TW200848884A - Liquid crystal alignment agent and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent and a liquid crystal display element, wherein the liquid crystal alignment agent has a liquid crystal alignment film that can maintain the voltage holding ratio while reduce accumulated charges and has excellent printability. The liquid crystal alignment agent comprises polymers and/or imide polymers thereof obtained by reacting certain tetracarboxylic acid dianhydrides with certain diamine compounds, a compound of formula (7), and a solvent; wherein X1 is an organic group with one valence of formulae (7-1) or (7-2), and m and n are independently an integer of 1 to 20; -R5(C2H4O)a(C3H6O)bR6 (7 - 1) -R5(C2H4O)aR6 (7 - 2) wherein R5 is independently methylene group or polymethylene group, R6 is alkyl, and a and b are independently an integer of 1 to 20.

Description

200848884 IX. Description of the Invention: The present invention relates to a liquid crystal alignment agent for forming a liquid crystal alignment film of a liquid crystal display element, and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent which can form a liquid crystal alignment film having good electrical properties and excellent printability, and a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment agent. [Prior Art] At present, as a liquid crystal display element, a ΤΝ-type liquid crystal display element having a so-called 扭曲 (twisted nematic) type liquid crystal cell is known, which is provided on a substrate surface of a transparent conductive film such as germanium (indium oxide-tin oxide). A liquid crystal alignment film formed of polyamic acid, polyimine or the like is formed thereon, and as a substrate for a liquid crystal display element, two substrates are opposed to each other, and a nematic type having positive dielectric anisotropy is formed in the gap. The layer of the liquid crystal constitutes a cell of the sandwich structure, and the long axis of the liquid crystal molecule is continuously twisted by 90 degrees from one substrate to the other substrate. Further, an STN (Super Twisted Nematic) type liquid crystal display element having a higher contrast ratio and a smaller angle dependence than that of the ΤΝ type liquid crystal display element has been developed. This STN type liquid crystal display element uses a liquid crystal in which a palmitic agent as an optically active substance is incorporated in a nematic liquid crystal as a liquid crystal by utilizing a continuous twist of the liquid crystal molecules between the substrates by 180 degrees. The birefringence effect produced by the state of the above amplitude. In addition, a vertical alignment type liquid crystal display element called MV Α (multi-domain vertical alignment) in which protrusions are formed on a transparent conductive film to control the alignment direction of liquid crystals has been proposed (refer to Patent Document 1 and Non-Patent Document 1). . 200848884 The liquid crystal display element of the MVA type is excellent not only in viewing angle and contrast, but also in the process of forming the liquid helium alignment g旲. It is also excellent in the manufacturing process. As the liquid crystal alignment film which is applied to the TN, STN and MVA systems described above, electrical performance such as short image erasing time of the liquid crystal display element is required. Further, as an alignment agent for forming these liquid crystal alignment films, it is required to have excellent printability in offset printing. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 6-222366. Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The purpose of the present invention is to provide a liquid crystal alignment agent capable of maintaining a high voltage holding ratio of a liquid crystal alignment film of a polyimide, while reducing accumulated charge, and having excellent printability, and a liquid crystal display element using the same. According to the present invention, the above object of the present invention, first, achieved by a liquid crystal alignment agent comprising: at least one selected from the group consisting of tetracarboxylic dianhydrides represented by the following formulas (1) and (2) and selected from the group consisting of a polymer obtained by reacting at least one of the diamines represented by the following formulas (3) to (6) and/or a quinone imidized polymer thereof; a compound represented by the following formula (7), and a solvent; 200848884

(wherein R1 to R4 are each independently a linear 200848884-like, branched or cyclic alkyl group having 1 to 40 carbon atoms or a linear or branched chain having 4 to 40 carbon atoms or The cyclic suspicion group, 1 to 15 of the hydrogen atoms of R1 to R4 may be substituted by a chlorine atom 'A1 and A2 are each independently a hydrogen atom or a methyl group), CH, I, H3C-Si- - ch3

(7) (wherein X1 is a monovalent group represented by the following formula (7-1) or (7_2), (5) and η are integers of 1 to 20), —R5(C2H40)a(C3H60)bR6 (7) -1 ) R5(C2H40)aR6 (7-2) (wherein R5 is a methylene group or a polymethylene group, R6 is an alkyl group, and & b are each independently an integer of from 1 to 20). According to the present invention, the above object of the present invention, and secondly, is achieved by a liquid crystal display member having a liquid crystal alignment film produced from the above liquid crystal alignment agent. [Embodiment] The liquid crystal alignment agent of the present invention contains at least one selected from the group consisting of tetrahydro acid dianhydrides represented by the above formulas (丨) and (2) and a diamine selected from the above formulas (3) to (6). The polymer obtained by at least one of the reactions (hereinafter referred to as "specific poly-proline acid") and/or its quinone imidized polymer. Hereinafter, tetracarboxylic dianhydride and diamine which can be used for the polymer contained in the liquid crystal alignment agent of the invention of 200848884 will be described. <tetracarboxylic dianhydride> The tetracarboxylic dianhydride used in the synthesis of the specific polyamic acid and/or its quinone imidized polymer contains 2,3,5- selected from the above formula (1). Tricarboxycyclopentyl acetic acid dianhydride and 5-(2,5-diketotetrahydro-3.furanyl)-3-methyl-3-cyclohexene-1,2- represented by the above formula (2) At least one of dicarboxylic anhydride (hereinafter referred to as "specific tetracarboxylic dianhydride"). In the synthesis of a specific polyamic acid and/or its quinone imidized polymer, in addition to the specific tetraphthalic acid dianhydride, other tetracarboxylic dianhydrides may be used in combination. Examples of the other tetracarboxylic dianhydride include an alicyclic tetracarboxylic dianhydride (excluding a specific tetracarboxylic dianhydride), an aliphatic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutane. Alkanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, hydrazine, 3-dichloro-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, cis_3,7-dibutylcyclooctane -1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2 : 3,5 : 6 -dianhydride, 2 , 3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,2,4-tricarboxycyclopentyl acetic acid dianhydride, tetracyclo[4,4,0,12'5,17,1°]12垸-3,4,8,9-tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5·dione-3-furanyl)- Nai [l,2-c]-purine-1,3-y, 1,3,3&,4,5,91>-hexahydro-10-200848884-5-methyl-5(tetrahydro- 2,5-diketo-3-furanyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-5-ethyl -5 (tetrahydro-2,5-diketo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro- 7-Methyl-5(tetrahydro-2,5-dione-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3,3& 4,5,91)-hexahydro-7-ethyl-5(tetrahydro-2,5-dione-3-furanyl)-naphthalene[l,2-c]-furan-1,3-di Ketone, 1,3,3&,4,5,9!3-hexahydro-8-methyl-5(tetrahydro-2,5-dione-3-furanyl)-naphthalene [1,2- (:]-furan-1,3-dione, 1,3,3&,4,5,913-hexahydro-8-ethyl-5(tetrahydro-2,5-dione-3-furanyl) -naphthalene [1,2-c]-furan-1,3-dione, 1,3,3&,4,5,91)-hexahydro-5,8-dimethyl-5(tetrahydro-2 ,5-diketo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, bicyclo[2.2.2]-oct-7-ene-2,3,5 ,6-tetracarboxylic dianhydride, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 3 ,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0''6]undecane-3,5, 8,10-tetraketone, a compound represented by the following formula (1) or (11), etc.

Π G

200848884 (wherein 'R7 and R9 represent a divalent organic group having an aromatic ring, R8 and R1() represent a hydrogen atom or an alkyl group, and a plurality of existing r8 and R1 may be the same or different). The aliphatic tetracarboxylic dianhydride may, for example, be butane alkyltetracarboxylic dianhydride or the like. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4,-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'- Diphenylphosphonium tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4' - Diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3,3',4,4,-tetraphenylnonane tetracarboxylic acid Dihydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4,-di 3,4-dimercaptophenoxy)diphenylphosphonium dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4 '-Perfluoroisopropylidene diphthalic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3, ,4,4 '-biphenyltetracarboxylic acid Anhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) k dianhydride, m-phenylene-bis(triphenylphthalic acid) Diacetate, bis(triphenylphthalic acid)_4,4,-diphenyl ether dianhydride, two ( Phenylphthalic acid)-4,4,-diphenylmethane dianhydride, ethylene glycol-di(hydroper trimellitate), propylene glycol-di(hydroper trimellitate), 1,4- Butanediol-di(dehydrated trimellitate), 1,6-hexanediol-di(hydrogen trimellitate), 1,8-octanediol-mono(anhydroelellitic acid ester), 2,2-bis(4-hydroxyphenyl)propane-di(hydrogen trimellitate), a compound represented by the following formulas (8) to (11), and the like. -12- 200848884

These other tetracarboxylic dianhydrides may be used alone or in combination of two or more. Among the above other tetracarboxylic dianhydrides, from the viewpoint of the liquid crystal alignment property which can exhibit good performance, as the alicyclic tetracarboxylic dianhydride, it is preferably -13 - 200848884 1,2,3,4-cyclobutane Alkane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane Tetracarboxylic acid dicyclopentane tetracarboxylic dianhydride, 1,2,4·tricarboxycyclopentyl acetic acid: -3,7-dibutylcyclooctane-1,5-diene-1,2,5, 6-tetracarboxylic dianhydride, benzyl-2-carboxynorbornane-2:3,5:6-dianhydride, 1,3,3a,4,5,9b hydrogen-2,5-diketo-3 -furyl)-naphthalene [1,2-(:]furan-] 1,3,3&,4,5,913-hexahydro-8-methyl-5-(tetrahydro-2,5-dione naphthalene [l,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-^-5-(tetrahydro-2,5-dione-3-furan Naphthalene [1,2-called furan-1 ring [2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxaoctane-2,4 a formula represented by the following formulas (12) to (14) in a compound represented by di-keto-6-spiro-3'-(tetrahydrofuran-2', 5'-dii(I) In the compound represented by the following formula (15): cyclobutane tetracarboxylic anhydride, 1,2,3,4-dianhydride Cis 3,5,6-tricarbonyl-hexahydro-5-(tetrakis-3-dione, -3 -furanyl)-5,8-~~* methyl, 3-diketone, bicyclol[ 3.2.1] 祠), a compound of the above formula or an upper compound,

(12)

14- (15) 200848884

As a particularly preferable one, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4·cyclobutane tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dione-3-furanyl)·naphthoquinone, 2 -c ]furan-1,3 -dione ,cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 1,2,4-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarbonyl-2·carboxynorbornane-2:3,5:6-dianhydride, 1,3,3&,4,5,913-hexahydro-8-methyl-5-(four Hydrogen-2,5-diketo-3-indolyl)-na[1,2-c]pyran-1,3 -1·嗣, 3-3⁄4雑bicyclo[3.2.1] octane·2 , 4-dione-6-spiro-3'-(tetrahydrofuran. 2', 5'-dione) or a compound represented by the above formula (12). Among the above other tetracarboxylic dianhydrides, preferred examples of the aliphatic tetracarboxylic dianhydride or the aromatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride, pyromellitic dianhydride, and 3,3. ',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4,-diphenylanthracene Tetracarboxylic dianhydride or 1,4,5,8-naphthalenetetracarboxylic dianhydride. As the other tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride is preferably used. When a specific polyamic acid is synthesized, when a specific tetracarboxylic dianhydride is used in combination with other tetracarboxylic dianhydrides, the use ratio of the specific tetracarboxylic dianhydride is preferably 5 with respect to the entire tetracarboxylic dianhydride. 0% or more. <Diamine> -15-200848884 The combination of a specific poly-proline and/or its ruthenium-based polymer is used. < /J? One (the diamine is selected from the above formula (3)~ Among the diamines represented by (6), it is referred to as "specific diamine". Further, in addition to the synthesis of the specific polyamine and/or its quinone imidized polymer, and the 7 specific diamine, other diamines may be used in combination. Examples of the other diamines include, for example, an aromatic diamine, an aliphatic or alicyclic diamine, a diamine having a two-stage amine group in the molecule, and a nitrogen atom other than the hydrazine-based amine group. Oxane and the like.

Examples of the aromatic diamine include p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine, and 2,5-dimethyl group. 1,4-phenylenediamine, 2,5-diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, m-phenylenediamine, 4 , 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Base, 2,2'-dimethyl-4,4,-diaminobiphenyl, 3,3'-dimethyl-4,4,-diaminobiphenyl, 4,4'-diamine Benzobenzidine, 4,4'-diaminodiphenyl, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4,-diaminobiphenyl, 5-amino -1-(4'-aminophenyl)-1,3,3-trimethylindan, ^anylphenyl)-1,3,3·trimethyl, 3,4'-di Aminodiphenyl ether, diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4,-diaminobenzophenone, 2,2-bis[4-(4-amine Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropene Institute, 22·bis[4-(4-aminophenoxy)phenyl]anthracene, 1,4- (4.Aminophenoxy)benzene, oxime-(4-aminophenoxy)benzene, i,3-di(3-aminophenoxy)benzene, 9 9-mono(4-aminobenzene) Base)-10-hydroquinone, 2,7-diaminopurine, 9,9-dimethyl-2,7-diamine 16 - 200848884 莽, 9,9-bis(4-aminophenyl) ), 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro-4,4,-diaminobiphenyl, 2,2'-di Chloro-4,4,-diamino-5,5'dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4' -(p-phenylene isopropylidene)diphenylamine, 4,4'-(m-phenyleneisopropylene)diphenylamine, 2,2'-bis[4-(4-amino-2-yl) Fluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino) -2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3, 6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, etc.; as the above aliphatic or alicyclic diamine, for example, 1,1-m-xylylenediamine, 1 , 3-propanediamine, butanediamine, pentamethylenediamine Hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4-diaminoheptyldiamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentane Diene diamine, hexahydro-4,7-methyl hydrazine dimethylene diamine, tricyclo[6.2.1.0'7]-undecene dimethyldiamine, 4,4'-methylene (cyclohexylamine) or the like; as the diamine having two primary amino groups in the molecule and a nitrogen atom other than k in the first-order amine group, for example, 2,3-diaminopyridine, 2,6- Diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyridinium, 5,6-diamino-2 ,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-trin, 1,4-bis(3-aminopropyl)piped, 2,4 -diamino-6-isopropoxy-1,3,5-trin, 2,4-diamino-6-methoxy-1,3,5-tri-trap, 2,4-diamine -6-phenyl-1,3,5-tri-trap, 2,4-diamino-6-methyl-s-trisole, 2,4.diamino-l,3,5-triad , 4,6-diamino-2-vinyl-S-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino- 17- 200848884 -1,3-Methyl uranyl steep, 3,5-diamine Base-1,2,4-tris-π, 6,9-diamino-2-oxoacyl lactate, 3,8-diamino-6-phenylphenanthridine, ι, 4 And the bis(4-aminophenyl)phenylamine;丨6) The compound represented by 等2Ν—^

(16) ί (wherein R11 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R11 groups may be the same or different, ρ is an integer of 1 to 3, and q is an integer of 1 to 2 0). These other diamines may be used alone or in combination of two or more. Among these other diamines, preferred are p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2-ethyl-1,4-phenylenediamine, and 2,5-dimethyl-1. 4-phenylenediamine, 2,5-diethyl-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diamino Diphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,5-diaminonaphthalene, 2,7- Diamino hydrazine, 9,9-dimethyl-2,7-diamino fluorene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-di (4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), 1,4--18- 200848884 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 or N-phenyl-3,6-diaminocarbazole, more preferably p-phenylenediamine, 2-methyl-1,4-phenylenediamine , 2-ethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-diethyl-1,4-phenylenediamine or 2,3, 5,6·tetramethyl-1,4-phenylenediamine. When the pretilt performance of the liquid crystal alignment agent of the present invention is to be improved, in addition to the specific diamine and optionally the above other diamine, it may be selected from the following formula (Q-1).

(wherein X2 is a single bond, -〇-, -CO-, -COO-, -〇C〇-, -NHCO -, -C〇NH_, _S_ or an arylene group, and Ri2 is a carbon atom of 10~ An alkyl group of 20, a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms or a fluorine atom-containing monovalent organic group having 6 to 20 carbon atoms) and the following formula (Q-1) 2) at least one diamine of the diamines indicated.

(wherein X3 is a single bond, -〇-, -C〇-, -C〇〇-, -〇C〇-, -NHCO-, _C〇NH-, -S- or an arylene group, and R13 is a carbon atom The divalent organic group having a cyclic -19-200848884 ring skeleton of 4 to 40 may be used alone or in combination of two or more. In the above formula (Q-1), the alkyl group having a carbon number of -20 represented by Rl2 may, for example, be an n-decyl group, a n-dodecyl group, a n-pentadecyl group or a n-hexadecyl group. Octadecyl, n-icosyl, and the like. The R1 of the above formula (Q-1) and the monovalent or divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms represented by R13 in the above formula (Q-2) may, for example, be exemplified. a group having an alicyclic skeleton derived from a cycloalkane such as cyclobutane, cyclopentane, cyclohexane or cyclodecane; a group having a steroid skeleton such as cholesterol or cholestyl alcohol; having a norbornene a group such as a bridged ring skeleton such as an alkane or adamantane. Among them, a group having a steroid skeleton is particularly preferred. The above-mentioned organic group having an alicyclic skeleton may have a part or all of a hydrogen atom which may be substituted by a halogen atom (preferably a fluorine atom) or a fluoroalkyl group (preferably a trifluoromethyl group). The fluorine atom-containing group having 6 to 20 carbon atoms represented by R12 in the above formula (Q-1) may, for example, be n-hexyl, n-octyl or n-decyl, and the number of carbon atoms is 6~. a linear alkyl group of 20; an alicyclic hydrocarbon group having 6 to 20 carbon atoms such as a cyclohexyl group or a cyclooctyl group; an organic group such as an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group or a biphenyl group; A group in which a part or all of a hydrogen atom is substituted with a fluorine atom or a fluoroalkyl group such as a trifluoromethyl group. X2 in the above formula (Q-1) and X3 in the above formula (Q-2) are a single bond, _〇_, -CO-, _C〇〇_, ·〇(:〇_, _NHC〇_, _C 〇NH_, _S_ or an arylene group, and examples of the arylene group include a phenylene group, a tolyl group, a biphenylylene group, a naphthylene group, etc. As X2 and X3, particularly preferably -〇_, - C〇〇-, -〇C〇- -20- 200848884 The group which is represented by the above formula (Q-1), and the dodecyloxy-2, 4-diaminobenzene, pentadecyldiaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxyaminobenzene or represented by the following formulas (17) to (26) Preferred compound oxy-2,4-yl-2,4-di

H2N

Nh2 (17)

-21 - 200848884

(twenty three)

(twenty four)

-22- (26) (25) 200848884 A preferable example of the diamine having a group represented by the above formula (Q-2) is a compound represented by the following formulas (27) to (29).

2 9) Among them, as a particularly preferable compound, a compound represented by the above formula (17), (18), (23), (24) or (27) can be given. When a specific diamine is used in combination with other diamines and/or a diamine represented by the above formula (Q-丨) or (Q-2) in the synthesis of a specific poly-proline, 'specific diamine-23-200848884 The use ratio is preferably 1 mol% or more, and particularly preferably 5 mol% or more, based on the entire diamine. <Synthesis of Specific Polylysine> Hereinafter, a method for synthesizing a specific polyamine which can be contained in the liquid crystal alignment agent of the present invention will be described. The specific polyamic acid may be preferably in an organic solvent, preferably at -20 ° C, by reacting the above specific tetracarboxylic dianhydride and other tetracarboxylic dianhydrides as needed with a specific diamine and, if necessary, other diamines. It is preferably synthesized at a temperature of from 0 to 150 ° C, more preferably from 0 to 100 ° C, for 0.5 to 7 hours. The ratio of the tetracarboxylic dianhydride to the diamine to be used in the synthesis reaction of the specific polyaminic acid is preferably 0.5 to 2 equivalents based on the amine group of the equivalent of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.5 to 2 equivalents. More preferably, it is made to have a ratio of 0.7 to 1.2 equivalents. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized specific polyamic acid, and examples thereof include 1-methyl-2-pyrrolidone and N,N-dimethylacetamidine. Amine, N,N-dimethylformamide, 3-butoxy-indole, hydrazine-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyl Aprotic solvents such as oxy-N,N-dimethylpropionamide, aprotic polar solvents such as dimethyl hydrazine, τ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamide; A phenolic solvent such as methyl phenol, xylenol, phenol or halogenated phenol. Further, the amount (α) of the organic solvent is preferably such that the ratio (mole concentration) of the total amount (Θ) of the tetracarboxylic dianhydride and the diamine compound to the total amount (α + 0 ) of the reaction solution is 0.1 〜 An amount of 30% by weight. -24- 200848884 In the above organic solvent, it is also possible to use a poor solvent alcohol, ketone, ester, ether or halogenated hydrocarbon of a specific polyamine in the range in which the specific polyamine acid is not precipitated. Classes, hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol, propylene glycol, and 1,4-butane. Glycol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, vinegar ^ Butyl acrylate, methyl methoxypropionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol positive Ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, Trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, iso-pentyl ether, and the like. As described above, a reaction solution in which a specific polyamine is dissolved is obtained. Then, the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or the reaction solution is evaporated under reduced pressure with an evaporator to obtain a polyamine. Further, the specific polylysine is redissolved in an organic solvent, and then precipitated with a poor solvent, or distilled under reduced pressure with an evaporator, and one or several times of this step, the specific polyamic acid can be purified. <Synthesis method of ruthenium iodide polymer of specific polyglycolic acid> -25- 200848884 Next, a method for synthesizing a ruthenium iodide polymer of a specific polyglycine which can be contained in the liquid crystal alignment agent of the present invention Be explained. The quinone imidized polymer of a specific polyamine can be synthesized by dehydration ring closure of a part or all of the proline structure of the above specific polyamic acid. The ratio of the repeating unit having a quinone ring in all the repeating units of the oxime imidized polymer which can be used in the present invention (hereinafter, also referred to as "deuterated imidization ratio") is 40 mol% or more. Good is 50% or more. By using a polymer having a ruthenium iodide ratio of 40 mol% or more, the afterimage erasing time of the obtained liquid crystal alignment film can be made shorter. The dehydration ring-closure reaction of the specific polyamine can be carried out by (i) heating a specific poly-proline, or (ii) dissolving a specific poly-lysine in an organic solvent, and adding a dehydrating agent and a dehydration ring-closing catalyst to the solution. And according to the method of heating required. In the above method (i) for heating a specific polyaminic acid, the reaction temperature is preferably from 50 to 200 ° C, more preferably from 60 to 170 ° C. When the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction may not proceed sufficiently. If the reaction temperature exceeds 200 ° C, the molecular weight of the obtained quinone imidized polymer may decrease. On the other hand, in the method of adding the dehydrating agent and the dehydration ring-closure catalyst to the specific polyaminic acid solution of the above (ii), as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent, depending on the desired hydrazine imidization ratio, is preferably 0.01 to 20 moles per 1 mole of the repeating unit of the specific polyamine. As the dehydration ring-closing catalyst, for example, an amine of 3-26 to 200848884 such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these. The amount of the dehydration ring-closing catalyst is preferably 0.01 to 10 mols per mol of the dehydrating agent used. The more the amount of the above-mentioned dehydrating agent and dehydration ring-closing catalyst, the higher the yield of ruthenium. The organic solvent used in the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used in the synthesis of a specific polyamine. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 ° C, more preferably 10 to 15 CTC. The obtained ruthenium iodide polymer can be purified by performing the same operation as in the specific polyamic acid purification method on the reaction solution thus obtained. <Terminal modified polymer> The specific polyaminic acid or its quinone imidized polymer used in the present invention may be a terminal modified polymer having a molecular weight adjusted. By using the terminal-modified polymer, the coating characteristics and the like of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. Such a terminal-modified polymer can be synthesized by adding a monobasic acid anhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system at the time of synthesis of a specific polyamine. Among them, examples of the monobasic acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, and n-hexadecane. Succinic anhydride and the like. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, and positive ten. II compound amine, Zheng 13 compound amine, Zheng 14th hospital amine, Zheng fifteen amine, Zheng Xieyuan amine, n-heptadecaneamine, n-octadecylamine, n-dodecylamine and so on. The monoisocyanate compound ′ is, for example, phenyl isocyanate or naphthyl isocyanate. -27- 200848884 <Solid viscosity of polymer> The specific polylysine and its quinone imidized polymer obtained above preferably have a viscosity of 20 to 800 mPa·s when formulated into a 10% solution, Good has a viscosity of 30~500mPa*s. Further, the solution viscosity (m P a · s) of the polymer was determined by using a predetermined solvent, and the solution having a solid content concentration of 10% was measured at 25 ° C using an E-type rotational viscometer. <Other Polymers> r ' In the liquid crystal alignment agent of the present invention, a part of the above specific polyaminic acid or its quinone imidized polymer may be selected from other polymerizations without impairing the effects of the present invention. At least one of the proline and its quinone imidized polymer (hereinafter referred to as "other polymer") is replaced. The above other polymer is not particularly limited as long as it is a polyamic acid other than a specific polyamic acid or a quinone imidized polymer thereof, and is preferably composed of the above other tetracarboxylic dianhydride and other diamines. The resulting polymer or its fci quinone imidized polymer is reacted. As the other tetracarboxylic dianhydride used herein, an alicyclic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride is preferable, and a 1,2,3,4-cyclobutane tetracarboxylic dianhydride is particularly preferable. Or pyromellitic dianhydride. As the other diamine used herein, an aromatic diamine is preferable, and a 4,4'-diaminodiphenyl phenyl group is particularly preferable. For the synthesis of such other polymers, other tetracarboxylic dianhydrides and other diamines may be used in place of the specific tetracarboxylic dianhydride and the specific diamine, as in the synthesis of the specific polyamine and its ruthenium iodide polymer. get on. -28 - 200848884 When the liquid crystal alignment agent of the present invention contains other polymers, the amount of other polymers used is preferably 8 in terms of the total amount of the specific polyamine and its ruthenium iodide polymer and other polymers. 0% by weight or less is more preferably 60% by weight or less. <Organic hydrazine compound> The liquid crystal alignment agent of the present invention further contains the compound represented by the above formula (7) (hereinafter referred to as "organoquinone compound"). The methylene group or the poly(subunit f^methyl group) of R5 which the group X1 in the above formula (7) has, specifically, for example, -CH2-, -(CH2)2-, _(CH2)3.' -(CH2)4-etc. The alkyl group of R6 is preferably an alkyl group having 1 to 10 carbon atoms. The proportion of the organic ruthenium compound used in the liquid crystal alignment agent of the present invention is a total amount of 100 parts by weight of the specific polyaminic acid and its ruthenium iodide polymer (hereinafter referred to as "the total amount of the polymer". When the liquid crystal alignment agent of the present invention contains other polymers, the "combination amount of the polymer" means the total amount of the specific LJ polyphthalic acid and its quinone imidized polymer and other polymers. It is 0.01 to 3 parts by weight, more preferably 0.1 to 2 parts by weight. By setting the amount to fall within this range, a liquid crystal alignment agent which is excellent in printability and can form a liquid crystal alignment film having excellent electrical properties can be obtained. <Other Additives> The liquid crystal alignment agent of the present invention contains at least one selected from the above specific polyaminic acid and its quinone imidized polymer, an organic hydrazine compound, and the following solvent as essential components, but does not impair Within the scope of the effects of the present invention, -29-200848884 may contain other additives. Examples of such other additives include a compound having two or more epoxy groups in the molecule, a functional decane-containing compound other than the above organic quinone compound (hereinafter referred to as "other functional decane-containing compound"), and the like. The compound having two or more epoxy groups in the above molecule (hereinafter referred to as "epoxy compound") may be added to further improve the printability of the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention. Specific examples of such an epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3 ,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-di(N,N-di Glycidylaminomethyl)cyclohexane, hydrazine, hydrazine, Ν', Ν'-tetraglycidyl_4,4'-diaminodiphenylmethane, 3-(Ν-allyl-Ν - glycidyl) aminopropyltrimethoxydecane, 3-(anthracene, fluorene-diglycidyl) aminopropyltrimethoxydecane, anthracene, hydrazine-diglycidyl-benzylamine, hydrazine, Ν-diglycidyl-aminomethylcyclohexane or the like. The ratio of use of the epoxy compound in the liquid crystal alignment agent of the present invention is preferably 50 parts by weight or less with respect to the total amount of the polymer of 1 part by weight, more preferably 0. 1 to 40 parts by weight, more preferably 1 ~30 parts by weight. The other functional decane-containing compound may be added from the viewpoint of further improving the adhesion of the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention to the substrate at an angle of -30 to 200848884. Specific examples of such other functional decane-containing compound include, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 2-aminopropyltrimethoxy. Decane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, 3-ureido-propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxylated-3-aminopropyltrimethoxy Baseline, N-ethoxycarbonyl-3-aminopropyltris-trimethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N.trimethoxydecylpropyltriethylenetriene Amine, 10-trimethoxydecane-1,4,7-$ azadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl- 3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane , N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxysulfonium , N · bis (oxyethylene) -3 - aminopropyl trimethoxy Silane, N - bis (oxyethylene) -3 - Qi limb triethoxysilane Silane like. The mixing ratio of these other functional decane-containing compounds is preferably 10 parts by weight or less, more preferably 〇 1 to 5 parts by weight, based on the total amount of the 〇 〇 parts by weight of the polymer. <Solvent> The solvent contained in the liquid crystal alignment agent of the present invention is preferably a solvent exemplified as the solvent used in the specific polyamido acid synthesis reaction. Further, it is also possible to appropriately select a solvent which is exemplified as a poor solvent which can be used in combination in a specific polyamido acid synthesis reaction. -31 - 200848884 Solvent. The organic solvent to be used in the liquid crystal alignment agent of the present invention may, for example, be 1-methyl-2-pyrrolidone, r·butyrolactone, r-butylide or N,N-dimethylformamidine. Amine, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, Ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol 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, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol single Ethyl acetate, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy-N,N-di Methyl acrylamide, diethyl carbitol, ethyl carbitol acetate, butyl carbitol, triglyme, isoamyl isobutyrate, isoamyl ether, and the like. They may be used singly or in combination of two or more. Particularly preferable solvent composition The composition obtained by combining the above solvents is a composition in which the polymer in the alignment agent is not precipitated and the surface tension of the alignment agent falls within the range of 25 to 40 mN/m. <Liquid Crystal Aligning Agent> The liquid crystal alignment agent of the present invention contains at least one selected from the above specific polyaminic acid and its quinone imidized polymer, an organic hydrazine compound and a solvent as essential components, and optionally contains other additives. It is preferably prepared so that the components other than the solvent in the liquid crystal alignment agent dissolve the solution state contained in the solvent. The concentration of the solid content in the liquid crystal alignment agent of the present invention (the total weight of the components other than the solvent other than -32 to 200848884 in the liquid crystal alignment agent divided by the total weight of the liquid crystal alignment agent) is selected in consideration of viscosity, volatility, etc., preferably. It is in the range of 1 to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film as a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the thickness of the coating film is too small, so that good liquid crystal cannot be obtained. On the other hand, when the solid content concentration exceeds 10% by weight, the thickness of the coating film is too thick, so that a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal alignment agent increases to cause coating. The condition of the application is deteriorated. Further, a particularly preferable solid content concentration range differs depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, when the spin coating method is employed, it is particularly preferably in the range of 1 · 5 to 4 · 5 % by weight. When the printing method is employed, it is particularly preferable to set the solid content concentration to a range of from 3 to 9 % by weight, so that the viscosity of the solution can be made to fall within the range of 12 to 50 mPa·s. When the ink jet method is employed, it is particularly preferable that the solid content concentration is in the range of 1 to 5 % by weight, so that the viscosity of the dissolved L) liquid falls within the range of 3 to 15 mPa·s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇 ° C to 200 ° C, more preferably 20 ° C to 60 °. (3. <Liquid Crystal Display Element> The liquid crystal display element of the present invention is characterized by having a liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention obtained as above. The liquid crystal display element of the present invention can be subjected to, for example, the following steps) (3) Manufacturing. -33- 200848884 (1) The liquid crystal alignment agent of the present invention is applied onto one surface of a substrate provided with a patterned transparent conductive film by an appropriate coating method such as an offset printing method, a spin coating method, or an inkjet printing method. Next, a coating film is formed by heating the coated surface. Here, as the substrate, for example, glass such as floating glass or soda lime glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime or polycarbonate can be used. As the transparent conductive film provided on one side of the substrate, an NESA film made of tin oxide (Sn〇2) (registered trademark of PPG, USA) and indium tin oxide (1112〇3 - Sn〇2) can be used. ◦ film and so on. The pattern of formation of these transparent conductive films is a photolithography method or a method in which a mask is used in advance when a transparent conductive film is formed. In the application of the liquid crystal alignment agent, in order to further improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, a functional decane-containing compound or a functional titanium-containing compound may be applied to the surface of the substrate in advance. . The heating temperature after the application of the liquid crystal alignment agent is preferably from 80 to 300 ° C, more preferably from 120 to 25 ° C. Further, the liquid crystal alignment agent of the present invention removes an organic solvent after application to form a coating film as an alignment film, and when the liquid crystal alignment agent of the present invention contains a polymer having a proline structure, it can be further formed after the coating film is formed. The proline structure is dehydrated and closed by heating to form a further yttrium-immobilized coating film. The thickness of the formed coating film is preferably 0.001 to 1 // m, more preferably 0.005 to 0.5 // m 〇 (2). Next, the surface of the coating film formed as described above is usually wrapped with, for example, nylon, rayon, The rolls of fabrics such as cotton are sanded in a certain direction • 34-200848884. Thus, the alignment energy of the liquid crystal molecules is generated on the coating film to form a liquid crystal alignment film. In addition, the liquid crystal alignment film which is formed by the liquid crystal alignment agent of the present invention is shown in, for example, Patent Document 2 (Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A process of partially irradiating ultraviolet rays to change the pretilt angle, or partially forming a protective film on the surface of the liquid crystal alignment film after performing the rubbing treatment as shown in Patent Document 4 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei. After the polishing treatment is performed in different directions, the protective film is removed, and the liquid crystal alignment of the liquid crystal alignment film can be changed, so that the field of view characteristics of the liquid crystal display element can be improved. (3) Two substrates for forming a liquid crystal alignment film as described in (1) or (2) above are formed, and the two substrates are placed opposite each other via a gap (cell gap) so that the polishing directions of the respective liquid crystal alignment films are perpendicular or antiparallel to each other. The peripheral portions of the two substrates are bonded together with a sealant, and liquid crystals are injected into the interstitial space partitioned from the surface of the substrate and the sealant to close the injection holes to form liquid crystal cells. Then, on the outer surface of the liquid crystal cell, that is, the other side surface of each of the substrates constituting the liquid crystal cell, the polarizing plate is bonded so that the polarizing direction thereof coincides with or is perpendicular to the rubbing direction of the liquid crystal alignment film formed on one side of the substrate. A liquid crystal display element can be obtained. Here, as the sealant, for example, an alumina ball-containing epoxy resin as a curing agent and a separator can be used. Examples of the liquid crystal include nematic liquid crystal and dish-shaped liquid crystal. For the nematic liquid crystal, for example, Schiff's base liquid crystal, oxidized azo liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl may be used. Liquid crystal, biphenyl ring-35- 200848884 hexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubic liquid crystal, etc. Further, for example, chlorinated bile can be added to these liquid crystals. A cholesteric liquid crystal such as sterol, cholesteryl phthalate or cholesteryl carbonate, and a palmitic agent sold under the trade names "C-15" and "CB-15" (manufactured by Merck). Can also A ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutyl cinnamate is used. As a polarizing plate bonded to the outer surface of the liquid crystal, a polyvinyl alcohol extending direction can be mentioned. A polarizing plate made of a polarizing plate or a ruthenium film itself obtained by absorbing iodine at the same time as a ruthenium film, which is sandwiched between a polarizing film and a ruthenium acetate protective film. [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to these examples. In the following examples and comparative examples, the evaluation of the prepared liquid crystal alignment agent was carried out in the following manner: I [Printability evaluation] Prepared in advance on one side A 1 27 mm (D) X 1 2 7 mm (W) X 1.1 mm (Η) glass substrate of a ΙΤ0 film as a transparent electrode was formed on the entire surface, and a liquid crystal alignment film coating printing machine was used (Japanese photo printing ( Manufactured in the model "Angstroη S-40L"), the liquid crystal alignment agent having a solid content concentration of 5% by weight prepared in each of the examples or the comparative examples was filtered through a micropore filter having a pore diameter of 〇·2 // m. After being applied to the glass substrate On the electrode surface, the coated substrate was removed by a hot plate-type pre-dryer set at 80 °C, and then heated for another 10 minutes at 200 °C at 200 °C. The film thickness of the base film is about //· 〇6 // m. Visual inspection and filming through the microscope, no porosity or uneven coating is judged as “excellent”, slight pores or uneven coating (film thickness is not The case of equalization was judged as "the case where the pores or uneven coating were observed was judged as "poor". [Evaluation of voltage holding ratio] A glass substrate having a pattern of about 1 mm thick on one side was used. Further, the liquid crystal alignment agent was prepared by using a liquid crystal having a solid content concentration of 3.6 wt% obtained in each of the examples, and a pair (two pieces) having a ratio of 0.0 6 / was produced in the same manner as in the above [printability evaluation]. / m of the coated glass substrate. Next, on each of the outer edges of the liquid crystal coating substrate of the pair of transparent electrodes/transparent substrates having the liquid crystal alignment film, a ring of alumina balls having a diameter of 5 · 5 // m is applied in addition to the liquid crystal. The oxygen tree agent then causes the liquid crystal alignment film surface to be relatively recombined and pressed to make it adhere. Then, the liquid crystal injection port is used to fill the inter-substrate between the substrates, manufactured by Merck, MLC-660 8), and the liquid crystal injection port is closed with an acrylic photo-polymerizing agent, and is attached to both sides of the substrate. Liquid crystal display element. A voltage of 5 V was applied to the liquid crystal cell at room temperature over a time span of 16.7 msec, the voltage application time was 60 microseconds, and then the voltage was released to a voltage holding ratio of 16.6 msec. The measuring device adopts VHR-1 manufactured by Dongyang Technology. The shape of the plate was observed to be good, and the formation of the bismuth or the ratio of the agent to the film was injected into the film to form a grease-bonding agent to fix the crystal (negatively cured adhesion polarization display element was determined from the use of (s) -37-200848884 [ Evaluation of residual image] A liquid crystal display element was produced in the same manner as in the above [Evaluation of Voltage Retention Rate] except that a glass substrate having a ruthenium film having a pattern as shown in Fig. 1 was used. A DC voltage of 6 · 0 V was applied to the electrode 24 for 24 hours at room temperature, and a DC voltage of 0.5 V was applied to the electrode B for 24 hours. After the voltage was released, the electrodes A and B were applied with a gradient of 0.1 V to 〇 1 to 5.0 V, respectively. The DC voltage is determined by the difference in luminance between the electrodes A and B at each voltage. That is, when the luminance difference is large, the afterimage characteristic is judged to be poor. No residual image is found as 〇, and a weak afterimage is generated. It is described as Δ. Synthesis Example <Synthesis Example of Specific Diamine> Synthesis Example A-1 (Synthesis of 1-(3,5-Diaminophenyl)-3-octadecylsuccinimide) Add in a 300 ml three-necked flask ventilated with nitrogen (, 12.81 g (0.07) Mol) 3,5-dinitroaniline and 70 ml of acetic acid were stirred while stirring with nitrogen to dissolve the solid matter. 24.64 g (0.07 mol) of octadecyl succinic anhydride was added thereto, and the mixture was refluxed under nitrogen for 20 hours. After the reaction solution was cooled to room temperature, 70 ml of methanol was added thereto, and the mixture was allowed to stand overnight. The precipitated solid was filtered, washed with methanol and dried to give 30 g (yield 8.3 %) 1 - (3,5 - Nitrophenyl)-3-octadecyl amber imine. Then, to a 500 ml flask ventilated with nitrogen, 30 g (0.058 mol) of the above synthesized 1-(3,5-dinitrophenyl group) was added. )-3-octadecyl-38- 200848884 Amber succinimide, l〇〇ml ethanol, 100ml tetrahydrofurine reduction catalyst palladium carbon (Pd/C), stirred at 70X: 1 into 42.5ml (4 3.7 5g) hydrazine monohydrate, heated to reflux 6 filtered out Pd / C, the filtrate was heated in a rotary evaporator to dissolve in N-methyl-2-pyrrolidone, then cooled 14.6g (0.032mol, yield 55 %) target product 1-(3,5 octadecyl succinimide. Synthesis Example A-2 (1-(3,5-diaminophenyl)-3-12

Synthesis of C) In the same manner as in the use of 18.76 g (0.07 mol) of dodecyl 24.64 g (0.07 mol) octadecyl succinic anhydride, llg (0.030 mol, yield 51 phenyl)-3- Dodecyl amber imine. Synthesis Example A-3 (Synthesis of 1-(3,5-diaminophenyl)-3-heptadelimine) (Addition of dimethyl maleic anhydride to a 2000 ml three-necked flask ventilated with nitrogen, 89.0 g (0.5 mol) of N-bromo 1.0 g (4.15 mmol) of dibenzoguanidine peroxide and 1500 ml were refluxed for 5 hours. The reaction solution was cooled to room temperature and filtered at room temperature. The filtrate was washed with water and then organic layer The obtained crude oily product was distilled under high vacuum (1 20 to obtain 20.0 g (0.1 mol, yield 39%) of intermediate 3-bromo acid anhydride. THF (25 g) and 25 g. The reaction is obtained by shrinking. The obtained crude product is recrystallized to give -diaminophenyl)-3-alkylsuccinimide succinic anhydride instead of the synthesis example A - 1 %) 1-(3,5-diamine Base group 4-methyl male to 31.5g (0.25mol) amber imine, carbon tetrachloride, heated for 1 night, and concentrated in the evaporator. 1 25 °C /2mmHg), A 4-methyl-Male-39-200848884 Then, 16.4 g (80 mmol) of the above-prepared 3-bromomethyl-4-methylmaleic anhydride was added to a 2000 ml three-necked flask ventilated with argon gas. 1.52 g (8.0 mmol) of copper iodide, 400 ml of diethyl ether and 1 After 60 ml of HMPA (hexamethylphosphonium triamine), it was cooled to -5 to 0 ° C under argon gas. ~ While stirring the mixture, a solution of 400 mmol of cetylmagnesium bromide dissolved in 400 ml of diethyl ether was added dropwise over about 20 minutes. The mixture was allowed to warm to room temperature and stirred for additional 8 hours. Then, after diluting with 600 ml of diethyl ether, 60 ml of 4N-sulfuric acid was added to make the solution acidic. The separated aqueous layer was further washed with 600 ml of diethyl ether and the organic layer was combined. The organic layer was washed with water and water was evaporated over sodium sulfate. The crude product was purified in a silica gel column eluting with petroleum ether/ethyl acetate (1: 1) as an eluting solvent to give 14.0 g (0.04 mol, yield 50%) of 3-heptadecyl- 4-methylmaleic anhydride. Then, 6.42 (0.035111〇1) of 3,5-dinitroaniline and 351111 acetic acid were placed in a 200 ml three-necked flask ventilated with nitrogen. The mixture was stirred while passing nitrogen gas to dissolve the solid matter. 12.3 g (0.035 mol) of the above-prepared 3-pentadecyl-4-methylmaleic anhydride was added thereto, and the mixture was refluxed under nitrogen for 20 hours to cause a reaction. After cooling the reaction mixture to room temperature, 35 ml of methanol was added and the mixture was allowed to stand overnight. The solid component was filtered off, washed with methanol and dried to give 14.4 g (0.029 mol, yield 81%) of 1-(3,5-dinitrophenyl)-3-heptadecyl-4-methyl. Yttrium. Then, to a 300 ml flask ventilated with nitrogen, 13.4 g (0.026 mol) of 1·(3,5-dinitrophenyl)-3-heptadecyl-4-methylma-40-200848884 was added. The imine, 50 ml of ethanol, 50 ml of THF, and 12.5 g of a reduction catalyst Pd/C were stirred at 70 ° C for 1 hour. Then, 19 ml (19.6 g) of hydrazine monohydrate was added, and the mixture was heated under reflux for 6 hours to cause a reaction. The Pd/C was filtered off and the filtrate was concentrated in a rotary evaporator. The obtained crude product was dissolved in N-methyl-2-pyrrolidone by heating, and recrystallized by cooling to obtain 6.6 g (0.01 5 m ο 1, yield of 5 6 %) of the desired product 1-(3,5-diamino group. Phenyl)-3-heptadecyl-4-methylmaleimide. Synthesis Example A-4 (1-(3,5-Diaminophenyl)-3-hexadecyloxymethyl·4_甲 f'"\

Synthesis of K-Mamalineimine) After adding 12.81 g (0.07 mol) of 3,5-dinitroaniline and 70 ml of acetic acid to a 300 ml three-necked flask ventilated with nitrogen, the mixture was stirred while passing nitrogen gas to make a solid. The substance dissolves. Thereto was added 14.35 g (0.07 mol) of 3-(bromomethyl)-4-methylmaleic anhydride synthesized in the same manner as the intermediate of the compound of Example A-3, and the mixture was refluxed under nitrogen for 20 hours. After the reaction solution was cooled to room temperature, 70 ml of methanol was added and the mixture was allowed to stand overnight. &lt; The solid component was filtered off, washed with methanol and dried to give 18.9 g (yel. 〇 51 mol ' yield 73%) 1-(3,5·dinitrophenyl)-3-bromomethyl-4- Methyl maleimide. Next, 18.1 g (0.049 mol) of 1-(3,5-dinitrophenyl)-3-bromomethyl-4-methylmaleimide was added to a 500 ml three-necked flask ventilated with nitrogen. After 12.9 g (〇.〇49 mol) of 1-hexadecanol sodium salt and 100 ml of dimethylarylene, the mixture was stirred at 100 ° C for 10 hours to cause a reaction. After cooling the reaction mixture to room temperature, 70 ml of methanol was added and the mixture was allowed to stand overnight. The solid component was filtered off and washed with methanol and dried to give 20.8 g (yield: 80% of yield: 0.039 mmol) of 1-(3,5--41-200848884 dinitrophenyl)-3-hexadecyloxymethyl 4-methylmaleimide. Then, to a 300 ml flask ventilated with nitrogen, 13.8 g (0.026 mol) of 1-(3,5-dinitrophenyl)-3-hexadecyloxymethyl-4-methylmalay was added. The imine, 50 ml of ethanol, 50 ml of THF and 12.5 g of a reduction catalyst Pd/C were stirred at 70 ° C for 1 hour. Then, I9 ml (19.6 g) of hydrazine monohydrate was added, and the mixture was heated under reflux for 6 hours to cause a reaction. The Pd/C was filtered off and the filtrate was concentrated in a rotary evaporator. The obtained crude product was dissolved in N-methyl-2-pyrrolidone by heating, and recrystallized by cooling to obtain 8.2 g (0.018 mol, yield 67%) of desired product 1-(3,5-diaminophenyl)-3. - Hexadecanyloxymethyl-4-methylmaleimide. &lt;Synthesis Example of Specific Polylysine and Its Purine-Iminylated Polymer&gt; Synthesis Example P-1 to P-8 To the N-methylpyrrolidone, the diamines of the compositions shown in Table 1 were added in this order and The tetracarboxylic dianhydride was mixed into a solution having a monomer concentration of 20% by weight, and allowed to react at 60 ° C for 4 hours to obtain a solution containing polyglycine (A-1) to (A-8). To each of the obtained polyaminic acid solutions, 3.0 times of molar pyridine and 3.0 times of molar acetic anhydride were added to the total amount of the proline units in the solution, and then heated at 1 1 ° C for 4 hours. Perform a dehydration ring closure reaction. The ruthenium imidized polymer (B-1) to (B-8) was obtained by precipitating the obtained solution in diethyl ether, recovering, and drying under reduced pressure. The oxime imidization ratio of these quinone imidized polymers is shown in Table 1. Synthesis Examples P - 9 and P - 10 0 Polyacetic acid (A-9) was produced in the same manner as in Synthesis Examples P-1 to P-8 except that the diamine and the tetracarboxylic dianhydride were used as listed in Table 1. ) and (A-10). Further, in addition to -42 to 200848884, in the synthesis examples P-9 and P-10, the dehydration ring closure reaction of polypergic acid was not carried out. Table 1 Synthesis Example Diamine Compound (Morby) Anhydride (Morby) Polyimide ruthenium imidized polymer 醯 imidization rate (%) Ρ-1 Specific diamine hydrazine (20), diamine 1 (80) Τ-1(20), Τ·2(80) Al Bl 88 Ρ-2 specific diamine hydrazine (20), diamine 1 (80) Τ-1 (50), Τ-2 (50) Α -2 Β-2 82 Ρ—3 specific diamine oxime (20), diamine 1 (80) Τ-1(20), Τ-2(80) Α-3 Β-3 86 Ρ—4 specific diamine Β (20), diamine 1 (80) Τ-1 (50), Τ-2 (50) Α-4 Β-4 81 Ρ—5 specific diamine C (20), diamine 1 (80) Τ-1 (20), Τ-2(80) Α-5 Β-5 87 Ρ-6 Specific diamine C(20), diamine 1 (80) Τ-1(50), Τ-2(50) Α-6 Β-6 83 Ρ-7 specific diamine D (20), diamine 1 (80) Τ-1 (20), Τ-2 (80) Α-7 Β-7 86 Ρ-8 specific diamine D (20 ), diamine 1 (80) Τ-1(50), Τ·2(50) Α-8 Β-8 80 Ρ-9 diamine 1 (100) Τ-3(100) Α-9 — — Ρ- 10 Diamine 1_ Τ-3(80), Τ-4(20) Α-10 — — -43- 200848884 In Table 1, for the diamine and tetracarboxylic dianhydride, the numbers in parentheses indicate the content ratio (mole) Ratio), the abbreviation in the table means the following ° <diamine> specific diamine A: 1-(3,5-diaminophenyl)-3- Eight hospitals based on the production of the imino-specific diamine B: M3,5 · diaminophenyl) -1 - 11 yards of the styrene-specific diamine C: 1- (3,5 -diamino Phenyl)·3 -17-yard-4-methylmaleimide-specific diamine D: 1-(3,5-diaminophenyl)-3-hexadecanyloxymethyl-4 -methylmaleimide diamine 1:4,4'-diaminodiphenylmethane&lt;tetracarboxylic dianhydride&gt; T-1: 2,3,5-tricarboxycyclopentylacetate Anhydride T-2: 5-(2,5-diketotetrahydro-3-furanyl)-3-methyl-3-cyclohexene (j-1,2-dicarboxylic anhydride T-3: isophthalic acid Tetraic acid dianhydride T 4: 1,2,3,4-cyclobutane tetracarboxylic dianhydride Example 1 The ruthenium iodide polymer B-1 obtained in Synthesis Example P-1 and Synthesis Example P a polyamic acid A-9 (weight ratio of 50:50) prepared in 9 and 0.005 parts by weight based on 100 parts by weight of the total amount of the polymer as a sulfonium compound KF-6011 ( Trade name, Shin-Etsu Chemical Industry Co., Ltd. -44- 200848884, PEG - 11 methyl ether dimethyl polyoxyalkylene) is soluble in butyrolactone / Ν · methyl _2 · 比 比 咯 嗣 / butyl cellosolve Mixed solution (weight ratio 4 0 : 3 0 In 3 0), two solutions having a solid content concentration of 3.5 wt% and 5% by weight were prepared. These solutions were separately filtered through a filter having a pore size of 0 · 2 / m to obtain two concentrations of liquid crystal alignment agent. The viscosity of the liquid crystal alignment agent having a solid content concentration of 3.5% by weight is shown in Table 2. Using these liquid crystal alignment agents, the printability, the voltage holding ratio, and the afterimage were evaluated in accordance with the above method. The results are shown in Table 5. &quot; Examples 2 to 3 6 In the same manner as in Example 1, except that the type and amount of the polymer and the organic ruthenium compound were as shown in Table 2, liquid crystal alignment agents of two concentrations of 3.5% by weight and 5% by weight were prepared. 3 6. The viscosity of the liquid crystal alignment agent having a solid content concentration of 3 · 5 % by weight is shown in Table 2. Further, the results of evaluation using these liquid crystal alignment agents in accordance with the above methods are shown in Table 5. -45- 200848884 Table 2 Example polymer (weight composition ratio) Organic germanium compound viscosity individual content 3.5% (mPa.s) 1 Bl/A-9 (50/50) KF-6011 6.2 2 KF-6012 6.2 3 SH3773M 6.2 4 SH3749 6.2 5 B-2/A-9(50/50) KF-6011 6.6 6 KF-6012 6.6 7 SH3773M 6.6 8 SH3749 6.6 9 B-3/A-9(50/50) KF-6011 6.1 10 KF-6012 6.1 11 SH3773M 6.1 12 SH3749 6.1 13 B-4/A-9(50/50) KF-6011 6.7 14 KF-6012 6.7 15 SH3773M 6.7 16 SH3749 6.7 17 B-5/A-9 (50/50 KF-6011 6.2 18 KF-6012 6.2 19 SH3773M 6.2 20 SH3749 6.2 21 B-6/A-9(50/50) KF-6011 6.8 22 KF-6012 6.8 23 SH3773M 6.8 24 SH3749 6.8 25 B-7/A -9(50/50) KF-6011 6.2 26 KF-6012 6.2 27 SH3773M 6.2 28 SH3749 6.2 29 B-8/A-9(50/50) KF-6011 6.6 30 KF-6012 6.6 31 SH3773M 6.6 32 SH3749 6.6 33 Bl/A-10(50/50) KF-6011 6.2 34 KF-6012 6.2 35 SH3773M 6.2 36 SH3749 6.2 -46- 200848884 In Table 2, the abbreviations of organic germanium compounds are as follows. KF — 601 1 : The trade name “Shinjuku Polyoxane KF — 601 1”, produced by Shin-Etsu Chemical Co., Ltd., PEG-11 methyl ether dimethyl polyoxyalkylene KF - 6012 : trade name "Shinjuku polyoxyalkylene KF — 6012”, manufactured by Shin-Etsu Chemical Co., Ltd., PEG/PPG-20/22 Butane Ether Dimethyl Oxane SH3773M: trade name, produced by Toray Dowcorning Silicone, polyoxyethylene methyl peroxide Alkyne copolymer SH3749: trade name, Toray Dowcorning Silicone (s) to produce 'r' k poly(oxyethylene oxypropylene) methyl polyoxyalkylene copolymer Example 3 7 Preparation of hydrazine prepared in Synthesis Example P-1 Imidized polymer B-1 and polylysine A-9 (weight ratio 50:50) prepared in Synthesis Example P-9, 0.005 parts by weight relative to 100 parts by weight of the total amount of the polymer as an organic ruthenium compound A polyoxyalkylene KF — 60 1 1 and 20 parts by weight of the total amount of the polymer relative to 1 part by weight of the polyethylene glycol diglycidyl ether (molecular weight: about 400) dissolved in 7 - Ding vinegar / N - methyl - 2 - 嗣 嗣 嗣 / butyl r I cellosolve mixed solution (weight ratio of 40:30:30) The two solutions having a solid content concentration of 3.6 wt% and 5% by weight. These solutions were separately filtered with a filter having a pore size of 0 · 2 / m to obtain two concentrations of liquid crystal alignment agents. The viscosity of the liquid crystal alignment agent having a solid content concentration of 3.5% by weight is shown in Table 3. Further, the results of evaluation by the above method using these liquid crystal alignment agents are shown in Table 5. Example 3 8 to 4 2 -47 to 200848884 A liquid crystal alignment agent of two concentrations was prepared in the same manner as in Example 3 except that the types of the organic chopping compound and the epoxy compound used were as shown in Table 3. The viscosity of the liquid crystal alignment agent having a solid content concentration of 3 · 5 % by weight is shown in Table 3. Further, the results of evaluation using these liquid crystal alignment agents in accordance with the above methods are shown in Table 5. Table 3 Example Polymer (weight composition ratio) Organic oxime compound epoxy compound viscosity Individual content 3.5% (mPa-s) 37 B-1/A-9 (50/50) KF-6011 Epoxy A 6.2 38 B — 1/A—9(50/50) KF-6011 Epoxy B 6.2 39 B — 1/A—9 (50/50) KF-6011 Epoxy C 6.2 40 B-1/A-9 ( 50/50) KF-6011 Epoxy D 6.2 41 B — 1/A—9 (50/50) KF-6011 Epoxy E 6.2 42 B — 1/A—9 (50/50) KF-6011 Ring Alkyl F 6.2 In Table 3, the meaning of the abbreviation of the organic hydrazine compound is the same as in Table 2. The meaning of the abbreviated abbreviation is as follows. Epoxy A: polyethylene glycol diglycidyl ether (molecular weight approx. 400) Epoxy B: 1,6-hexanediol diglycidyl ether Epoxy C·· N, N, N,, N' -tetraglycidyl-2,2,-dimethyl-4,4'-diaminobiphenylyloxy D: N,N,N',N'-tetraglycidyl-4,4,- Diaminodiphenylmethane epoxy E: 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane-48- 200848884 Epoxy F: N,N,N ' , N ' -tetraglycidyl-m-xylylenediamine Comparative Examples 1 to 8 were the same as Examples 1, 5, 9, 13 3, 17, 2, 25, and 29 except that the organic ruthenium compound was not used. Two concentrations of each liquid crystal alignment agent were prepared. The viscosity of the liquid crystal alignment agent having a solid content concentration of 3.5% by weight is shown in Table 4. The 'junctions' evaluated by the above method using these liquid crystal alignment agents are shown in Table 5. Table 4 Comparative Example Polymer (weight composition ratio) Organic germanium compound viscosity / solid content 3.5% (mPa * s) ---- __〆 ^ 1 Β-1 / Α-9 (50 / 50) &gt; fnr Till 6.2 A ___一^ 2 Β-2/Α-9(50/50) 4τγΤ. ιιιι~ J\\\ 6.6 _____--^ 3 Β-3/Α-9(50/50) &gt;fnT τπτ : 6.1 一^— 4 Β-4/Α-9(50/50) /frrr 1111: j\\\ 6.7 一__〆^ 5 Β-5/Α-9(50/50) ArrC. Mil: J \\\ 6.2 _^ __-— 6 Β-6/Α-9(50/50) &gt;frrr. ΙΙΠΤ J\\\ 6.8 ----* ____一^ 7 Β-7/Α-9( 50/50) &gt;fntl uTT J\\\ 6.2 ------ 8 Β-8/Α-9(50/50) &gt;frrr. itrr: j\\\ 6.6 __- -49- 200848884 Printing SJE retention rate afterimage Example 1 Good &gt; 99% 〇 Example 2 Good &gt; 99% 〇 Example 3 Good &gt; 99% 〇 Example 4 Good &gt; 99% 〇 Example 5 Good &gt; 99% Example 6 Good &gt; 99% 〇 Example 7 Good &gt; 99% 〇 Example 8 Good &gt; 99% 〇 Example 9 Good &gt; 99% 〇 Example 10 Good &gt; 99% 〇 Example 11 Good &gt;99% 〇Example 12 Good &gt;99% 〇Example 13 Good &gt;99% 〇Example 14 Good &gt;99% 〇Example 15 Good &gt;99% Example 16 Good &gt; 99% 〇 Example 17 Good &gt; 99% 〇 Example 18 Good &gt; 99% 〇 Example 19 Good &gt; 99% 〇 Example 20 Good &gt; 99% 〇 Example 21 Good &gt;99% 〇Example 22 Good &gt;99% 〇Example 23 Good &gt;99% 〇Example 24 Good &gt;99% 〇Example 25 Good &gt;99% 〇【Simple description of the chart】 Table 5 Printing Example 2: Good &gt; 99% 〇 Example 27 Good &gt; 99% 〇 Example 28 Good &gt; 99% 〇 Example 29 Good &gt; 99% 〇 Example 30 Good &gt; 99% Example 31 Good &gt; 99% 〇 Example 32 Good &gt; 99% 〇 Example 33 Good &gt; 99% 〇 Example 34 Good &gt; 99% 〇 Example 35 Good &gt; 99% 〇 Example 36 Good &gt;99% 〇Example 37 Excellent &gt;99% 〇Example 38 Excellent &gt;99% 〇Example 39 Excellent &gt;99% 〇Example 40 Excellent &gt;99% 〇Example 41 Excellent &gt;99% 〇 Example 42 Excellent &gt; 99% 〇 Comparative Example 1 Bad 96% Δ Comparative Example 2 Bad 97% Δ Comparative Example 3 Bad 96% Δ Comparative Example 4 Bad 97% Δ Comparative Example 5 Bad 97% Δ Comparative Example 6 No Good 97% Δ Comparative Example 7 Poor 96% Δ Comparative Example 8 Poorness 97% Δ Fig. 1 is a view showing the ITO electrode pattern of the liquid crystal display element produced in the evaluation of the residual image in the examples and the comparative examples. [Main component symbol description] Μ 〇 j\\\ -50-

Claims (1)

200848884 X. Patent application scope: 1. A liquid crystal alignment agent comprising: at least one selected from the group consisting of tetracarboxylic dianhydrides represented by the following formulas (1) and (2) and selected from the following formula ( 3) a polymer obtained by reacting at least one of the diamines represented by (6) and/or a quinone imidized polymer thereof; a compound represented by the following formula (7); and a solvent; -51 - 200848884 Wherein R1 to R4 are each independently a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms or a linear, branched or cyclic group having 4 to 40 carbon atoms; The alkenyl group, 1 to 15 of the argon atoms of R1 to R4 may be substituted by a fluorine atom, and each of A1 and A2 is independently a hydrogen atom or a methyl group, -52- 200848884 ch3 I H3C—Si—O ch3 (7) wherein X1 is a monovalent group represented by the following formula (7-1) or (7-2), m and η are integers of 1 to 20, and R5(C2H4〇)a(C3H60)bR6 ( 7-1) - R5(C2H40)aR6 (7-2) wherein R5 is a methylene group or a polymethylene group, R6 is an alkyl group, and a and b are each independently an integer of from 1 to 20. 2. The liquid crystal alignment agent of claim 1, which further comprises a compound having two or more epoxy groups in the molecule. A liquid crystal display element characterized by having a liquid crystal alignment film produced by a liquid crystal alignment agent according to claim 1 or 2. -53-