ON 99.3 99.5 99.0 〇s Os 99.3 預傾角 0 V〇〇〇 CC 〇〇 oo oo 〇〇〇〇〇〇〇〇〇〇〇〇 OO oo §8 液晶配向性良好良好良好良好良好良好良好良好良好良好良好良好良好 ^使用的聚合物比例 (重量份） § 1 g § 名稱聚醯胺酸(OPA-2) 聚醯胺酸(0PA-2) 聚醯胺酸(0PA-2) 聚醯胺酸(0PA-2) 1 1 聚醯胺酸(OPA-l) 聚醯胺酸(0PA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 液晶配向劑1 比例 (重量份） Ο 〇名稱聚醯亞胺(B-56) 聚醯亞胺(B-56) 聚醯亞胺(B-56); 聚醯亞胺(B-56) 聚醯亞胺(B-56) I 聚醯亞胺(B-56) 聚醯亞胺(B-57) 聚醯亞胺(B-58) 聚醯亞胺(B-59) 聚醯亞胺(B-60) 聚醯亞胺(B-61) 聚醯亞胺(B-62) 聚醯亞胺(B-63) 實施例59 實施例60 實施例61 實施例62 實施例63 實施例64 實施例65 實施例66 實施例67 實施例68 實施例69 實施例70 實施例71 201113328 Ο S 〇〇 S 〇 CS 〇〇 - 92.0 92.0 92.4 ON 88.5 86.7 89.0 84.6 85.2 寸 81.2 82.2 84.7 81.7 86.0 91.4 91.6 91.8 94.5 88.0 85.9 j 88.6 82.8 84.5 83.9 80.9 81.6 81.3 85.6 m 〇< ON 99.5 99.3 99.3 1 99.5 〇\ 〇\ 99.5 99.6 99.5 99.2 99.4 99.6 99.2 99.3 99.4 99.5 〇〇〇〇 OO CO 00 OO OO OO £5 £ 〇〇 δ £5 \〇〇〇〇〇良好良好良好良好良好良好良好良好良好良好良好良好良好良好良好良好 g g g g g 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(0PA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(0PA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯胺酸(OPA-2) 聚醯亞胺(B-64) 聚醯亞胺(B-65) 聚醯亞胺(B-66) 聚醯亞胺(B-67) 聚醯胺酸(R-l) 聚醯胺酸(R-2) 聚醯胺酸(R-3) 聚醯胺酸(R4) 聚醯胺酸(R-5) 聚醯胺酸(R-6) 1 聚醯亞胺(S-7) 聚醯亞胺(S-8) 聚醯亞胺(S-9) 聚醯亞胺(S-10) 聚醯亞胺(S-11) 聚醯亞胺(S-12) 實施例72 實施例73 實施例74 實施例75 比較例1 比較例2 比較例3 j 比較例4 比較例5 比較例6 比較例7 比較例8 比較例9 比較例10 比較例11 比較例12 201113328 【圖式簡單說明】 Μ 。 >ι\\ 【主要元件符號說明】〇 -53-Nh2 exemplifies (A-1-1) (A-1-2) H2N—^~~0—(CH2)17CH3 (A-1-4) NH2 In the above formula (Al), 'a and b are preferably different Is 0. In the above formula (A-3), Rni, 1^ and Rv are preferably a hydrogen atom which is attached to the benzene ring of the above formula (A-3), and the two amine groups are preferably 2,4-position with respect to nitrogen. . The compound represented by the above formula (A-3), preferably N,N-di-2,4-diaminoaniline, can be used as a diamine for synthesizing the aforementioned polyaminic acid. The diamine of the structure, the diamine diamine represented by the above formula (A-Ο) and (A-3) may be used together, and examples thereof include aliphatic alicyclic diamines, aromatic diamines, and diamines other than the above. Based on organic oxane and the like. The atom has a diamine other than the allylic group, and as a specific example of it, -17-201113328, respectively, as the aliphatic diamine, for example, 1,1-m-xylenediamine, 1,3-propene Diamine, 1,4-butanediamine, 1,5,pentanediamine, 1,6-hexanediamine, etc.; as the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, etc.; as the aromatic diamine, for example, p-phenylenediamine, 4, 4 '-Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diamine Biphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diaminofuran, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-di[4-(4-amino) Phenoxy)phenyl]hexafluoropropane, 2,2-bis(4.aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediphenylene)bis(aniline), 4 , 4'-(meta-phenylphenylene)-di() Amine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4- Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N -ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, 1!^'-bis(4-aminophenyl)-benzidine, 1 - Bis(4-aminophenyl)-indole, Ν'-dimethylbenzidine, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene , 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid cholesteryl ester 3,5-diaminobenzoic acid lanthyl alkyl ester, etc.; as a monoamine The organic-organic oxo oxime can be exemplified by, for example, 1,3 bis(3-aminopropyl)-tetramethyldioxane, -18-201113328, and the use of Patent Document 7 (Japanese Patent Laid-Open No. 2010-97188) : Diamine described. [Composition of diamine] The diamine used for the synthesis of the poly-proline in the present invention is a diamine containing a diamine having a photoreactive structure, and may further contain the above formula ( Group consisting of A-0) and (A-3) At least the amine and other diamines selected. As the diamine used for synthesizing the polyamic acid in the present invention, the phase diamine preferably contains 50 to 99 mol%, more preferably 70 to 95. The diamine of the reactive structure; preferably contains 1 to 50 mol%, more preferably the mol% is selected from the group consisting of the above formulas (A-0) and (A-3). An amine; may contain 20 mol% or less of the other diamine in a range of 10 mol% or less with respect to the entire diamine; the diamine used for synthesizing the polyglycolic acid in the present invention is preferably only A diamine having a photoreactive structure and at least one diamine selected from the group consisting of the above formulae (A-0) and (A). [Molecular weight modifier] In synthesizing the aforementioned polyaminic acid, a terminal polymer can be synthesized by using an appropriate molecular agent together with the tetracarboxylic acid diamine and the diamine as shown above. By forming the terminal-modified polymer', the coating property (printability) of the liquid crystal alignment agent can be improved without the effect of the invention. In the above, any one of the above-mentioned packages has 2 to 20 kinds of measurements on the whole ί ear%, and the above-mentioned has -3) constitutes a quantity regulating end modification damage -19-201113328 As the aforementioned molecular weight modifier, it can be enumerated For example, an acid monoanhydride, a monoamine compound, a monoisocyanate compound, or the like. Specific examples thereof include, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl salicylic anhydride, n-dodecyl salicylic anhydride, and tetradecyl. An alkyl salicylic anhydride, n-hexadecyl salicylic anhydride or the like; examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine. The monoisocyanate compound may, for example, be phenyl isocyanate or naphthyl isocyanate. The ratio of use of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 1 〇 k or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine used. <Synthesis of Polylysine> The ratio of use of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of polyproline is an acid anhydride of tetracarboxylic dianhydride with respect to 1 equivalent of the amine group of the diamine The ratio is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at Ot ~ 100 ° C, preferably 0.1 to 120 hours, more preferably 0.5 to 48 hours. Among them, examples of the organic solvent include N-methyl-2-pyrrolidone 'N,N-dimethylacetamide, hydrazine, hydrazine-dimethylformamide, dimethyl sulfoxide, and r-butyl. Aprotic polar solvents such as lactone, tetramethylurea, hexamethylphosphonium triamine; -20- 201113328 phenolic solvents such as cresol, xylenol, phenol, halogenated phenol. The amount (a) of the organic solvent is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine is from 1 to 50% by weight based on the total amount (a + b) of the reaction solution. The reaction solution in which the polylysine is dissolved can be obtained as described above. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after separating the polyamic acid contained in the reaction solution, or purifying the separated polyamic acid for preparing a liquid crystal alignment. Agent. When polypyridic acid is dehydrated and closed to form polyimine, the above reaction solution can be directly used for dehydration ring closure reaction; or the polylysine contained in the reaction solution can be separated and used for dehydration ring closure reaction; or separation After the polyamic acid is refined, it is used for the dehydration ring closure reaction. The separation and purification of polylysine can be carried out by a known method. <Synthesis of Polyimine> The above polyiminoimine can be obtained by imidating dehydration of the polyglycine synthesized above. The polyimine in the present invention may be a complete hydrazine imide of a glycosidic acid structure in which the prolyl acid structure as a precursor thereof is dehydrated and closed; or a part of the proline structure may be dehydrated and closed, and the guanamine A partial quinone imide that has an acid structure and a quinone ring structure. The ruthenium imidization ratio of the polyimine in the present invention is preferably 30% or more, more preferably 40 to 90%. The ruthenium imidization ratio is a ratio indicating the number of ruthenium ring structures in the percentage of the amount of the guanidine structure of the polyimine and the total amount of the quinone ring structure. The dehydration ring closure of polylysine is preferably carried out by heating the poly-proline acid in the square-21 - 201113328 method, or by dissolving the polyaminic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, as needed The heating method is carried out. Among them, it is preferred to carry out the method by the latter. In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the polyamic acid solution, examples of the dehydrating agent include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mols based on the structure of the proline of 1 mol of the prolylamine. The dehydrated closed-loop catalyst may, for example, be a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine. The amount of the dehydration ring-closure catalyst used is preferably 0.01 to 10 moles per 1 mol of the dehydrating agent. The organic solvent used in the dehydration ring closure reaction may, for example, be an organic solvent exemplified as a solvent used for the synthesis of polyamic acid. The reaction temperature as the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours. Thus, a reaction solution containing polyimine can be obtained. The reaction solution can be directly used for preparing a liquid crystal alignment agent, or can be used for preparing a liquid crystal alignment agent after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution; and can also be used for preparing a liquid crystal alignment agent after separating the polyimine. Or after the isolated polyimine is refined, it is used to prepare a liquid crystal alignment agent. These refining operations fp can be carried out according to a known method. <Other components> The liquid crystal alignment film of the present invention contains the above specific polymer as a must-have component, and may contain other components as needed. -22-201113328, for example, a polymer other than the above specific polymer (hereinafter referred to as another polymer) and a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy") Compound "), a functional decane compound, and the like. [Other Polymers] The above other polymers can be used to improve solution properties and electrical properties. The other polymer is a polymer other than the specific polymer as described above, and examples thereof include polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine having no diamine having a photoreactive structure (hereinafter, It is called "other poly-proline"), a polyimine formed by dehydration of the poly-proline (hereinafter referred to as "other polyimine"), polyphthalate, polyester, polyfluorene An amine, a polyoxyalkylene, a cellulose derivative, a polyacetal, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, or the like. Among them, other polyamines and other polyimines are preferred, and other polyphthalamides are more preferred. The tetracarboxylic dianhydride used for the synthesis of the above-mentioned other polyaminic acid or other polyimine, 'the same tetracarboxylic dianhydride as the above-mentioned tetracarboxylic dianhydride for synthesizing a specific polymer, At least one selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride is preferably used. Examples of the diamine used for the synthesis of other polyamines or other polyimines include diamines other than the diamines having a photoreactive structure, and the use of the diamines for synthesizing a specific polymer. All diamines, preferably containing more than 50% by mole, more preferably containing more than 80% by mole, selected from the group consisting of -23-201113328 phenyldiamine, 4,4-diaminodiphenylmethane and 4, At least one of the group consisting of 4_diaminodiphenyl ether. The ratio of use of the other polymer is preferably 90% 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 described above), and more preferably 50 to 80% by weight. [Epoxy compound] Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether 'propylene glycol diglycidyl ether', tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl alcohol. Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromopentyl glycol diglycidyl ether, 1,3,5 ,6-tetraglycidyl-2,4-hexanediol 'Ν,Ν,Ν',Ν'-tetraglycidyl-m-xylylenediamine, 1,3-bis(Ν,Ν-diglycidyl Aminomethyl)cyclohexane, hydrazine, hydrazine, hydrazine, Ν'-tetraglycidyl- 4,4'-diaminodiphenylmethane, anthracene, fluorene-diglycidyl-benzylamine , hydrazine, hydrazine-diglycidyl-aminomethylcyclohexane, and the like. The mixing ratio of the epoxy group-containing compound 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 of the polymer. [Functional sand compound] The functional decane compound may, for example, be 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane or amylpropyltrimethoxydecane. 2-Aminopropyltriethoxydecane, N-(2-aminoethyl)-3.aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Methyl dimethoxy decane, 3- guanidinyl propyl trimethoxy decane, 3- guanidinium propyl-24- 201113328 based triethoxy oxalate 'N-ethoxy fluorenyl-3-aminopropyl Trimethoxy silane, N. ethoxycarbonyl-3-aminopropyl triethoxy decane, triethoxymethoxymethyl propyl triethylamine, N-trimethoxyformane Propyl triethylidene triamine, 10-trimethoxycarbamimidyl-1,4,7-triazadecane, 1〇·triethoxycarbamido-1,4,7-triazole Heteroane, 9-trimethoxyformamidin, 3,6-diazaindolyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N -benzyl-3-aminopropyltrimethoxyphthalate, N-nodal-3-aminopropyltriethoxylate, N-phenyl-3-amine-propyl Trimethoxy oxatane, fluorenyl phenyl-3-aminopropyltriethoxy decane, Ν_bis (oxidized exoethyl)-3-aminopropyltrimethoxy sand, Ν-II (oxidation Ethylene)_3_aminopropyltriethoxydecane, and the like. The mixing ratio of these functional decane compounds is preferably 2 parts by weight or less, more preferably 〇 2 to 0.2 parts by weight, based on 100 parts by weight of the total of the polymer. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention is preferably obtained by dissolving and dissolving the above specific polymer and other additives optionally mixed as needed in an organic solvent. The organic solvent which can be used for the liquid crystal alignment agent of the present invention is exemplified as a solvent which is used as a solvent for the synthesis reaction of polyglycine. Further, it is also possible to appropriately select an organic solvent which has been confirmed as a poor solvent of polylysine and polyimine. Preferable examples of the organic solvent include, for example, fluorene-methyl-2-pyrrolidone, r-butyrolactone, r-butyrolactone 'N,N-dimethylformamide, hydrazine, hydrazine- Dimethylethyl-25- 201113328 decylamine, 4-carbyl-4-methyl-2.pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate 'methyl methoxypropionate Ethyl ethoxy 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 glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, Diisoamyl ether and the like. They may be used singly or in combination of two or more. The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the organic solvent to the total weight of the liquid crystal alignment agent in the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., preferably 1 ~ 1 〇% by weight range. That is, the liquid crystal alignment agent of the present invention can form a coating film of a liquid crystal alignment film by applying it to the surface of the substrate to remove the organic solvent, but when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small, possibly It is difficult to obtain a good liquid crystal alignment film; on the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large, and it may be difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent is increased, and coating is performed. The nature may be insufficient. The range of the particularly preferable solid content concentration varies depending on the method employed in coating the liquid crystal alignment agent on the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is used, the solid content concentration is in the range of 3 to 9 wt%, and thus the solution viscosity -26-201113328 is particularly preferably in the range of 12 to 50 mPa·s. When the inkjet method is used, the solid content concentration is 1 to 5 wt%, and the solution viscosity is particularly preferably in the range of 3 to 15 mPa·s. <Method of Forming Liquid Crystal Alignment Film> The liquid crystal alignment agent of the present invention is suitably used for forming a liquid crystal alignment film by a photo-alignment method. As a method of forming a liquid crystal alignment film, for example, a liquid crystal alignment agent is applied onto a substrate to form a coating film, and the coating film is irradiated with polarized or non-polarized ultraviolet rays from a direction inclined with respect to the coating film surface, or from the opposite coating. A method in which a polarized ultraviolet ray is irradiated onto the coating film in a direction perpendicular to the film surface to impart a liquid crystal alignment energy to the coating film. First, the liquid crystal alignment agent of the present invention is applied to the transparent conductive film side of the substrate on which the pattern-like transparent conductive film is provided by an appropriate coating method such as a light coating method, a spin coating method, a printing method, or an inkjet method. After coating, the coated film is formed by preheating (prebaking) the coated surface and then firing (post-baking). The pre-baking conditions are, for example, carried out at 40 to 120 ° C for 5 minutes, and the post-baking conditions are preferably 120 to 300 ° C, more preferably 150 to 250 ° C, preferably 5 to 200 minutes. Better for 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.0 0 1 to 1//m ' more preferably 〇. 〇〇 5 ~ 0.5 " m. As the substrate ', for example, glass such as float glass or soda glass; plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate can be used. Transparent substrate, etc. -27-201113328 As the transparent conductive film, a NESA film formed of Sn 2 , an ITO film formed of ImCh-SnO 2 , or the like can be used. In order to form the pattern of these transparent conductive films, a photolithography method or a method of using a mask when forming a transparent conductive film, or the like can be used. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate or the transparent conductive film and the coating film, a functional decane compound, a titanate compound or the like may be applied to the substrate and the transparent conductive film in advance. Next, by applying a polarized or non-polarized ultraviolet ray, a liquid crystal alignment energy is imparted to the coating film, and the coating film serves as a liquid crystal alignment film. Here, as the radiation, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm, preferably ultraviolet rays having a wavelength of 300 to 400 nm can be used. When the radiation to be used is polarized (linearly polarized or partially polarized), it may be irradiated from a direction perpendicular to the surface of the coating film, or may be irradiated from an oblique direction in order to impart a pretilt angle. On the other hand, when the non-polarized light is irradiated, the irradiation must be performed in a direction inclined with respect to the opposite coating film surface. As the light source for irradiating the radiation, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light in the preferred wavelength region can be obtained by a means for using the above-mentioned light source together with, for example, a filter 'diffraction grating or the like. The irradiation amount of the radiation is preferably U/m2 or more, less than 10,000 J/m2, more preferably 10 to 3,000 gram/m2. In addition, when the liquid crystal alignment energy is imparted to the coating film formed of the currently known liquid crystal alignment agent by the photo-alignment method, it is necessary to have a radiation irradiation amount of 10,000 J/m 2 or more. However, when the 280-201113328 liquid crystal alignment agent of the present invention is used, the amount of radiation irradiation in the photo-alignment method may be 3,000 Å/m 2 or less, further 1 000 J/m 2 or less, or more preferably 300 J/m 2 or less. Good liquid crystal alignment energy helps to reduce the manufacturing cost of liquid crystal display elements. <Manufacturing Method of Liquid Crystal Display Element> The liquid crystal display element of the present invention has a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. The liquid crystal display element of the present invention can be produced, for example, as follows. Two substrates on which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal cells were formed by disposing liquid crystal between the two substrates. When manufacturing a liquid crystal cell, for example, the following two methods can be cited. The first method is a currently known method. First, in order to arrange the liquid crystal alignment films in the opposite direction, the two substrates are arranged to face each other through a gap (box gap), and the peripheral portions of the two substrates are bonded together using a sealant, and are separated by the surface of the substrate and the sealant. After filling the liquid crystal into the interstitial space, the injection hole is sealed to manufacture a liquid crystal cell. The second method is a method called the ODF (One Drop Fill) method. A predetermined position on one of the two substrates forming the liquid crystal alignment film is coated with, for example, a UV curable sealant, and then liquid crystal is dropped on the liquid crystal alignment film surface, and the other substrate is bonded to the liquid crystal alignment film. Opposite, then 'the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby the liquid crystal cell can be manufactured. -29- 201113328 In the case of either method, it is desirable to heat the liquid crystal cell to the temperature of the liquid crystal isotropic used, and then slowly cool to room temperature to remove the flow alignment during liquid crystal injection. Then pass 'on the outside of the liquid crystal cell. The liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on the surface. When the liquid crystal alignment film is horizontally aligned, by adjusting the angle formed by the polarization direction of the linearly polarized radiation and the angle between each substrate and the polarizing plate in the two substrates on which the liquid crystal alignment film is formed, it is possible to obtain a TN type or an STN type. A liquid crystal display element of a liquid crystal cell. On the other hand, when the liquid crystal alignment film has a vertical alignment property, the liquid crystal cell is formed in parallel with the direction of the easily aligned axis of the two substrates forming the liquid crystal alignment film, and the polarizing plate is bonded thereto to have a polarization direction thereof. The easily aligning axis forms an angle of 45°, and a liquid crystal display element having a vertically aligned liquid crystal cell can be formed. As the sealant, for example, an epoxy resin containing an alumina sphere as a separator and a curing agent can be used. As the liquid crystal, for example, a nematic liquid crystal 'disc liquid crystal or the like is preferably used. When it is a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic liquid crystal having a positive dielectric anisotropy is preferable, and for example, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, or a triplet can be used. a benzene liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclohistamine liquid crystal, a cubic liquid crystal, or the like. Further, a cholesteric liquid crystal such as chopsty1 chloride, cholesterol 壬201113328 acid ester or cholesterol carbonate may be further added to the 'liquid crystal liquid'; and the trade names "C-15" and "CB-15" (Merck) A chiral reagent sold by the company; a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate. On the other hand, in the case of a vertical alignment type liquid crystal cell, a nematic liquid crystal having a negative dielectric anisotropy is preferably used, for example, a dicyanobenzene liquid crystal, a germanium well liquid crystal, a Schiff base liquid crystal, or the like. An azo-based liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, or the like. The polarizing plate used for the outer side of the liquid crystal cell may be a polarizing film formed by sandwiching a polarizing film called absorbing iodine called "H film" with a cellulose acetate protective film while extending the alignment of the polyvinyl alcohol, or by the ruthenium film itself. A polarizing plate is formed. The liquid crystal display element of the present invention thus produced is excellent in display performance, and the display performance is not deteriorated even when used for a long period of time. [Examples] Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by these examples. The solution viscosity of the polymer and the ruthenium iodide ratio of the polyimine in the following synthesis examples were evaluated by the following methods. [Solid viscosity of the polymer] The solution viscosity (mPa.s) of the polymer was measured at 25 ° C for each polymer solution using a Ε-type rotational viscometer. -31 - 201113328 <Rigmine imidization ratio of polyimine> A polyimine-containing solution obtained in each synthesis example was fractionated, poured into pure water, and the obtained precipitate was filtered to separate polyimine. The polyimine was sufficiently dried under reduced pressure at room temperature, dissolved in dimethyl hydrazine hydride, and the z-NMR measured from room temperature using tetramethyl decane as a reference material, by the following mathematics Equation (1) is obtained.醯 imidization ratio (%) = (l-A'/A, a)xl00 (1) (In the mathematical formula (1), A1 is the peak area of the proton from the NH group which appears near the chemical shift l〇ppm , A2 is the peak area from other protons, and α is the ratio of the number of other protons to the protons of the sulfhydryl group in the precursor of poly(imine). <Synthesis Example and Comparative Synthesis Example of Specific Polymer> [Synthesis Example of Polylysine] Synthesis Examples 1 to 4 2 and Comparative Synthesis Examples 1 to 6 The kinds and amounts of diamines and IVs shown in Table 1 The carboxylic acid dianhydride was mixed, and dissolved in 135 g of hydrazine-methyl-2-pyrrolidone in this order, and the total weight of the diamine and the tetracarboxylic dianhydride was 10% by weight based on the total weight of the reaction solution. The solution was reacted at 60 ° C for 6 hours to obtain 150 g each of 10% by weight of polyamines (A-1) to (A-42) and (R-1) to (R-6). Solution. The viscosity of each solution obtained here is shown in Table 1. [Synthesis of Polyimine] Synthesis Examples 43 to 65 and Comparative Synthesis Examples 7 to 12 - 32 to 201113328 The kinds and amounts of diamine and tetracarboxylic dianhydride shown in Table 2 were mixed 'in this order, added to 1 3 g of N·methyl-2-pyrrolidone dissolved in 'and formed a total weight of diamine and tetracarboxylic dianhydride relative to the total weight of the reaction solution of 10% by weight of the solution, at 60 ° C The next reaction was carried out for 6 hours' to obtain 150 g each of a solution containing 10% by weight of polyamic acid. The viscosity of each solution obtained here is shown in Table 2. Next, pyridine and acetic anhydride in an amount shown in Table 2 were added to each of the solutions containing each polyamic acid, 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 N-methyl-2-pyrrolidone (by this operation, the pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system), thereby obtaining 1 respectively. A solution of 5 wt% polyimine (B-45) ~ (B-67) and (S-7) ~ (S-12). The yield of each solution, a small amount of each solution was taken out, and N-methyl-2-pyrrolidone was diluted to 10% by weight to determine the solution viscosity and the ruthenium imidization ratio of each polyimine was shown in Table 2, respectively. -33- 201113328 [Table 1] Diamine tetracarboxylic acid dianhydride polyamine acid type Dosage solution viscosity (g) Mo ear) Species (g) (mole) Name (mPa.s) Synthesis example 1 d-1 9.7 0.021 t-1 5.3 0.021 Al 25 Synthesis Example 2 d-2 9.9 0.020 t-1 5.1 0.020 A-2 16 Synthesis Example 3 d-3 10.0 0.020 t-1 5.0 0.020 A-3 16 Synthesis Example 4 d-4 10.2 0.019 t-1 4.8 0.019 A-4 19 Synthesis Example 5 d-5 9.6 0.022 M 5.4 0.022 A-5 23 Synthesis Example 6 d-6 10.4 0.018 t-1 4.6 0.018 A-6 20 Synthesis Example 7 d-6 10.4 0.018 T-2 4.6 0.018 A-7 22 Synthesis Example 8 d-7 10.1 0.020 t-1 4.9 0.020 A-8 21 Synthesis Example 9 d-7 10.1 0.020 t-2 4.9 0.020 A-9 15 Synthesis Example 10 d-8 12.1 0.012 t-1 2.9 0.012 A-10 22 Synthesis Example 11 d-8 12.1 0.012 t-2 2.9 0.012 A-ll 16 Synthesis Example 12 d-9 10.2 0.019 t-1 4.8 0.019 A-12 21 Synthesis Example 13 d-9 10.2 0.019 t-2 4.8 0.019 A-13 20 Synthesis Example 14 d-10 10.5 0.018 t-1 4.5 0.018 A-14 19 Synthesis Example 15 d-10 10.5 0.018 t-2 4.5 0.018 A-15 15 Synthesis Example 16 d- 11 12.2 0.011 t-1 2.8 0.011 A-16 19 Synthesis Example 17 d-12 12.0 0.012 t-1 3.0 0.012 A-17 20 Synthesis Example 18 d-13 12 .1 0.012 t-1 2.9 0.012 A-18 25 Synthesis Example 19 d-14 10.7 0.017 t-1 4.3 0.017 A-19 20 Synthesis Example 20 d-14 10.7 0.017 t-2 4.3 0.017 A-20 25 Synthesis Example 21 d -14 10.3 0.016 t-1 4.3 0.017 A-21 19 -34- 201113328 d-15 0.4 0.001 Synthesis Example 22 d-6 9.9 0.018 t-1 4.6 0.019 A-22 15 d-16 0.4 0.001 Synthesis Example 23 d-7 9.6 0.019 t-1 4.9 0.020 A-23 24 d-16 0.4 0.001 Synthesis Example 24 d-8 11.8 0.011 t-1 3.0 0.012 A-24 21 d-16 0.3 0.001 Synthesis Example 25 d-9 9.7 0.018 t-1 4.9 0.019 A-25 16 d-16 0.4 0.001 Synthesis Example 26 d-10 10.0 0.017 t-1 4.6 0.018 A-26 24 d-16 0.4 0.001 Synthesis Example 27 d-14 10.3 0.016 t-1 4.3 0.017 A-27 21 d -16 0.4 0.001 Synthesis Example 28 d-14 10.3 0.016 t-2 4.3 0.017 A-28 18 d-16 0.4 0.001 Synthesis Example 29 d-6 10.0 0.018 t-1 4.7 0.019 A-29 20 d-17 0.4 0.001 Synthesis Example 30 d-7 9.7 0.019 t-1 5.0 0.020 A-30 22 d-17 0.4 0.001 -35- 201113328 [Table 1] Continued Table Diamine Tetracarboxylic Acid Dihydride Polyamine Application Amount of Solution Viscosity (g) ( Moer) Type (g) (Mohr) Name (mPa.s) d-8 11.8 0.011 A -31 Synthesis Example 31 d-17 0.2 0.001 t-1 3.0 0.012 21 d-9 9.8 0.018 A-32 Synthesis Example 32 d-17 0.4 0.001 t-1 4.9 0.019 24 d-10 10.1 0.017 A-33 Synthesis Example 33 d -17 0.3 0.001 t-1 4.6 0.018 21 d-14 10.3 0.016 A-34 Synthesis Example 34 d-17 0.3 0.001 t-1 4.3 0.017 24 d-14 10.3 0.016 A-35 Synthesis Example 35 d-17 0.3 0.001 t- 2 4.3 0.017 25 d-6 10.3 0.018 A-36 Synthesis Example 36 d-19 0.2 0.001 t-1 4.8 0.019 16 d-7 10.0 0.019 A-37 Synthesis Example 37 d-19 0.2 0.001 t-1 5.1 0.020 23 d- 8 12.3 0.012 A-38 Synthesis Example 38 d-19 0.1 0.001 t-1 3.1 0.012 20 d-9 10.1 0.019 A-39 Synthesis Example 39 d-19 0.2 0.001 t-1 5.0 0.020 20 Synthesis Example 40 d-10 10.4 0.018 T-1 4.7 0.019 A-40 24 -36- 201113328 d-19 0.2 0.001 Synthesis Example 41 d-14 10.7 0.017 t-1 4.5 0.018 A-41 21 d-19 0.2 0.001 Synthesis Example 42 d-14 10.7 0.017 t- 2 4.5 0.018 A-42 23 d-19 0.2 0.001 Comparative Synthesis Example 1 d-6 10.7 0.019 t-3 4.3 0.019 Rl 19 Comparative Synthesis Example 2 d-7 10.4 0.020 t-3 4.6 0.020 R-2 19 Comparative Synthesis Example 3 D-8 12.3 0.012 t-3 2.7 0.012 R-3 18 Comparative Synthesis Example 4 d-9 10.5 0.020 t-3 4.5 0.020 R-4 20 Comparative Synthesis Example 5 d-10 10.8 0.019 t-3 4.2 0.019 R-5 22 Comparative Synthesis Example 6 d-11 12.5 0.011 T-3 2.5 0.011 R-6 21 5 -37- 201113328 -¥ 醯i-imidized polymer solution viscosity (mPa*s) OO ON cn 03 CN CN 醯imination rate (%) ίο CN cn to cn On ίο Solution yield (g) ?—Η 2 ON m OO cn T—HI·1 1 Os cn r-^ 03 T—^ Name Β-45 B-46 B-47 B-48 B-49 B-50 B-51 B-52 Sniping dosage (g) 1.88 1.46 OO 〇〇1-( 1 2.00 2.00 1 - < ON 1 i 1 —^ 0.92 Os 0.92 Os r—H 1.52 On 1.52 Kinds of acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride 1 pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine poly phthalic acid solution Viscosity (mPa, s) OO OO to name Α-46 A-47 A-48 A-49 A-50 A-51 A-52 A-53 The amount of tetracarboxylic dianhydride is good 0.018 0.018 0.020 0.020 0.012 0.012 0.019 0.019 3 On 〇\ On Os CS oq oq Type 1—Η csi i—H CN 1 t csi 1 ' < cs dosage 0.018 0.018 0.020 0.020 0.012 1 0.012 0.019 0.019 3 10.39 10.39 10.09 10.09 12.09 12.09 10.18 10.18 Species v〇X3 X3 OO ΤΪ3 OO Os crs τΐί Synthesis Example 43 Synthesis Example 44 Synthesis Example 45 Synthesis Example 46 Synthesis Example 47 Synthesis Example 48 Synthesis Example 49 Synthesis Example 50 _8ε_201113328 CO CSJ OO rj On CN cn un m wn On r-1 1 Η r H oo CO . < On cn JO B-53 B-54 Β-55 B-56 B-57 B-58 B-59 B-60 oq 1-^ v〇〇〇 5^ I < cn l_ <TH VO v〇CO 〇\ 00 1 1 T*—^ fH CN CN 1—^ 0.94 Acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride mouth ratio steep oo R- 卜 A-54 A-55 Α-56 A-57 A-58 A-59 i A-60 A-61 0.018 0.018 0.017 0.017 0.017 0.019 1 0.020 0.012 1〇CO cn cn vq On 1 ) 03 • t CN T-i T-( 1 < τ—^ 0.018 0.018 1 0.017 0.017 0.016 0.001 0.018 0.001 i- 0.019 0.001 0.011 0.001 10.47 10.47 1 10.73 1 1 10.73 10.3 inch 〇 \ vo cK oq cn d-10 d-10 d-14 d-14 d-14 D-15 X3 d-16 3 d-16 oo d-16 Synthesis Example 51 Synthesis Example 52 Synthesis Example 53 Synthesis Example 54 Synthesis Example 55 Synthesis Example 56 Synthesis Example 57 Synthesis Example 58 _6 ε — 5 201113328 漱千 [CS1 Overview] 醯Amidated polymer solution viscosity (mPa.s) cn CM oo 醯 imidization rate (%) _ CN CN VO csj OO ON Solution yield (§) On mr-Η , < 1 · 1—^ et i i r —^ Name B-61 B-62 B-63 B-64 B-65 B-66 爷t tm off m dosage (g) 1.98 cn f-l. 1.86 1.44 i 1 v〇cn· 1 i 1.76 \〇cn 3.52 2.73 r ' < kind of acetic anhydride pyridine acetic anhydride pyridine 1 acetic anhydride mouth ratio steep acetic anhydride pyridine acetic anhydride pyridine acetic anhydride polyamine acid solution viscosity (mPa.s) VO oo name A-62 A-63 A-64 i A-65 A-66 A-67 tetracarboxylic dianhydride dosage is good 0.019 0.018 0.017 ! :0.017 0.017 0.017 μ as MD CO CO CO CO kind r-ii-H r-H l~( T- < Dosage (mole) 0.018 0.001 0.017 0.001 0.016 0.001 0.016 0.001 0.016 0.001 0.016 10.0 inch · CO Production _ H inch · CO 〇 inch · CO cn ! Type 〇 \ d-16 d-10 d-16 d-14 d -16 d-14 d-16 d-14 d-16 d-14 Synthesis Example 59 Synthesis Example 60 Synthesis Example 61 Synthesis Example 62 Synthesis Example 63 Synthesis Example 64 0 inch·s 201113328 ON σ> OO σ\ CN 〇 <m cn cn oo m VO 1 <1" i ο f—Η Ο 1—^ B-67 OO εΛ ο\ <h S-10 S-ll S-12 τ-Η 1 1.77 i 1.37 r-HT-^ 2.07 $ >"·Η 0.94 2.03 oo rnl*'1 1 i 1.16 0.90 pyridine acetic anhydride mouth ratio steep Anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride pyridine acetic anhydride _ VO οο as [>· 1 1 A-68 j 1 1 ck OO ώ ώ R-10 R-ll R-12 0.017 0.019 0.020 0.012 0.020 0.019 0.011 CO cn vq v〇(N ν〇CN r—( CO ΓΟ CO cn cn 0.001 0.016 0.001 0.019 0.020 0.012 0.020 1 0.019 0.011 m cn o CO 1 10.74 10.45 12.34 10.53 1 10.81 12.45 1 d-17 d-14 D-18 \o X3 ΟΟ τΪ3 〇\ ~a d-10 d-11 Synthesis Example 65 Comparative Synthesis Example 7 Comparative Synthesis Example 8 Comparative Synthesis Example 9 Comparative Synthesis Example 10 Comparative Synthesis Example 11 Comparative Synthesis Example 12 201113328 In addition, Table 1 The abbreviations of the diamine and the tetracarboxylic dianhydride in Table 2 are respectively the following meanings. [Diamine] Diamine d-Ι having a photoreactive structure: represented by the above formula (A-2-1-1) Compound d-2: Compound d - 3 represented by the above formula (A-2-1-2): Compound d-4 represented by the above formula (A - 2 - 1 - 3 ): the above formula (A-2- 1-4) shown Compound d-5: Compound d-6 represented by the above formula (A-2-2-1): Compound d-7 represented by the above formula (A-2-1-5): the above formula (A-2- 1-6) Compound d-8: Compound d-9 represented by the above formula (A-2-1-7): Compound d-oxime represented by the above formula (A-2-1-8): Compound d-ΙΙ represented by the above formula (A-2-1-9): Compound d-12 represented by the above formula (A-2-1-10): the above formula (A-2-1-11) Compound d-13: Compound d-14 represented by the above formula (A-2-1-12): the compound represented by the above formula (A-2-1-13) is represented by the above formula (A-1) Diamine d-15: Compound d-16 represented by the above formula (A-1-1): Compound d-17 represented by the above formula (A-1-2): the above formula (A-1-3) Compound d-18 shown: Compound represented by the above formula (A-1-4)-42-201113328 Diamine d-19 represented by the above formula (Α·3): Ν, Ν-diallyl- 2,4-diaminoaniline other diamine d-20: 3,5-diaminobenzoic acid cholesteryl ester [tetracarboxylic dianhydride] t-Ι : 3,5,6-tricarboxy-2 -carboxymethylnorbornane-2:3,5:6-dianhydride t-2 : 2,4,6,8-tetracarboxybicyclo[3·3.0]octane·2:4,6:8- Diacetate t-3: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride <Synthesis Example of Other Polymer> [Synthesis of Other Polylysine] Synthesis Example OPA-1 98 g (〇_50 mol) of tetracarboxylic dianhydride as 1,2,3,4·cyclobutene Alkane tetracarboxylic dianhydride and 1 10 g (0.50 mol) of pyromellitic dianhydride and 200 g (1.0 mol) of 4,4,-diaminophenylmethane as a diamine dissolved in 230 g of N - In a mixed solvent of 2 - 10 g of methyl-2-pyrrolidone and r-butyrolactone, after reacting at 40 ° C for 3 hours, '1,350 g of r -butyrolactone was added to obtain Ίο% by weight of a solution of polyaminic acid (OPA-1). The solution viscosity of the polylysine solution was 125 mPa_s. Synthesis Example OPA-2 will be 2002 as a tetracarboxylic dianhydride (1.0 moles, 2,3,4·cyclobutane tetracarboxylic dianhydride and 210 g (1.0 mole) as a diamine 2, 2 Dimethyl-4,4'-diaminobiphenyl dissolved in a mixed solvent of 370 g of N-methyl-2-indole ketone and 3300 g of r-butyrolactone 'at 40 Reaction at ° C for 3 hours '-43- 201113328 A solution containing 10% by weight of polyaminic acid (OPA-2) was obtained. The solution viscosity of the polyaminic acid solution was 160 mPa-s. Example 1 I. Liquid Crystal Aligning Agent Preparation of a polyglycine (PA-1)-containing solution obtained as the above-mentioned synthesis example PA-1 of the polymer and a solution containing poly-proline (OPA-1) obtained in the above-mentioned synthesis example OPA-1 Polylysine (PA-1): poly (proline) (OPA-1) = 20:80 (by weight), in which τ-butyrolactone (BL), N-methyl-2-pyrrolidone ( NMP) and butyl cellosolve (BC) were thoroughly stirred to form a solution having a solvent composition of BL:NMP:BC = 30:20:50 (weight ratio) and a solid concentration of 3% by weight. The solution was filtered using a pore size of 1 am. Filtering to prepare liquid crystal alignment agent II. Fabrication of liquid crystal cell The liquid crystal alignment agent prepared above was applied onto the transparent electrode surface of the glass substrate having the transparent electrode of the ITO film by a spin coating method, and heated on a hot plate of 80° for 1 minute (prebaking) to remove After the solvent, it was heated in an oven at 200 ° C in a nitrogen atmosphere in a box for 40 minutes (post-baking) to form a coating film having an average film thickness of 1,000 A. Next, on the surface of the coating film, an Hg-Xe lamp and The Glan-Taylor prism is irradiated with a polarized ultraviolet ray of 200 J/m2 containing a ray of a wavelength of 313 nm from the direction in which the substrate normal is inclined by 40 Å to impart alignment property to the liquid crystal to form a liquid crystal alignment film. The same operation is repeated to produce a pair (two Block) A substrate having a liquid crystal alignment film. -44 - 201113328 An epoxy resin bonded to an alumina ball having a diameter of 5.5 // m by screen printing is applied to the outer periphery of a surface of a substrate having a liquid crystal alignment film. After the agent, the liquid crystal alignment films of the pair of substrates were placed facing each other, and the pressure was applied so that the ultraviolet light axes of the respective substrates were reversely parallel to the projection direction of the substrate surface, and the adhesive was thermally cured at 150 ° C for 1 hour. then, In the liquid crystal injection port, the negative liquid crystal (MLC-6608, manufactured by Merck, Inc.) is sealed in the gap between the substrates, and the liquid crystal injection port is sealed by an epoxy-based adhesive. Then, in order to remove the flow alignment during liquid crystal injection, After heating to 1200 ° C, the film was slowly cooled to room temperature to produce a liquid crystal cell. The liquid crystal alignment, the pretilt angle, and the voltage holding ratio were evaluated for the liquid crystal cell by the following methods, respectively. The evaluation results are shown in Table 3. III. Evaluation of Liquid Crystal Cell (1) Evaluation of Liquid Crystal Alignment When the 5 V voltage was turned ON (applied and released) at 25 ° C by a polarizing microscope, there was no abnormal region. In the case of an abnormal region, the liquid crystal alignment property was evaluated as "good". (2) Evaluation of the pretilt angle according to Non-Patent Document 2 (TJ Scheffer et. al., J. Appl. Phys. vol. 48, pl783 (1977)) and Non-Patent Document 3 (F. Nakano, et. al., The method described in JPN. J. Appl. Phys. vol. 19, p2013 (1980)) measures the pretilt angle by a crystal rotation method using He-Ne laser. -45-201113328 (3) Evaluation of light resistance The liquid crystal cell produced by the above-mentioned liquid crystal cell was applied at a temperature of 70 ° C at an application time of 60 μsec and a voltage of 5 V at a time of 167 msec, and then manufactured by Toyo Technica Co., Ltd. "VHR-Γ measured the voltage holding ratio (initial voltage holding ratio (VHIN)) after the application was released for 167 msec. Then, the liquid crystal cell was irradiated with a weathering instrument using a carbon arc as a light source for 5,000 hours. The voltage holding ratio (voltage holding ratio (VHAF) after irradiation) was measured again in the same manner as described above for the liquid crystal cell after the light irradiation. At this time, the rate of retention of the voltage holding ratio ((VHAF) / (VHIN)) When it is 90% or more, the light resistance is considered to be "good", and when it is less than 90%, the light resistance is considered to be "not good". (4) Evaluation of residual DC voltage For the liquid crystal cell produced above, at 60 ° C At a temperature of 2 hours, a rectangular wave of 30 Hz and 3 V with a direct current of 5 V was superimposed, and a voltage (residual DC voltage) remaining in the liquid crystal cell after the DC voltage was cut by the flash elimination method was obtained. This is an indicator of the afterimage property. When the 値 is approximately 1 500 mV or less, The afterimage property is good, and when the enthalpy is about 50 mV or less, the afterimage property is particularly excellent. Examples 2 to 75 and Comparative Examples 1 to 12 In addition to the above-described Example 1, the types shown in Table 3 were used as the polymer. A liquid crystal alignment agent was prepared in the same manner as in Example 1, and liquid crystal cells were produced and evaluated. The evaluation results are shown in Table 3. -46-201113328 u嗽一 Evaluation result Residual DC voltage (mV) - CS cn 〇〇v 〇to Co C5 1〇Lightfastness retention rate (VHAF/VHINX%) 94.4 94.6 91.5 92.7 93.7 1 94.0 CS Os 93.3 93.0 94.5 95.2 92.3 92.4 92.6 92.7 Voltage retention after irradiation VHAF(%) 94.0 90.7 [ 93.2 91.6 92.6 92.3 94.5 91.8 91.7 91,7 92.0 Initial voltage holding ratio VHIN(%) 99.5 cK ON as On 99.3 99.3 〇\ON 99.5 99.2 99.2 99.6 cn σ < ο «·〇 σ < Os 99.3 ON 99.2 Pretilt angle 0 5 S5 £ 5 〇〇£5 £5 S5 oo OO 〇〇〇〇Good liquid crystal alignment good good good good good good good good good good good good good good good good liquid crystal alignment agent Polymer ratio (parts by weight) § g § gggsg § Name polyglycine (OPA-1) polyglycine (OPA-l) poly-proline (OPA-l) poly-proline (OPA-l) Proline (OPA-l) Poly-proline (OPA-2) 1 Poly-proline (OPA-2) Poly-proline (OPA-2) Poly-proline (OPA-2) Poly-proline ( OPA-2) Polyaminic Acid (OPA-2) Polyaminic Acid (OPA-2) Polyglycine (OPA-2) Polyglycine (OPA-2) Polyaminic Acid (OPA-2) Proportion (Parts by weight). 8 R Name Polyaminic Acid (A-1) Poly (A-2) Poly (A-3) Poly (A-4) Polylysine (A) -5) Polyglycine (A-6) Poly (A-7) Poly (A-8) Poly (A-9) Poly (A-10) Polyfluorene Amino acid (A-11) polylysine (A-12) polylysine (A-13) polylysine (A-14) polylysine (A-15) Example 1 Example 2 Implementation Example 3 Example 4 Example 5 Example 6 Implementation 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 201113328 5 〇〇〇〇〇〇\ S δ CO ITi s § 93.8 as 93.9 95.2 cn wS σ\ 94.4 92.8 92.3 92.3 [ 94.0 92.4 93.7 93.6 CO ON 93.0 94.3 93.6 , 1 94.3 1 93.8 | 94.4 93.5 92.2 91.9 Γ 91.7 i 93.6 91.8 93.3 93.0 92.6 99.2 99.2 99.6 丨〇\ 〇\ 99.6 99.0 cS ON 99.3 99.6 99.3 99, 99.4 99.6 99.4 99.5 〇〇 δ 〇〇〇〇§ S Good Good Good Good Good Good Good Good Good Good Good Good 1 Good Good Good Good 1 1 1 • 8 g § § 1 1 1 • Polyglycine (0PA-1) Proline (OPA-2) Poly (transaminic acid) (OPA-2) Polyglycine (0PA-2) Polyglycine (0PA-2) Polyglycine (OPA-2) Polyproline (OPA) -2) Polyglycine (OPA-2) Polyglycine (OPA-2) Polyglycine (OPA-2) Polyglycine (OPA-2) Ο ο 8 醯 Polyamide (Α -(6) Polyglycine (A-17) Poly (a-18) Polyglycine (A-19) Poly (A-19) Polyglycine (Α-19) Polyamide Acid (A-19) Polylysine (A-19) Acid amide (A-19) Polyamide acid (A-20) < i 狴m inlaying proline (A-22) 1 1 polyaminic acid (A-23) polylysine (A-24) polylysine (A-25) Example 16 Example 17 Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23 Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 Example 28 Example 29 Example 30 _8 inch · 201113328 I general «K嗽] Evaluation Results Residual DC voltage (mV) VO VD δ s S Light resistance maintenance rate (VHAF/VHINX%) 95.0 oi Os CO 〇\ 92.8 92.8 93.3 J 93.7 91.5 93.0 Η ON 98.3 99,0 98.6 Voltage retention after irradiation VHAF (% 94.2 91.6 1 92.3 92.0 92.4 92.9 93.0 90.8 92.4 91.3 97.8 to oo ON 98.0 Initial voltage holding ratio VHIN(%) 99.2 99.5 99.2 as 99.6 99.5 99.3 99.3 99.4 σ < ON 99.4 99.4 99.4 Pretilt angle 0 〇\CO 〇〇〇\ 〇〇 Liquid crystal alignment Good Good Good Good Good 1 Good Good Good Good Good Good Good Good <!□ Embedded S wang m π ratio (parts by weight) sgggg name polyaminic acid (OPA-2) polyglycine (OPA-2) polyglycine (OPA-2) poly-proline (OPA- 2) Polyaminic acid (OPA-2) polyglycine (0ΡΑ-2) polyglycine (OPA-2) polyglycine (OPA-2) polyglycine (0PA-2) polyamine Acid (OPA-2) Poly-proline (OPA-2) Poly-proline (OPA-2) Poly-proline (OPA-2) ΤΓ SK Proportion (parts by weight) 8 Name Polyglycine (A-26) Poly-alanine (A-27) Poly (A-28) Poly (A-29) Poly (A-30) Poly-Aminic Acid (Α-31) Polylysine (A-32) Poly (A-33) Poly (A-34) Poly (A-35) Poly (A-36) Poly-Amino Acid (A-37) Polylysine (A-38) Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example 13 Example 13 201113328 s CN 〇〇cn vrj mm - 5 97.4 97.2 97.3 97.3 92.5 92.0 92.3 ! 94.3 94.5 93.8 91.4 94.2 92.2 96.6 96.6 96.5 96.9 92.0 90.6 1 91.6 91.9 93.9 93.9 93.4 90.6 94.2 93.5 91.4 CN 〇 < ON 99.4 ON ON 99.5 99.4 99.5 99.6 99.6 99.6 99.3 99.5 σί ON 99.0 99.2 σ < ON 〇〇Ό 〇〇CO \〇〇〇\〇〇〇OO 〇〇Good Good Good Good Good Good Good Good Good Good Good Good! Good Good Good Good S § gg Polyglycine (OPA-2) Poly Aminic acid (OPA-2) polyglycine (OPA-2) polyglycine (0PA-2) polyglycine (OPA-2) polyglycine (OPA-2) polyglycine (0PA- 2) Poly (proline) (OPA-2) Poly (proteroic acid) (OPA-2) Poly (prolonged acid) (0PA-2) ! Poly (Amino Acid) (0PA-2) Poly (Amino Acid) (OPA-2) Aminic acid (OPA-2) polyaminic acid (OPA-2) polyglycine (OPA-2) polyglycine (A-39) polyglycine (A-40) polylysine (A- 41) Polyglycine (A42) Polyimine (B-45) Polyimine (B-46) Polyimine (B-47) Polyimine (B-48) Polyimine ( B-49) Polyimine (B-50) Polyimine (B-51) i-1 Polyimine (B-52) Polyimine (B-53) Polyimine (B- 54) Polyimine (B-55) Example 44 Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 Example 51 Example 52 Example 53 Example 54 Example 56 Example 56 Example 57 Example 58 s -s- 2011 13328 Evaluation result Residual DC voltage (mV) r〇5 VO S VO CO m CO 5 Light resistance maintenance rate (VHAF/VHINX%) On 93.0 94.5 92.3 94.5 95.2 92.5 CS 94.3 〇\ 92.9 93.3 92.7 Voltage retention rate after irradiation VHAF ( %) 91.7 92.3 93.9 91.7 94,4 92.2 91.5 93.7 92.6 92.0 92.5 92.0 Initial voltage holding ratio VHIN(%) 99.5 99.3 99.4 99.3 99.5 Γ—Μ σ < ON 99.6 cn cK ON 99.3 99.5 99.0 〇s Os 99.3 Pretilt angle 0 V〇〇〇CC 〇〇oo oo 〇〇〇〇〇〇〇〇〇〇〇〇OO oo §8 Liquid crystal alignment is good, good, good, good Good good good good good good good good good ^ use polymer proportion (parts by weight) § 1 g § name polyglycine (OPA-2) polyglycine (0PA-2) polyglycine (0PA-2) Polylysine (0PA-2) 1 1 Polyaminic Acid (OPA-1) Polyglycine (0PA-2) Poly (proline) (OPA-2) Poly (amine) (OPA-2) Polyamide Acid (OPA-2) Poly-proline (OPA-2) Poly-proline (OPA-2) Poly-proline (OPA-2) Liquid Crystal Alignment Agent 1 Proportion (parts by weight) Ο 〇 Name Polyimine ( B-56) Polyimine (B-56) Polyimine (B-56); Polyimine (B-56) Polyimine (B-56) I Polyimine (B-56) Polyimine (B-57) Polyimine (B-58) Polyimine (B-59) Polyimine (B-60) Polyimine (B-61) Polyimine (B-62) Polyimine (B-63) Example 59 Example 60 Example 61 Example 62 Example 63 Example 64 Example 65 Example 66 Example 67 Implementation Example 68 Example 69 Example 70 Example 71 201113328 Ο S 〇〇S 〇CS 〇〇- 92.0 92.0 92.4 ON 88.5 86.7 89.0 84.6 85.2 Inch 81.2 82.2 84.7 81.7 86.0 91.4 91.6 91.8 94.5 88.0 85.9 j 88.6 82.8 84.5 83.9 80.9 81.6 81.3 85.6 m 〇 < ON 99.5 99.3 99.3 1 99.5 〇\ 〇\ 99.5 99.6 99.5 99.2 99.4 99.6 99.2 99.3 99.4 99.5 〇〇〇〇OO CO 00 OO OO OO £5 £ 〇〇δ £5 \〇〇〇〇〇Good good good good Good good good good good good good good good good good good good good ggggg polyglycine (OPA-2) polyglycine (OPA-2) polyglycine (OPA-2) polyglycine (OPA-2) Proline (OPA-2) Polyglycine (OPA-2) Polyglycine (OPA-2) Polyglycine (0PA-2) Polyglycine (OPA-2) Polyproline (OPA) -2) Polyglycine (0PA-2) Polyglycine (OPA-2) Polyaminic Acid (OPA-2) Polyglycine (OPA-2) Polyglycine (OPA-2) Polyfluorene Amino acid (OPA-2) Polyimine (B-64) Polyimine (B-65) Polyimine (B-66) Polyimine (B-67) Polylysine (Rl) Polylysine (R-2) Poly (transamine) (R-3) Poly (reutere) (R4) Poly (reutere) (R-5) Poly (transamine) (R-6) 1 Polyimine (S -7) Polyimine (S-8) Polyimine (S-9) Polyimine (S-10) Polyimine (S-11) Polyimine (S-12) Example 72 Example 73 Example 74 Example 75 Comparative Example 1 Comparative Example 6 Comparative Example Comparative Example 2 Comparative Example 3 j Example 4 Comparative Example 5 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative 12 201 113 328] [Brief Description of the drawings [mu]. >ι\\ [Main component symbol description] 〇 -53-

Claims

201113328 七、申請專利範圍： 1. 一種液晶配向劑，其特徵在於：包含由四羧酸二酐和二胺反應得到的聚醯胺酸以及該聚醯胺酸脫水閉環形成的聚醯亞胺構成的群組中選出的至少一種聚合物，其中四羧酸二酐包含由3,5,6-三羧基-2-羧甲基降冰片烷 -2:3,5:6-二酐和 2,4,6,8-四羧基二環[3.3.0]辛烷- 2:4,6:8-二酐構成的群組中選出的至少一種，二胺包含具有光反應性結構的二胺。 2.如申請專利範圍第1項之液晶配向劑，其中該具有光反應性結構的二胺中的光反應性結構是下式（A-2)所示的結構，201113328 VII. Patent application scope: 1. A liquid crystal alignment agent, which comprises: a poly-proline acid obtained by reacting tetracarboxylic dianhydride and a diamine, and a polyamidene formed by dehydration ring closure of the polyglycine At least one polymer selected from the group consisting of 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride and 2, At least one selected from the group consisting of 4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, the diamine comprising a diamine having a photoreactive structure. 2. The liquid crystal alignment agent of claim 1, wherein the photoreactive structure in the diamine having a photoreactive structure is a structure represented by the following formula (A-2).

(式（A-2)中，d是0或1，A1和A2分別是碳原子數爲1~6 的烷基、碳原子數爲1〜6的烷氧基、鹵原子或氰基，e 和f分別是0〜4的整數，“ 分別表示連接鍵）。 3.如申請專利範圍第2項之液晶配向劑，其中該式（A-2)所示的結構是選自由下式（A-2-1)和（A-2-2)分別表示的結構的至少一種結構， -54- 201113328(In the formula (A-2), d is 0 or 1, and A1 and A2 are each an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group, and e. And f are an integer of 0 to 4, respectively, and "the connection key is respectively indicated." 3. The liquid crystal alignment agent of claim 2, wherein the structure represented by the formula (A-2) is selected from the following formula (A) -2-1) and (A-2-2) at least one structure of the structure respectively, -54- 201113328

(A-2-2) (式（A-2-1)和（A-2-2)中，a1' A2、d、e 和 f 分別和上式（A-2) 中的定義相同， R1和Rn分別是碳原子數爲1〜20的烷基、碳原子數爲1~8 的氟代烷基或具有脂環結構的碳原子數爲4 ~ 30的烴基’ X11 和 X111 分別是- 0·、-CO·、-CO-0-、-O-CO-、-NR-、 -NR-CO-、-CO-NR-、-NR-C0-0-、-O-CO-NR-、-NR-CO-NR-或- 0-C0-0-(其中，R是氫原子或碳原子數爲1〜4的烷基）， Rni分別是亞甲基、伸芳基、2價的脂環基、-Si(CH3)2-、 -CH = CH-或-Cs C-，其中RnI所具有的氫原子的一個或兩個以上可以被氰基、鹵原子或碳原子數爲1〜4的烷基取代， h是1〜6的整數， i是0〜2的整數，存在多個上述Xn和尺…時，它們可以相互相同，也可以不同， j是〇或1，而且“ 分別表示連接鍵）。 -55- 201113328 4.如申請專利範圍第1至3項中任一項之液晶配向劑，其中該二胺進一步含有由下式（A_0)和（A_3)表示的二胺構成的群組中選出的至少一種，(A-2-2) (In the formulas (A-2-1) and (A-2-2), a1' A2, d, e, and f are the same as defined in the above formula (A-2), respectively, R1 And Rn are each an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms, or a hydrocarbon group having 4 to 30 carbon atoms having an alicyclic structure. X11 and X111 are -0, respectively. ·, -CO·, -CO-0-, -O-CO-, -NR-, -NR-CO-, -CO-NR-, -NR-C0-0-, -O-CO-NR-, -NR-CO-NR- or - 0-C0-0- (wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and Rni is a methylene group, an aryl group, and a divalent fat, respectively. a cyclic group, -Si(CH3)2-, -CH=CH- or -CsC-, wherein one or more of the hydrogen atoms of RnI may be a cyano group, a halogen atom or a carbon number of 1 to 4 The alkyl group is substituted, h is an integer of 1 to 6, and i is an integer of 0 to 2. When a plurality of the above Xn and the ruler are present, they may be the same as or different from each other, j is 〇 or 1, and "respectively The liquid crystal alignment agent of any one of Claims 1 to 3, wherein the diamine further contains a diamine represented by the following formulas (A_0) and (A_3). At least one of the selected groups,

(式（A-Ο)中’ X1表示單鍵、亞甲基、碳原子數爲2或3 的亞gS、！!!-〇-、*-COO-、*-〇CO-、*-X，-R1-、*-R1-X’-或IX’-RLX、其中，X’分別表示、〇.、、C〇0 -或+ -〇co-(其中“+”表示帶有其的連接鍵朝向式（A-ο)的左方向）， y分別是碳原子數爲2或3的伸烷基，帶的連接鍵和二胺基苯基連接）， Ring1和Ring2各自獨立地是伸環己基或伸苯基， X"是單鍵、、0-、+-C00-或者+-OCO-(其中“+”表示帶有其的連接鍵朝向式（A-Ο)的左方向）， a是0或l，b是0~3的整數， b爲2以上時，多個存在的X"和Ring2分別相互相同，也可以不同，a爲〇時，位於式（A-Ο)的最左邊的X’’是單鍵， c是0〜20的整數，α和召分別是0~2c+l的整數，其中 α +β =2c+l > 而且 a + b = 0 時，c 不是〇);(In the formula (A-Ο), 'X1 represents a single bond, a methylene group, a sub-gS having a carbon number of 2 or 3, !!!-〇-, *-COO-, *-〇CO-, *-X , -R1-, *-R1-X'- or IX'-RLX, where X' denotes respectively, 〇., C〇0 - or + -〇co- (where "+" denotes the connection with it The bond is oriented toward the left direction of the formula (A-o), y is an alkylene group having 2 or 3 carbon atoms, and the bond of the bond is bonded to the diaminophenyl group. Ring1 and Ring2 are each independently a ring. Hexyl or phenyl, X" is a single bond, 0-, +-C00- or +-OCO- (where "+" means that the bond with it is oriented to the left of the formula (A-Ο)), a It is 0 or l, b is an integer of 0~3, and when b is 2 or more, X" and Ring2 existing in different numbers are the same or different, and when a is 〇, it is located at the leftmost side of the formula (A-Ο) X'' is a single bond, c is an integer from 0 to 20, and α and call are integers of 0~2c+l, respectively, where α + β = 2c + l > and when a + b = 0, c is not 〇 );

-56- 201113328 (式（A-3)中，R1"各自獨立地是氫原子或碳原子數爲卜；^ 的烷基，RIV和Rv各自獨立地是氫原子或亞甲基）。 5.如申請專利範圍第1至3項中任一項之液晶配向劑，其進一步包含由聚醯胺酸和將該聚醯胺酸脫水閉環形成聚醯亞胺構成的群組中選出的至少一種聚合物，該聚醯胺酸係使四羧酸二酐和不含上述第二種二胺的二胺反應而得。 6· —種液晶配向膜，其特徵在於：由如申請專利範圍第1 至5項中任一項之液晶配向劑形成。 7_—種液晶顯示元件，其特徵在於：具有如申請專利範圍第6項之液晶配向膜。 8. —種聚醯胺酸，該聚醯胺酸係由四殘酸二酐和二胺反應而得，其中四羧酸二酐包含由3,5,6-三羧基-2-羧甲基降冰片烷-2:3,5:6-二酐和2，4,6,8-四羧基二環[3.3.0]辛烷 •2:4,6:8 -二酐構成的群組中選出的至少一種，二胺包含具有光反應性結構的二胺。 9. 一種聚醯亞胺，其係將如申請專利範圍第8項之聚醯胺酸脫水閉環而形成。 -57- 201113328 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:-56- 201113328 (In the formula (A-3), R1" are each independently a hydrogen atom or an alkyl group having a carbon atom; and RIV and Rv are each independently a hydrogen atom or a methylene group). 5. The liquid crystal alignment agent according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of polylysine and dehydration of the polyamic acid to form a polyimine. A polymer obtained by reacting a tetracarboxylic dianhydride with a diamine containing no such second diamine. A liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 5. A liquid crystal display element comprising: a liquid crystal alignment film according to claim 6 of the patent application. 8. A poly-proline acid obtained by reacting a tetra-residual dianhydride and a diamine, wherein the tetracarboxylic dianhydride comprises 3,5,6-tricarboxy-2-carboxymethyl a group consisting of norbornane-2:3,5:6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane•2:4,6:8-dianhydride At least one selected, the diamine comprises a diamine having a photoreactive structure. A polyimine which is formed by dehydration and ring closure of a polyglycolic acid according to item 8 of the patent application. -57- 201113328 IV. Designation of Representative Representatives: (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: